TWI890843B - Polyorganosilsesquioxane, curable composition, cured product, hard coating film, transfer film, and adhesive sheet - Google Patents

Abstract

The present invention provides a polyorganosilsesquioxane that can form a cured product having both high heat resistance and high surface hardness and flexibility, which is characteristic of polyorganosilsesquioxanes, and is suitable as a material for a hard coat film. The polyorganosilsesquioxane of the present invention contains a silsesquioxane, which is a condensate obtained by condensing two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3), and composition formula (4), and has a molecular weight of 8000 or less. Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ Formula (4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ [The explanations in the formulas are as described in this manual]

Description

Polyorganosilsesquioxane, curable composition, cured product, hard coating film, transfer film, and adhesive sheet

This invention relates to a polyorganosilsesquioxane, a curable composition containing the polyorganosilsesquioxane, a cured product thereof, and a hardcoat film formed from the cured product. This invention also relates to a transfer film containing the curable composition as a hardcoat layer. Furthermore, this invention relates to an adhesive sheet containing the curable composition as an adhesive layer. This application claims priority to Japanese Patent Application No. 2020-145085 filed in Japan on August 28, 2020, the contents of which are incorporated herein by reference.

Polyorganosilsesquioxanes (silsesquioxanes) are network-structured polymers or polyhedral clusters obtained by hydrolyzing trifunctional silanes. Silsesquioxanes are known to have random, ladder, and cage structures. Currently known high-molecular-weight silsesquioxanes, such as those with molecular weights of 3000 or greater, mostly have random or ladder structures. Such high-molecular-weight silsesquioxanes are described, for example, in Patent Document 1 below.

Cage-type silsesquioxanes are a general term for substances with a structure in which the rings are three-dimensionally closed via siloxane bonds, with a cubic structure of silicon oxide as the center and organic functional groups at each vertex. Known examples of this cubic structure include octameric silsesquioxane (T ₈ ), which has a regular hexahedral structure, and decameric silsesquioxane (T ₁₀ ), which has a pyramidal pentagonal structure. This cage-type silsesquioxane is described, for example, in Patent Document 2 below. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2013-35918 [Patent Document 2] Japanese Patent Application Publication No. 2000-334881

[The problem that the invention aims to solve]

However, the cured products obtained from currently available high-molecular-weight polysilsesquioxanes or cage-type silsesquioxanes tend to be insufficiently hard and have limited flexibility when bent. Consequently, these cured products cannot be used in applications requiring high hardness and high bending resistance, limiting their use as materials suitable for hard coatings. Furthermore, as the molecular weight of currently available high-molecular-weight silsesquioxanes increases, they become less soluble in organic solvents and other solvents, making them difficult to process into materials suitable for hard coatings.

Therefore, the present invention aims to provide a polyorganosilsesquioxane that can be produced into a cured product that combines the high heat resistance characteristic of polyorganosilsesquioxane with high surface hardness and flex resistance, and is suitable as a material for hardcoats. Furthermore, the present invention aims to provide a polyorganosilsesquioxane that has a high molecular weight and high solubility in solvents such as organic solvents.

Another object of the present invention is to provide a curable composition containing the polyorganosilsesquioxane. Further, another object of the present invention is to provide a cured product of the curable composition, and a hardcoat film having a hardcoat layer serving as the cured product. Further, another object of the present invention is to provide a transfer film having a hardcoat layer containing the curable composition. Further, another object of the present invention is to provide an adhesive sheet having an adhesive layer containing the curable composition. [Technical Means for Solving the Problem]

The inventors of the present invention have discovered that a curable composition containing a silsesquioxane having a structure formed by condensing two or more cage-shaped silsesquioxanes of a specific formula and having a molecular weight of 8,000 or less exhibits both high heat resistance and excellent surface hardness and flex resistance, making the resulting cured product extremely useful as a hard coat layer in hard coat films or transfer films, or as an adhesive layer in adhesive sheets. Furthermore, the inventors discovered that the silsesquioxane has a high molecular weight and is highly soluble in solvents such as organic solvents. The present invention was completed based on this knowledge.

That is, the present invention provides a polyorganosilsesquioxane containing a silsesquioxane, wherein the silsesquioxane is a condensate obtained by condensing two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3), and composition formula (4), and has a molecular weight of 8000 or less.・Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (In formula (1), R ¹ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (In formula (2), R ² are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (In formula (3), R ³ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (In formula (4), R ⁴ each independently represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom)

Furthermore, the present invention provides the above-mentioned polyorganosilsesquioxane, wherein the above-mentioned group containing a polymerizable functional group is the following formula (1A): [In formula (1A), R ^1A represents a linear or branched alkylene group] A group represented by the following formula (1B) [In formula (1B), R ^1B represents a linear or branched alkylene group] A group represented by the following formula (1C): [In formula (1C), R ^1C represents a linear or branched alkylene group], or a group represented by the following formula (1D) [In the formula (1D), R ^1D represents a linear or branched alkylene group]

The present invention also provides the above-mentioned polyorganosilsesquioxane, wherein the ratio of groups containing polymerizable functional groups relative to the total of R ¹ in the above-mentioned composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), and R ⁴ in the composition formula (4) is 30% or more.

The present invention also provides the above-mentioned polyorganosilsesquioxane, wherein the molar ratio of the constituent units represented by the following formula (I) to the constituent units represented by the following formula (II) [constituent units represented by formula (I)/constituent units represented by formula (II)] is 1 to 500. [ ^RaSiO3 _/2 ] (I) [In formula (I), ^Ra represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom] [ ^RbSiO2 _/2 ( ^ORc )] (II) [In formula (II), ^Rb represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; ^Rc represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]

The present invention also provides the polyorganosilsesquioxane having a number average molecular weight of 2,000 to 50,000.

The present invention also provides the polyorganosilsesquioxane having a molecular weight dispersion (weight average molecular weight/number average molecular weight) of 1.0 to 4.0.

The present invention also provides a curable composition containing the above-mentioned polyorganosilsesquioxane.

The present invention also provides the above-mentioned curable composition further comprising a curing catalyst.

Furthermore, the present invention provides the aforementioned curable composition, wherein the curing catalyst is a photo- or thermal-polymerization initiator.

The present invention also provides the aforementioned curable composition, which further contains a polymerization stabilizer.

The present invention also provides the above-mentioned curable composition, which is a curable composition for forming a hard coating layer.

The present invention also provides the aforementioned curable composition, which is a curable composition for an adhesive.

Furthermore, the present invention provides a cured product of the curable composition.

The present invention also provides a hard coating film comprising a substrate and a hard coating layer formed on at least one surface of the substrate, which is the hardened material.

The present invention also provides a transfer film comprising a substrate and a hard coating layer formed on a release layer formed on at least one surface of the substrate, wherein the hard coating layer contains the above-mentioned curable composition.

The present invention also provides the transfer film described above, wherein an anchor coat layer and an adhesive layer are sequentially layered on the hard coat layer.

The present invention also provides the above-mentioned transfer film, which further comprises at least one colored layer.

The present invention also provides the transfer film, wherein the hard coating layer has a thickness of 3 to 150 μm.

The present invention also provides an adhesive sheet comprising a substrate and an adhesive layer. The adhesive layer is located on at least one surface of the substrate and is a layer containing the aforementioned curable composition.

The present invention also provides an adhesive sheet comprising a substrate, an adhesion-promoting coating layer, and an adhesive layer. The adhesion-promoting coating layer and the adhesive layer are located on at least one side of the substrate. The adhesion-promoting coating layer contains a silane coupling agent, and the adhesive layer is a layer containing the aforementioned curable composition. The adhesive layer is disposed on the surface of the adhesion-promoting coating layer. [Effects of the Invention]

Cured products (e.g., hard coats) obtained from curable compositions containing the polyorganosilsesquioxane of the present invention exhibit high heat resistance, high surface hardness, and high flexural resistance. Therefore, using hard coat films or transfer films containing such hard coats enables the production of molded articles (products) with high surface hardness and flexural resistance. Furthermore, the polyorganosilsesquioxane of the present invention is a high molecular weight polyorganosilsesquioxane and has high solubility in solvents such as organic solvents. Therefore, hardcoat films or transfer films containing the polyorganosilsesquioxane of the present invention can reduce the amount of solvent used. Furthermore, the uncured or semi-cured hardcoat layer does not stick, allowing it to be rolled up and handled. This allows for roll-to-roll processing, resulting in excellent quality and cost. Furthermore, curable compositions containing the polyorganosilsesquioxane of the present invention as an essential component can form cured products (adhesives) with high heat resistance and excellent flexibility, making them ideal for use as adhesives (e.g., curable compositions for laminated semiconductors).

[Polyorganic silsesquioxane] The polyorganic silsesquioxane of the present invention contains silsesquioxane. The silsesquioxane (hereinafter sometimes referred to as "condensed silsesquioxane of the present invention") is a condensate obtained by condensing two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3) and composition formula (4), and has a molecular weight of 8000 or less (preferably 1500-7500, more preferably 1800-7000, and even more preferably 2000-6500).・Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (In formula (1), R ¹ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (In formula (2), R ² are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (In formula (3), R ³ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (In formula (4), R ⁴ each independently represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom)

The constituent unit represented by [R ¹ SiO _3/2 ] in the composition formula (1), the constituent unit represented by [R ² SiO _3/2 ] in the composition formula (2), the constituent unit represented by [R ³ SiO _3/2 ] in the composition formula (3), and the constituent unit represented by [R ⁴ SiO _3/2 ] in the composition formula (4) are included in the constituent unit represented by the following formula (I) (hereinafter sometimes referred to as "T3 form" in this specification). [R ^a SiO _3/2 ] (I)

Furthermore, the constituent unit represented by [R ¹ SiO _2/2 (OR ^c )] in the composition formula (1), the constituent unit represented by [R ² SiO _2/2 (OR ^c )] in the composition formula (2), the constituent unit represented by [R ³ SiO _2/2 (OR ^c )] in the composition formula (3), and the constituent unit represented by [R ⁴ SiO _2/2 (OR ^c )] in the composition formula (4) are included in the constituent unit represented by the following formula (II) (hereinafter sometimes referred to as "T2 body" in this specification). [R ^b SiO _2/2 (OR ^c )] (II)

In the above formula (I), R ^a and R ^b in the above formula (II) represent a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. Furthermore, in the above formula (II), R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

If the structural unit represented by the above formula (I) is further described in detail, it is represented by the following formula (I'). Furthermore, if the structural unit represented by the above formula (II) is further described in detail, it is represented by the following formula (II'). In the structure represented by the following formula (I'), the three oxygen atoms bonded to a silicon atom are each bonded to another silicon atom (a silicon atom not shown in formula (I')). On the other hand, in the structure represented by the following formula (II'), the two oxygen atoms located above and below the silicon atom are each bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, the T3 form and the T2 form are both silsesquioxane constituent units (so-called T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

^Ra in formula (I'), ^Rb , and ^Rc in formula (II') are the same groups as described above. The alkyl group in ^Rc in formula (II) is typically derived from an alkyl group that forms an alkoxy group in a hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane of the present invention (e.g., the alkoxy groups ^X1 to ^X3 in formulas (A) to (C) below).

The cage-type silsesquioxane represented by the above composition formula (1) is a silsesquioxane having a cage-type structure formed by eight structural units represented by [R ¹ SiO _3/2 ] (T3 form) and one structural unit represented by [R ¹ SiO _2/2 (OR ^c )] (T2 form) mutually bonding via siloxane bonds (Si-O-Si). The specific structure of the cage-type silsesquioxane represented by the above composition formula (1) is not particularly limited as long as it satisfies the above composition formula (1). For example, the cage-type silsesquioxane represented by the following formula (1') can be cited.

In formula (1'), R ^1a to R ¹ⁱ each independently have the same meaning as R ¹ in formula (1). R ^c in formula (1') also has the same meaning as R ^c in formula (1).

The cage-type silsesquioxane represented by the above composition formula (2) is a silsesquioxane having a cage-type structure formed by six structural units represented by [R ² SiO _3/2 ] (T3 form) and two structural units represented by [R ² SiO _2/2 (OR ^c )] (T2 form) mutually bonding via siloxane bonds (Si-O-Si). The specific structure of the cage-type silsesquioxane represented by the above composition formula (2) is not particularly limited as long as it satisfies the above composition formula (2). For example, the cage-type silsesquioxane represented by the following formula (2') or (2'') can be cited.

R ^2a to R ^2h in formula (2') and R ²ⁱ to R ^2p in formula (2'') each independently have the same meaning as R ² in formula (2). R ^c in formulas (2') and (2'') also each independently have the same meaning as R ^c in formula (2).

The cage-type silsesquioxane represented by the above composition formula (3) is a silsesquioxane having a cage-type structure formed by eight constituent units represented by [R ³ SiO _3/2 ] (T3 form) and two constituent units represented by [R ³ SiO _2/2 (OR ^c )] (T2 form) mutually bonding via siloxane bonds (Si-O-Si). The specific structure of the cage-type silsesquioxane represented by the above composition formula (3) is not particularly limited as long as it satisfies the above composition formula (3). For example, the cage-type silsesquioxane represented by the following formula (3'), (3'') or (3''') can be cited.

R ^3a to R ^3j in formula (3'), R ^3k to R ^3t in formula (3''), R ^3u to R ^3z , and R ^3aa to R ^3dd in formula (3''') each independently have the same meaning as R ³ in formula (3). R ^c in formulas (3'), (3''), and (3''') also each independently have the same meaning as R ^c in formula (3).

The cage-type silsesquioxane represented by the above composition formula (4) is a silsesquioxane having a cage-type structure formed by ten constituent units represented by [R ⁴ SiO _3/2 ] (T3 form) and two constituent units represented by [R ⁴ SiO _2/2 (OR ^c )] (T2 form) mutually bonding via siloxane bonds (Si-O-Si). The specific structure of the cage-type silsesquioxane represented by the above composition formula (4) is not particularly limited as long as it satisfies the composition formula (4). For example, the cage-type silsesquioxane represented by the following formula (4') or (4'') can be cited.

R ^4a to R ^4l in formula (4') and R ^4m to R ^4x in formula (4'') each independently have the same meaning as R ⁴ in formula (4). R ^c in formulas (4') and (4'') also each independently have the same meaning as R ^c in formula (4).

The condensed silsesquioxane of the present invention may also include cage-type silsesquioxanes represented by composition formulas other than the above-mentioned composition formulas (1), (2), (3), and (4), within the scope that does not impair the effects of the present invention. Examples of composition formulas other than the above-mentioned composition formulas (1), (2), (3), and (4) include the following composition formulas (5) to (8).・Formula (5): [R ⁵ SiO _3/2 ] ₆ [R ⁵ SiO _2/2 (OR ^c )] ₃ (In formula (5), R ⁵ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c is independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (6): [R ⁶ SiO _3/2 ] ₈ [R ⁶ SiO _2/2 (OR ^c )] ₃ (In formula (6), R ⁶ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (7): [R ⁷ SiO _3/2 ] ₁₀ [R ⁷ SiO _2/2 (OR ^c )] ₁ (In formula (7), R ⁷ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (8): [R ⁸ SiO _3/2 ] ₁₂ [R ⁸ SiO _2/2 (OR ^c )] ₁ (In formula (8), R ⁸ are independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom)

The condensed silsesquioxane of the present invention also includes a mixture of the cage-type silsesquioxanes represented by the above-mentioned composition formulas (1) to (8). That is, the condensed silsesquioxane of the present invention may be a condensate obtained by condensing two or more cage-type silsesquioxanes selected from the group consisting of the cage-type silsesquioxanes represented by the above-mentioned composition formulas (1), (2), (3), (4), (5), (6), (7), and (8).

Furthermore, even when a cage-type silsesquioxane having three hydroxyl groups represented by -OR ^c as shown in the above-mentioned composition formula (5) and composition formula (6) is included, the case where two of them are condensed is also included in the condensed silsesquioxane of the present invention. Furthermore, when all of the three hydroxyl groups represented by -OR ^c in the above-mentioned composition formula (5) and composition formula (6) are condensed, as long as the effect of the invention is not impaired, it is also considered to be included in the condensed silsesquioxane of the present invention.

The "cationically polymerizable functional group" in the aforementioned group containing a polymerizable functional group is not particularly limited as long as it is cationic polymerizable. Examples thereof include an epoxy group, an oxobutyl group, a vinyl ether group, and a vinylphenyl group. The "radical polymerizable functional group" in the aforementioned group containing a polymerizable functional group is not particularly limited as long as it is radical polymerizable. Examples thereof include a (meth)acryloyloxy group, a (meth)acrylamide group, a vinyl group, and a vinylthio group. From the perspective of achieving a surface hardness of the cured product (e.g., 4H or higher), epoxy groups and (meth)acryloyloxy groups are preferred, with epoxy groups being more preferred.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and R ⁵ in the composition formula (5) The group containing a polymerizable functional group in R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), ^Ra in formula (I), and R ^b in formula (II) is not particularly limited, but is preferably a group containing an epoxy group. From the viewpoint of the curability of the curable composition, the surface hardness or heat resistance of the cured product, it is preferably a group represented by the following formula (1A), a group represented by formula (1B), a group represented by formula (1C), or a group represented by formula (1D). More preferably, it is a group represented by the following formula (1A) or a group represented by formula (1C). Still more preferably, it is a group represented by the following formula (1A).

In the above formula (1A), R ^1A represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include a linear or branched alkylene group having 1 to 10 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. From the perspective of the surface hardness and hardenability of the cured product, R ^1A is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, trimethylene group, or propylene group, and even more preferably an ethylene group or trimethylene group.

In the above formula (1B), R ^1B represents a linear or branched alkylene group, and examples thereof include the same groups as for R ^1A . From the perspective of the surface hardness and curability of the cured product, R ^1B is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

In the above formula (1C), R ^1C represents a linear or branched alkylene group, and examples thereof include the same groups as for R ^1A . From the perspective of the surface hardness and curability of the cured product, R ^1C is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

In the above formula (1D), R ^1D represents a linear or branched alkylene group, and examples thereof include the same groups as for R ^1A . From the perspective of the surface hardness and curability of the cured product, R ^1D is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and R ⁵ in the composition formula (5) The group containing a polymerizable functional group in R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), ^Ra in formula (I), and R ^b in formula (II) is preferably a group containing an epoxy group, and more preferably a group represented by the above formula (1A) in which R ^1A is an ethylene group [wherein, 2-(3',4'-epoxycyclohexyl)ethyl].

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and R ⁵ in the composition formula (5) The aryl group in the substituted or unsubstituted aryl group of R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), ^Ra in formula (I), and R ^b in formula (II) can be exemplified by phenyl, tolyl, naphthyl, and the like.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and R ⁵ in the composition formula (5) , R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), ^Ra in formula (I), and R ^b in formula (II) The above-mentioned arylalkyl groups in the substituted or unsubstituted arylalkyl groups include, for example, benzyl and phenethyl.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and R ⁵ in the composition formula (5) , R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), ^Ra in formula (I), and R ^b in formula (II) are substituted or unsubstituted cycloalkyl groups, for example, cyclobutyl, cyclopentyl, cyclohexyl, etc.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z and R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and R ⁵ in the composition formula (5) The alkyl group in the substituted or unsubstituted alkyl groups of R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), ^Ra in formula (I), and R ^b in formula (II) can be, for example, a linear or branched alkyl group such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl.

As R ¹ in the above-mentioned composition formula (1), R ^1a to R ¹ⁱ in the formula (1'), R ² in the composition formula (2), R ^2a to R ^2h in the formula (2'), R ²ⁱ to R ^2p in the formula (2''), R ³ in the composition formula (3), R ^3a to R ^3j in the formula (3'), R ^3k to R ^3t in the formula (3''), R ^3u to R ^3z , R ^3aa to R ^3dd in the formula (3'''), R ⁴ in the composition formula (4), R ^4a to R ^4l in the formula (4'), R ^4m to R ^4x in the formula (4''), and ^Ra in the formula (I), R in the composition formula (5) ^5. The alkenyl group in the substituted or unsubstituted alkenyl groups of R ⁶ in formula (6), R ⁷ in formula (7), R ⁸ in formula (8), and R ^b in formula (II) may include, for example, straight-chain or branched alkenyl groups such as vinyl, allyl, and isopropenyl.

The number of groups containing a polymerizable functional group in R ¹ in the above composition formula (1) is preferably 3 to 9, more preferably 5 to 9, further preferably 7 to 9, further more preferably 9 (all of which are groups containing a polymerizable functional group). The number of groups containing a polymerizable functional group in R ² in the above composition formula (2) is preferably 3 to 8, more preferably 5 to 8, further preferably 7 to 8, further more preferably 8 (all of which are groups containing a polymerizable functional group). The number of groups containing a polymerizable functional group in R ³ in the above composition formula (3) is preferably 3 to 10, more preferably 5 to 10, further preferably 7 to 10, further more preferably 10 (all of which are groups containing a polymerizable functional group). The number of groups containing polymerizable functional groups in ^R₄ in the above composition formula (4) is preferably 3 to 12, more preferably 5 to 12, further preferably 7 to 12, further more preferably 12 (all of which are groups containing polymerizable functional groups). The number of groups containing polymerizable functional groups is preferably larger from the viewpoint of the curability of the curable composition and the surface hardness of the cured product.

Furthermore, in the polyorganosilsesquioxane of the present invention, the ratio of groups containing polymerizable functional groups (e.g., groups containing epoxy groups) to the total of R ¹ in the above-mentioned composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), and R ⁴ in the composition formula (4)) (the number of groups containing polymerizable functional groups/the total number of R ¹ to R ⁴ ) is, for example, 30% or more, preferably 50% or more, and more preferably 80% or more. The ratio of groups containing polymerizable functional groups is preferably higher from the viewpoint of the curability of the curable composition and the surface hardness of the cured product, and is preferably higher than the above value.

Regarding the polyorganosilsesquioxane of the present invention, the molar ratio of the constituent unit (T3 form) represented by the above formula (I) to the constituent unit (T2 form) represented by the above formula (II) [constituent unit represented by formula (I)/constituent unit represented by formula (II); T3 form/T2 form] is, for example, not less than 1 and not more than 500. Furthermore, the constituent unit represented by the above formula (I) and the constituent unit represented by the above formula (II) include the T3 form and T2 form of the cage-type silsesquioxane represented by the above composition formula (1), composition formula (2), composition formula (3), and composition formula (4), and further include the T3 form and T2 form of all silsesquioxanes other than these (complete cage-type silsesquioxane, ladder-type silsesquioxane, random silsesquioxane, etc.).

As described above, the lower limit of the ratio [T3 body/T2 body] is 1, preferably 2, more preferably 3, more preferably 4, more preferably 6, more preferably 7, more preferably 8, more preferably 8, more preferably 10, more preferably 20, and further preferably 40. By setting the ratio [T3 body/T2 body] to 1 or greater, the surface of an uncured or semi-cured hard coat layer becomes less sticky, the blocking resistance is improved, and the material can be easily wound into a roll, making it suitable for use as a component of a hard coat layer having flex resistance. Furthermore, the surface hardness and adhesion of the cured product or hard coat layer are significantly improved. On the other hand, the upper limit of the ratio [T3 body/T2 body] is preferably 500, more preferably 400, more preferably 300, more preferably 100, more preferably 50, more preferably 40, more preferably 30, more preferably 25, more preferably 20, more preferably 18, and further preferably 18. By setting the ratio [T3 body/T2 body] to 500 or less, compatibility with other components in the curable composition is improved and viscosity is suppressed, thereby facilitating handling and coating as a hard coating layer.

In addition to the aforementioned silsesquioxane constituent units [RSiO _3/2 ] (T units), the polyorganosilsesquioxane of the present invention may further include at least one siloxane constituent unit selected from the group consisting of constituent units represented by [(R) ₃ SiO _1/2 ] (i.e., M units), constituent units represented by [(R) ₂ SiO _2/2 ] (i.e., D units), and constituent units represented by [SiO _4/2 ] (i.e., Q units). Furthermore, as silsesquioxane constituent units other than the constituent units represented by formula (I), constituent units represented by [HSiO _3/2 ] may also be exemplified. Furthermore, R in the aforementioned formula represents a hydrogen atom or a monovalent organic group.

The ratio [T3 form/T2 form] in the polyorganosilsesquioxane of the present invention can be determined, for example, by ^29Si -NMR spectroscopy. In the ^29Si -NMR spectrum, the silicon atoms in the structural unit represented by formula (I) (T3 form) and the silicon atoms in the structural unit represented by formula (II) (T2 form) exhibit signals (peaks) at different positions (chemical shifts). Therefore, the ratio [T3 form/T2 form] is determined by calculating the integral ratio of these peaks. The signal for the silicon atoms in the structure represented by formula (I) (T3 form) appears at -64 to -70 ppm, while the signal for the silicon atoms in the structure represented by formula (II) (T2 form) appears at -54 to -60 ppm. Therefore, the ratio [T3 body/T2 body] can be obtained by calculating the integral ratio of the signal between -64 and -70 ppm (T3 body) and the signal between -54 and -60 ppm (T2 body).

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane of the present invention can be measured, for example, using the following apparatus and conditions. Measuring apparatus: "Brucker AVANCE (600 MHz)" (manufactured by Brucker Corporation) Solvent: Deuterated chloroform Accumulated times: 8000 Measurement temperature: 25°C Sample: Polyorganosilsesquioxane/chromium(III) acetylacetonate/deuterated chloroform (1% tetramethylsilane) = 2.0:0.10:4.0 (weight ratio)

The ratio [T3 form/T2 form] of 1 to 500 in the polyorganosilsesquioxane of the present invention means that the amount of the T2 form in the polyorganosilsesquioxane of the present invention is equal to or relatively less than the T3 form, allowing the hydrolysis and condensation reactions of the silanol to proceed.

The ratio of the silsesquioxane constituent units in the polyorganosilsesquioxane of the present invention can be appropriately adjusted by adjusting the composition of the raw materials (hydrolyzable trifunctional silane) used to form the constituent units.

The condensate obtained by condensing two or more of at least one of the cage-type silsesquioxanes represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3) and composition formula (4) is the condensed silsesquioxane of the present invention, which refers to the condensation of two or more (for example, 2 to 5, preferably 2 to 3, and more preferably 2) of one of the cage-type silsesquioxanes represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3) and composition formula (4) or the condensation of two or more (for example, 2 to 5, preferably 2 to 3, and more preferably 2) of two or more of the cage-type silsesquioxanes represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3) and composition formula (4). Here, "condensation" refers to the dehydration of the hydroxyl groups represented by -OR ^c in the above-mentioned formulas (1), (2), (3), and (4) (hydroxyl groups formed by hydrolysis when -OR ^c is an alkoxy group) to form siloxane bonds (Si-O-Si).

Since the cage-type silsesquioxanes represented by the above-mentioned composition formula (2), composition formula (3) and composition formula (4) have two groups represented by -OR ^c in the molecule, the polyorganosilsesquioxane of the present invention formed by condensing these cage-type structures has a structure in which these cage-type structures are connected in a straight line.

Since the cage-type silsesquioxane represented by the above composition formula (1) has only one group represented by -OR ^c in the molecule, condensation occurs at the terminal portion of the structure in which the cage-type structure is connected in a straight line.

Furthermore, the condensed silsesquioxane of the present invention may be obtained by condensing two cage-type silsesquioxanes represented by the above-mentioned composition formula (1) without the cage-type structure derived from the cage-type silsesquioxanes represented by the above-mentioned composition formula (2), composition formula (3), and composition formula (4).

Regarding the condensed silsesquioxane of the present invention, the condensation form of each cage-type constituent unit derived from the cage-type silsesquioxane represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3) and composition formula (4) is not particularly limited and can be random or block type.

For example, when the condensed silsesquioxane of the present invention includes a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (2'), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (2a).

The symbols in the above formula (2a) have the same meanings as those in the above formula (2'). Furthermore, when the condensed silsesquioxane of the present invention comprises a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (2''), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (2b).

The symbols in the above formula (2b) have the same meanings as those in the above formula (2''). For example, when the condensed silsesquioxane of the present invention includes a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (3'), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (3a).

The symbols in the above formula (3a) have the same meanings as those in the above formula (3'). Furthermore, when the condensed silsesquioxane of the present invention comprises a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (3''), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (3b).

The symbols in the above formula (3b) have the same meanings as those in the above formula (3''). Furthermore, when the condensed silsesquioxane of the present invention comprises a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (3'''), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (3c).

The symbols in the above formula (3c) have the same meanings as those in the above formula (3'''). For example, when the condensed silsesquioxane of the present invention includes a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (4'), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (4a).

The symbols in the above formula (4a) have the same meanings as those in the above formula (4'). Furthermore, when the condensed silsesquioxane of the present invention comprises a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (4''), the molecule has a repeating structure of the cage-type silsesquioxane structure represented by the following formula (4b).

The reference numerals in the above formula (4b) have the same meanings as those in the above formula (4''). For example, when the condensed silsesquioxane of the present invention includes a cage-type structure derived from the cage-type silsesquioxane represented by the above formula (1'), the cage-type silsesquioxane structure represented by the following formula (1a) and/or the cage-type silsesquioxane structure represented by the following formula (1b) may be present at both ends or at one end.

The symbols in the above formula (1a) have the same meanings as in the above formula (1'). R ^1j to R ^1r in the above formula (1b) have the same meanings as R ^1a to R ¹ⁱ in the above formula (1').

The condensed silsesquioxanes of the present invention include, for example, two or more condensates of one type, such as a condensate of two cage-type silsesquioxanes represented by the composition formula (1), and two or more condensates of different types, such as a condensate of a cage-type silsesquioxane represented by the composition formula (1) and a cage-type silsesquioxane represented by the composition formula (2). Among them, the condensed silsesquioxane of the present invention is preferably a condensation product of one cage-type silsesquioxane represented by the above-mentioned composition formula (1) and another cage-type silsesquioxane represented by the above-mentioned composition formula (1), or a condensation product of one cage-type silsesquioxane represented by the above-mentioned composition formula (1) and any one of the cage-type silsesquioxanes represented by the composition formula (2), the composition formula (3) and the composition formula (4).

Among the condensed silsesquioxanes of the present invention, examples of silsesquioxanes that are condensates of one cage-type silsesquioxane represented by the above-mentioned composition formula (1) and one cage-type silsesquioxane represented by the above-mentioned composition formula (2) include: a condensed silsesquioxane represented by the following formula (1a-2a) formed by condensing the group represented by -OR ^c in the above-mentioned formula (1') with one of the two groups represented by -OR ^c in the above-mentioned formula (2'). Furthermore, the substituents (R ^1a to R ¹ⁱ and R ^2a to R ^2h ) in the formulas (1a-2b) are the same as those in the formulas (1a) and (2b).

Among the condensed silsesquioxanes of the present invention, examples of silsesquioxanes that are condensates of one cage-type silsesquioxane represented by the above-mentioned composition formula (1) and another cage-type silsesquioxane represented by the above-mentioned composition formula (1) include: condensed silsesquioxanes represented by the following formulas (1a-1b) formed by condensing two groups represented by -OR ^c in the above-mentioned formula (1'). Furthermore, the substituents (R ^1a to R ^1r ) in formulas (1a-1b) are the same as those in formulas (1a) and (1b).

Among the condensed silsesquioxanes of the present invention, examples of silsesquioxanes that are condensates of one cage-type silsesquioxane represented by the above-mentioned composition formula (2) and another cage-type silsesquioxane represented by the above-mentioned composition formula (2) include: a condensed silsesquioxane represented by the following formula (2a-2a) formed by condensing two groups represented by -OR ^c in the above-mentioned formula (2'). Furthermore, the substituents (R ^2a to R ^2h ) in formula (2a-2a) are the same as those in formula (2a).

In addition to the condensed silsesquioxanes of the present invention, the polyorganosilsesquioxanes of the present invention may also include cage-type silsesquioxanes (i.e., complete cage-type silsesquioxanes) in which the stereostructure of silicon oxide, such as a regular hexahedral structure, is completely undecomposed, and cage-type silsesquioxanes such as those represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3), and composition formula (4) that are not condensed (i.e., incomplete cage-type silsesquioxanes). In this specification, the above-mentioned complete cage-type silsesquioxanes and incomplete cage-type silsesquioxanes are collectively referred to as monomer cage-type silsesquioxanes. The content of the cage-type silsesquioxane monomer in the polyorganosilsesquioxane of the present invention is, for example, 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more, and for example, 50% by weight or less, preferably 40% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the polyorganosilsesquioxane of the present invention. If the content of the cage-type silsesquioxane monomer is within the above range, the surface hardness of the resulting cured product can be further improved.

The polyorganosilsesquioxane of the present invention may also have cage-type silsesquioxanes other than the condensed silsesquioxanes of the present invention. Furthermore, the polyorganosilsesquioxane of the present invention may have ladder-type or random-type silsesquioxane structures in addition to cage-type silsesquioxanes. Furthermore, the polyorganosilsesquioxane of the present invention may have a combination of two or more of these silsesquioxane structures.

The content of the condensed silsesquioxane of the present invention in the polyorganosilsesquioxane of the present invention is 20% by weight or greater (preferably 25-90% by weight, more preferably 30-80% by weight, and even more preferably 40-70% by weight) relative to the total weight of the polyorganosilsesquioxane of the present invention. The content of the cage-type silsesquioxane is, for example, 40-99.5% by weight, preferably 45-98% by weight, and even more preferably 50-96% by weight relative to the total weight of the polyorganosilsesquioxane of the present invention.

The polyorganosilsesquioxane of the present invention has a number average molecular weight (Mn) calculated based on standard polystyrene as determined by gel permeation chromatography, for example, from 2,000 to 50,000, preferably from 2,500 to 40,000, and even more preferably from 3,000 to 30,000. A number average molecular weight of 2,000 or greater makes the surface of an uncured or semi-cured hard coat less sticky, improving blocking resistance and making it easier to roll up. Therefore, a number average molecular weight of 2,000 or greater makes it ideal for use as a component of a hard coat for transfer films used in in-mold injection molding, further enhancing the heat resistance, scratch resistance, and adhesive properties of the cured product. On the other hand, by setting the number average molecular weight to 50,000 or less, the compatibility with other components in the curable composition is improved, further improving the heat resistance of the cured product.

The molecular weight dispersion (Mw/Mn) of the polyorganosilsesquioxane of the present invention, as measured by gel permeation chromatography, is, for example, 1.0 to 4.0, preferably 1.1 to 3.0, and even more preferably 1.2 to 2.5. A molecular weight dispersion of 4.0 or less improves solubility in solvents, further enhancing the surface hardness and adhesion of the cured product. On the other hand, a molecular weight dispersion of 1.1 or greater facilitates liquidification, tending to improve workability.

Furthermore, the number average molecular weight and molecular weight dispersion of the polyorganosilsesquioxane of the present invention can be determined by GPC measurement. Furthermore, the content of the aforementioned monomeric cage-type silsesquioxane and condensed silsesquioxane in the polyorganosilsesquioxane of the present invention can be determined based on the area ratio of the corresponding peaks in the GPC measurement. GPC measurement can be performed using the following apparatus and conditions. Measurement Apparatus: GPC Semi-Micro System (Shimadzu Corporation) Detector: RI detector (Shoko Scientific Co., Ltd.) Columns: KF-G4A (guard column), KF-602, and KF-603 (Shoko Scientific Co., Ltd.) Flow Rate: 0.6 mL/min Measurement Temperature: 40°C Measurement Time: 13 min Injection Volume: 20 μL Eluent: THF, Sample Concentration: 0.1–0.2 wt% Molecular Weight: Standard Polystyrene Equivalent

The 5% weight loss temperature ( _Td5 ) of the polyorganosilsesquioxane of the present invention in an air environment is not particularly limited, but is preferably 330°C or higher (e.g., 330-450°C), more preferably 340°C or higher, and even more preferably 350°C or higher. A 5% weight loss temperature of 330°C or higher tends to further improve the heat resistance of the cured product. The polyorganosilsesquioxane of the present invention has a ratio [T3 form/T2 form] of 1 to 500, a number average molecular weight of 2,000 to 50,000, and a molecular weight dispersion of 1.0 to 4.0, thereby achieving a 5% weight loss temperature of 330°C or higher. Furthermore, the 5% weight loss temperature is an indicator of heat resistance. It is the temperature at which the weight of the material decreases by 5% compared to the pre-heating weight when heated at a certain heating rate. This 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) in an air environment at a heating rate of 5°C/minute.

The polyorganosilsesquioxane of the present invention can be produced by any known or commonly used polysiloxane production method, without particular limitation. For example, it can be produced by hydrolyzing and condensing one or more hydrolyzable silane compounds. The hydrolyzable silane compound must be a hydrolyzable trifunctional silane compound (a compound represented by the following formula (A)).

More specifically, for example, by using a hydrolyzable silane compound for forming the silsesquioxane constituent unit (T unit) in the polyorganosilsesquioxane of the present invention, i.e., a compound represented by the following formula (a), and optionally further hydrolyzing and condensing a compound represented by the following formula (b) and a compound represented by the following formula (c), the above-mentioned composition formula (1), composition formula (2), composition formula (3) and/or composition formula (4) are generated. The cage-type silsesquioxane represented by formula (4) can be subjected to further hydrolysis and condensation reactions to produce the polyorganosilsesquioxane of the present invention containing the condensed silsesquioxane of the present invention. The condensed silsesquioxane of the present invention is obtained by condensing two or more of one type of cage-type silsesquioxane represented by formula (1), formula (2), formula (3) and formula (4), or condensing two or more of two types of cage-type silsesquioxane represented by formula (4).

The compound represented by the above formula (A) is a compound that forms the constituent unit represented by [ ^RASiO3 _/2 ] or [ ^RASiO2 _/2 ( ^ORc )] in the condensed silsesquioxane of the present invention. ^RA in formula (A) represents a group containing a polymerizable functional group, similarly to ^R1 in the above composition formula ( ¹ ), R2 in the composition formula (2), ^R3 in the composition formula (3), and ^R4 in the composition formula (4) (i.e., the substituent in the cage-type silsesquioxane). Regarding ^RA in formula (A), as the group containing a polymerizable functional group, preferably, the group represented by the above-mentioned formula (1A), the group represented by the above-mentioned formula (1B), the group represented by the above-mentioned formula (1C), or the group represented by the above-mentioned formula (1D), more preferably, the group represented by the above-mentioned formula (1A) or the group represented by the above-mentioned formula (1C), further preferably, the group represented by the above-mentioned formula (1A), further preferably, the group represented by the above-mentioned formula (1A) wherein ^RA is an ethylene group [in which case, 2-(3',4'-epoxycyclohexyl)ethyl] is present.

In the above formula (A), ^X1 represents an alkoxy group or a halogen atom. Examples of the alkoxy group in ^X1 include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy. Examples of the halogen atom in ^X1 include fluorine, chlorine, bromine, and iodine. Among them, ^X1 is preferably an alkoxy group, and more preferably a methoxy or ethoxy group. Furthermore, the three X1 ^groups may be the same or different.

The compound represented by formula (B) above forms the constituent unit represented by [ ^RBSiO3 _/2 ] or [ ^RBSiO2 _/2 ( ^ORc )] in the condensed silsesquioxane of the present invention. In formula (B), ^RB represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. In formula (B), ^RB is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.

In the above formula (B), ^X₂ represents an alkoxy group or a halogen atom. Specific examples of ^X₂ include those exemplified for ^X₁ . Among them, ^X₂ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Furthermore, the three X₂ ^groups may be the same or different.

The compound represented by formula (C) above forms a constituent unit represented by [HSiO _3/2 ] or [HSiO _2/2 (OR ^c )] in the condensed silsesquioxane of the present invention. In formula (C), X ³ represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified for X ^1. Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Furthermore, the three X ³ groups may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by formulas (A) to (C) above may be used in combination. Examples thereof include hydrolyzable trifunctional silane compounds other than the compounds represented by formulas (A) to (C) above, hydrolyzable monofunctional silane compounds forming M units, hydrolyzable difunctional silane compounds forming D units, and hydrolyzable tetrafunctional silane compounds forming Q units.

The amount or composition of the hydrolyzable silane compound can be appropriately adjusted based on the desired structure of the polyorganosilsesquioxane of the present invention. For example, the amount of the compound represented by formula (A) is not particularly limited, but is preferably 30-100 mol%, more preferably 55-100 mol%, even more preferably 65-100 mol%, and even more preferably 80-99 mol%, relative to the total amount of the hydrolyzable silane compound used (100 mol%).

The amount of the compound represented by formula (B) used is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, further preferably 0 to 40 mol%, and further preferably 1 to 15 mol%, relative to the total amount of the hydrolyzable silane compound used (100 mol%).

Furthermore, the ratio (total amount ratio) of the compound represented by formula (A) to the compound represented by formula (B) relative to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 80 to 100 mol%.

When two or more hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the reactions are carried out sequentially, the order of the reactions is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in a single stage or in two or more stages. To efficiently produce the polyorganosilsesquioxane of the present invention, the hydrolysis and condensation reaction is preferably carried out in two or more stages (preferably two stages). The following describes an embodiment of the hydrolysis and condensation reaction of the hydrolyzable silane compound carried out in two stages, but the method for producing the polyorganosilsesquioxane of the present invention is not limited thereto.

When the hydrolysis and condensation reaction of the present invention is carried out in two stages, it is preferred that in the first stage of the hydrolysis and condensation reaction, a polyorganosilsesquioxane having a ratio [T3 form/T2 form] of 1 or greater and less than 20 and a number average molecular weight of, for example, 1000 to 3000 (hereinafter referred to as the "intermediate polyorganosilsesquioxane") is obtained. In the second stage, the intermediate polyorganosilsesquioxane is further subjected to a hydrolysis and condensation reaction to obtain the polyorganosilsesquioxane of the present invention.

The hydrolysis and condensation reaction in the first stage can be carried out in the presence of a solvent or in the absence of a solvent. It is preferably carried out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; diethyl ether, dimethoxyethane, tetrahydrofuran, dimethoxyethane, and dimethoxyethane. Examples of the solvent include ethers such as alkane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and alcohols such as methanol, ethanol, isopropyl alcohol, and butanol. Among these solvents, ketones and ethers are preferred. The solvents may be used alone or in combination of two or more.

The amount of solvent used in the hydrolysis and condensation reaction of the first stage is not particularly limited and can be appropriately adjusted within the range of 0 to 2000 parts by weight relative to 100 parts by weight of the total amount of the hydrolyzable silane compound, depending on the desired reaction time, etc.

The hydrolysis and condensation reactions in the first stage are preferably carried out in the presence of a catalyst and water. The catalyst can be either an acid catalyst or a base catalyst. Base catalysts are preferred to inhibit the decomposition of polymerizable functional groups such as epoxy groups. Examples of acid catalysts include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; and Lewis acids such as ferric chloride. Examples of the alkaline catalyst include: hydroxides of alkaline metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkaline earth metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; bicarbonates of alkaline metals such as lithium bicarbonate, sodium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; organic acid salts of alkaline metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (e.g. Acetate); organic acid salts of alkaline earth metals such as magnesium acetate (e.g., acetate); alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium tert-butoxide; alkali metal phenoxides such as sodium phenoxide; amines (such as tertiary amines) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridine, and 1,10-phenanthroline. The catalyst may be used alone or in combination of two or more. Furthermore, the catalyst can be used in a state of being dissolved or dispersed in water or a solvent.

The amount of the catalyst used in the hydrolysis and condensation reaction of the first stage is not particularly limited and can be appropriately adjusted within the range of 0.002 to 0.200 mol per 1 mol of the total amount of the hydrolyzable silane compound.

The amount of water used in the hydrolysis and condensation reaction of the first stage is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 mol relative to 1 mol of the total amount of the hydrolyzable silane compound.

The method for adding the water in the first stage of the hydrolysis and condensation reaction is not particularly limited. The total amount of water used (the entire amount used) may be added all at once, or it may be added incrementally. In the case of incremental addition, it may be added continuously or intermittently.

As for the reaction conditions for the first-stage hydrolysis and condensation reaction, it is important to select reaction conditions such that the ratio [T3 form/T2 form] of the intermediate polyorganosilsesquioxane is 1 or greater and less than 20. The reaction temperature for the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 40-100°C, more preferably 45-80°C. By controlling the reaction temperature within this range, the ratio [T3 form/T2 form] tends to be more efficiently controlled to 1 or greater and less than 20. Furthermore, the reaction time for the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.1-10 hours, more preferably 1.5-8 hours. The hydrolysis and condensation reactions in the first stage can be carried out under normal pressure, elevated pressure, or reduced pressure. Furthermore, the environment in which the hydrolysis and condensation reactions in the first stage are carried out is not particularly limited. Examples include an inert gas environment such as nitrogen or argon, or an environment in the presence of oxygen such as air. An inert gas environment is preferred.

The intermediate polyorganosilsesquioxane can be obtained through the hydrolysis and condensation reaction in the first stage. After the hydrolysis and condensation reaction in the first stage, it is preferably neutralized with a catalyst to inhibit the decomposition of polymerizable functional groups, such as epoxy ring opening. The intermediate polyorganosilsesquioxane can be isolated and purified by separation methods such as water washing, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation methods. The reaction solution containing the intermediate polyorganosilsesquioxane can be subjected to the hydrolysis and condensation reaction in the first stage.

The polyorganosilsesquioxane of the present invention can be produced by subjecting the intermediate polyorganosilsesquioxane obtained in the first-stage hydrolysis and condensation reaction to the second-stage hydrolysis and condensation reaction. The second-stage hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. When the second-stage hydrolysis and condensation reaction is carried out in the presence of a solvent, the solvents listed for the first-stage hydrolysis and condensation reaction can be used. The solvent for the second-stage hydrolysis and condensation reaction can be the intermediate polyorganosilsesquioxane containing the reaction solvent or extraction solvent used in the first-stage hydrolysis and condensation reaction, either directly or after partial or complete distillation. Alternatively, the solvent can be replaced by adding a higher-boiling-point solvent than the solvent used in the first-stage hydrolysis and condensation reaction to the reaction solution containing the intermediate polyorganosilsesquioxane, followed by heating and distillation. Furthermore, the solvent may be used alone or in combination of two or more.

When a solvent is used in the hydrolysis and condensation reaction of the second stage, its amount is not particularly limited and can be appropriately adjusted within the range of 0 to 2000 parts by weight relative to 100 parts by weight of the intermediate polyorganosilsesquioxane, depending on the desired reaction time and other factors.

The hydrolysis and condensation reaction in the second stage is preferably carried out in the presence of a catalyst and water. The catalysts listed for the hydrolysis and condensation reaction in the first stage can be used. To inhibit the decomposition of polymerizable functional groups such as epoxy groups, alkaline catalysts are preferred, particularly alkaline metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; and alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate. The catalysts may be used singly or in combination. The catalysts may be dissolved or dispersed in water or a solvent. Furthermore, the catalyst used in the hydrolysis and condensation reaction in the first stage can be directly used in the hydrolysis and condensation reaction in the second stage.

The amount of the catalyst used in the hydrolysis and condensation reaction of the second stage is not particularly limited and can be appropriately adjusted within a range of preferably 0.01 to 10,000 ppm, more preferably 0.1 to 1,000 ppm, relative to the intermediate polyorganosilsesquioxane (1,000,000 ppm).

The amount of water used in the second-stage hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within a range of preferably 10-100,000 ppm, more preferably 100-20,000 ppm, relative to the intermediate polyorganosilsesquioxane (1,000,000 ppm). If the amount of water used exceeds 100,000 ppm, it may be difficult to control the polyorganosilsesquioxane ratio (T3 form/T2 form) or number average molecular weight within the specified range.

The method for adding the water in the second-stage hydrolysis and condensation reaction is not particularly limited. The total amount of water used (the entire amount) may be added all at once, or it may be added incrementally. Incremental addition may be continuous or intermittent. Furthermore, the water used in the first-stage hydrolysis and condensation reaction may be used directly, or the water remaining after a portion of the distillation reaction has been removed may be used.

As for the reaction conditions for the second-stage hydrolysis and condensation reaction, it is important to select reaction conditions such that the ratio [T3 form/T2 form] of the polyorganosilsesquioxane of the present invention is 20 to 500, and the number average molecular weight is 2,000 to 50,000. The reaction temperature for the second-stage hydrolysis and condensation reaction varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200°C, more preferably 30 to 150°C, and even more preferably 80 to 120°C. By controlling the reaction temperature within this range, the ratio [T3 form/T2 form] and number average molecular weight can be more efficiently controlled within the desired range. The reaction time of the second-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours, and even more preferably 5 to 200 hours. Also, by allowing the hydrolysis and condensation reactions to proceed within the aforementioned reaction temperature range while sampling is performed at appropriate intervals, and the reaction is conducted while measuring the aforementioned ratio [T3 form/T2 form] and number average molecular weight, the polyorganosilsesquioxane of the present invention having the desired ratio [T3 form/T2 form] and number average molecular weight can be obtained.

The hydrolysis and condensation reaction in the second stage can be carried out under normal pressure, elevated pressure, or reduced pressure. Furthermore, the environment in which the hydrolysis and condensation reaction in the second stage is carried out is not particularly limited; for example, it can be carried out in an inert gas environment such as nitrogen or argon, or in the presence of oxygen such as air. An inert gas environment is preferred.

The polyorganosilsesquioxane of the present invention can be obtained through the hydrolysis and condensation reaction in the second stage. After the hydrolysis and condensation reaction in the second stage, it is preferably neutralized with a catalyst to inhibit the decomposition of polymerizable functional groups, such as epoxy ring opening. Furthermore, the polyorganosilsesquioxane of the present invention can be isolated and purified by separation methods such as water washing, acid washing, alkaline washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation methods.

The polyorganosilsesquioxane of the present invention, which contains a linear condensation structure of two or more cage-type silsesquioxanes, is believed to exhibit superior curability compared to conventional polyorganosilsesquioxanes. Consequently, a cured product of a curable composition containing the polyorganosilsesquioxane of the present invention exhibits high surface hardness and excellent heat resistance. Furthermore, the polyorganosilsesquioxane of the present invention exhibits excellent solubility in solvents such as organic solvents. "Two or more cage-type silsesquioxanes are condensed in a linear chain" means that two or more cage-type silsesquioxanes represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3), and/or composition formula (4) are condensed in series rather than three-dimensionally, resulting in a linear condensation compound. In addition, even if the polyorganosilsesquioxane of the present invention includes a cage-type silsesquioxane having three hydroxyl groups represented by -OR ^c as shown in the above-mentioned composition formula (5) and composition formula (6), when two of them are condensed, it is equivalent to "two or more cage-type silsesquioxanes are condensed in a linear chain." Furthermore, the above-mentioned mechanism is only a presumption and should not be interpreted as the invention of this case being limited to such mechanism.

[Curing Composition] The curable composition of the present invention is a curable composition (curable resin composition) containing the aforementioned polyorganosilsesquioxane of the present invention as an essential component. As described below, the curable composition of the present invention may further contain other components such as a curing catalyst (e.g., a photopolymerization initiator or a free radical polymerization initiator), a surface conditioner or modifier, a polymerization stabilizer, or a silane coupling agent. Depending on the intended use, the curable composition of the present invention can be used as a curable composition for forming a hard coat layer or as a curable composition for an adhesive (e.g., a curable composition for laminated semiconductors). The polyorganosilsesquioxane of the present invention may be used alone or in combination of two or more.

The content (blend amount) of the polyorganosilsesquioxane of the present invention in the curable composition of the present invention is not particularly limited. However, relative to the total weight of the curable composition excluding the solvent (100 weight%), it is preferably 70 weight% or greater but less than 100 weight%, more preferably 80 to 99.8 weight%, and even more preferably 90 to 99.5 weight%. A polyorganosilsesquioxane content of 70 weight% or greater tends to further improve the surface hardness and adhesion of the cured product. Furthermore, a polyorganosilsesquioxane content of less than 100 weight% allows for the inclusion of a curing catalyst, which tends to enable more efficient curing of the curable composition.

The ratio of the polyorganosilsesquioxane of the present invention relative to the total amount of the cationic curing compound or radical curing compound (100 weight%) in the curable composition of the present invention is not particularly limited, but is preferably 70-100 weight%, more preferably 75-98 weight%, and even more preferably 80-95 weight%. By setting the polyorganosilsesquioxane content of the present invention to 70 weight% or greater, the surface hardness and adhesion of the cured product tend to be further improved.

The curable composition of the present invention preferably further contains a curing catalyst. In order to further shorten the curing time until the material becomes non-sticky, it is preferred to include a photo- or thermal-polymerization initiator as the curing catalyst, and more preferably, a cationic polymerization initiator or a free-radical polymerization initiator. Furthermore, the curable composition of the present invention may contain a single curing catalyst or a combination of two or more.

The cationic polymerization initiator is a compound capable of initiating or accelerating the cationic polymerization reaction of the cationic-curable compound, such as the polyorganosilsesquioxane, of the present invention. The cationic polymerization initiator is not particularly limited, and examples thereof include photo-catalytic polymerization initiators (photoacid generators) and thermal cationic polymerization initiators (thermal acid generators).

As the photocatalytic polymerization initiator, known or commonly used photocatalytic polymerization initiators can be used, such as coronium salts (salts of coronium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), and salts of transition metal complex ions and anions. These salts can be used alone or in combination of two or more.

Examples of the coronium salt include [4-(4-biphenylthio)phenyl]-4-biphenylphenyl coronium tris(pentafluoroethyl)trifluorophosphate, triphenyl coronium salt, tri-p-toluene coronium salt, tri-o-toluene coronium salt, tris(4-methoxyphenyl) coronium salt, 1-naphthyldiphenyl coronium salt, 2-naphthyldiphenyl coronium salt, tris(4-fluorophenyl) coronium salt, tris-1-naphthyl coronium salt, tris-2-naphthyl coronium salt, tris(4-hydroxyphenyl) coronium salt, diphenyl[4-(phenylthio) [0014] triaryl stearyl salts such as [(4-(p-tolylthio)phenyl) stearyl salt, 4-(p-phenylthio)phenyl di(p-phenyl) stearyl salt; diaryl stearyl salts such as diphenylbenzylmethyl stearyl salt, diphenyl 4-nitrobenzylmethyl stearyl salt, diphenylbenzyl stearyl salt, diphenylmethyl stearyl salt; monoaryl stearyl salts such as phenylmethylbenzyl stearyl salt, 4-hydroxyphenylmethylbenzyl stearyl salt, 4-methoxyphenylmethylbenzyl stearyl salt; trialkyl stearyl salts such as dimethylbenzylmethyl stearyl salt, phenacyl tetrahydro thiophenium salt, dimethylbenzyl stearyl salt, etc.

Examples of the diphenyl[4-(phenylthio)phenyl]copperium salt include diphenyl[4-(phenylthio)phenyl]copperium hexafluoroantimonate and diphenyl[4-(phenylthio)phenyl]copperium hexafluorophosphate.

Examples of the iodine salts include: "UV9380C" (manufactured by Maitu Advanced Materials Japan Co., Ltd., bis(4-dodecylphenyl)iodine = 45% alkyl epoxypropyl ether solution of hexafluoroantimony), "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., tetrakis(pentafluorophenyl)borate = [(1-methylethyl)phenyl](methylphenyl)iodine), "WPI-124" (manufactured by Wako Junyaku Industries Co., Ltd.), diphenyliodine, di-p-tolueneiodine, bis(4-dodecylphenyl)iodine, and bis(4-methoxyphenyl)iodine.

Examples of the selenium salts include triaryl selenium salts such as triphenylselenium salt, tri-p-toluene selenium salt, tri-o-toluene selenium salt, tri(4-methoxyphenyl)selenium salt, and 1-naphthyldiphenylselenium salt; diaryl selenium salts such as diphenylbenzylmethylselenium salt, diphenylbenzylselenium salt, and diphenylmethylselenium salt; monoaryl selenium salts such as phenylmethylbenzylselenium salt; and trialkyl selenium salts such as dimethylbenzylmethylselenium salt.

Examples of the ammonium salt include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt; pyrrolidinium salts such as N,N-dimethylpyrrolidinium salt and N-ethyl-N-methylpyrrolidinium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt and N,N'-diethylimidazolinium salt; tetrahydropyrimidinium salt); N,N'-dimethyl tetrahydropyrimidinium salt, N,N'-diethyl tetrahydropyrimidinium salt, etc. tetrahydropyrimidinium salt; N,N-dimethyl Phonium salt, N,N-diethyl Phonium salts, etc. Morpholinium salt; piperidinium salts such as N,N-dimethylpiperidinium salt and N,N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; imidazolium salts such as N,N'-dimethylimidazolium salt; quinolium salts such as N-methylquinolinium salt; isoquinolinium salts such as N-methylisoquinolinium salt; thiazolium salts such as benzylbenzothiazolium salt; acridinium salts such as benzylacridinium salt, etc.

Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-toluenephosphonium salt, and tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; and tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylbenzylmethylphosphonium salt.

Examples of the salts of the transition metal complex ions include salts of chromium complex cations such as (η5-cyclopentadienyl)(η6-toluene)Cr ⁺ and (η5-cyclopentadienyl)(η6-xylene)Cr ⁺ ; and salts of iron complex cations such as (η5-cyclopentadienyl)(η6-toluene)Fe ⁺ and (η5-cyclopentadienyl)(η6-xylene)Fe ⁺ .

_Examples of anions constituting the above ^- mentioned salts include SbF6- ^, _PF6- ^, _BF4- , ( _CF3CF2 ) _3PF3- , ( _{CF3CF2CF2 )} ^3PF3- , ( _{C6F5 ) 4B-} , _{( C6F5 ) 4Ga- ,} sulfonate ^anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, ^{p - toluenesulfonate} anion _, etc. ⁾ , _{( CF3SO2 ) 3C- , ( CF3SO2} ) _2N- , perhalide ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuth ions, carboxylate ions, aryl borate ions, thiocyanate ions, nitrate ions, etc.

Examples of the thermal cationic polymerization initiator include aryl stibnium salts, aryl iodonium salts, aromatic hydrocarbon-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride-amine complexes.

Examples of the aforementioned aryl antimony salts include hexafluoroantimony salts. Commercially available products such as "SP-66" and "SP-77" (produced by ADEKA Co., Ltd.) and "San-Aid SI-60L," "San-Aid SI-80L," "San-Aid SI-100L," and "San-Aid SI-150L" (produced by Sanshin Chemical Industries Co., Ltd.) can be used in the curable composition of the present invention. Examples of the aforementioned aluminum chelates include ethylaluminum diisopropyl acetoacetate and tris(ethyl acetoacetate)aluminum. Examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

The free radical polymerization initiator is a compound capable of initiating or accelerating the free radical polymerization reaction of the radical curable compound, such as the polyorganosilsesquioxane, of the present invention. Examples of the free radical polymerization initiator include photo-radical polymerization initiators and thermal-radical polymerization initiators.

Examples of the photoradical polymerization initiator include benzophenone, acetophenone dibenzoyldione, dibenzoyldione dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfide, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate (produced by Nippon Kayaku Co., Ltd., trade name "Kayacure EPA"), 2,4-diethyl-9-sulfuronium, (Nippon Kayaku Co., Ltd., trade name "kayacure DETX", etc.), 2-methyl-1-[4-(methyl)phenyl]-2- Linoacetone-1 (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 907", etc.), 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 184", etc.), 2-dimethylamino-2-(4- 2-amino-2-benzyl-1-phenylalkane compounds such as 1-phenyl-2-oxo-1-phenylpropane, tetra(tert-butylperoxycarbonyl)benzophenone, diphenylethylenedione, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, aminobenzene derivatives such as 4,4-bisdiethylaminobenzophenone, imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (produced by Hodogaya Chemical Co., Ltd., trade name "B-CIM"), 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazol-1-one, Isohalogenated trimethylol Compound, 2-trichloromethyl-5-(2-benzofuran-2-yl-vinyl)-1,3,4- oxadiazole and other halogenated methyl A photosensitizer may be added as needed.

Examples of thermal radical polymerization initiators include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides (specifically, benzoyl peroxide, tert-butyl peroxy(2-ethylhexanoate), 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, tert-butyl peroxybenzoate, tert-butyl peroxide, and isopropylbenzene hydroperoxide). , diisophenylpropyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzyl peroxide, 1,4-bis(2-tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl peroxy(2-ethylhexanoate), etc.) and other organic peroxides.

The content (incorporation amount) of the curing catalyst in the curable composition of the present invention is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 1.0 parts by weight (e.g., 0.3 to 1.0 parts by weight), relative to 100 parts by weight of the total amount of the polyorganosilsesquioxane and other cationic curable compounds described below. By setting the curing catalyst content to 0.01 parts by weight or greater, the curing reaction proceeds efficiently and fully, tending to further improve the surface hardness and adhesion of the cured product. On the other hand, by setting the curing catalyst content to 3.0 parts by weight or less, the shelf life of the curable composition is further improved, or discoloration of the cured product is tended to be suppressed.

The curable composition of the present invention may further contain a cationic-curing compound other than the polyorganosilsesquioxane of the present invention (sometimes referred to as "other cationic-curing compound") and/or a radical-curing compound other than the polyorganosilsesquioxane of the present invention (sometimes referred to as "other radical-curing compound"). Other cationic-curing compounds can be used, including known or commonly used cationic-curing compounds other than the polyorganosilsesquioxane of the present invention, such as epoxy compounds, cyclobutane compounds, and vinyl ether compounds. Furthermore, in the curable composition of the present invention, the other cationic-curing compound may be used alone or in combination of two or more.

As the epoxy compound, any known or commonly used compound having one or more epoxy groups (ethylene oxide rings) in the molecule can be used without particular limitation. Examples thereof include aliphatic epoxy compounds (aliphatic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), and aliphatic epoxy compounds (aliphatic epoxy resins).

As the above-mentioned alicyclic epoxy compounds, there can be cited known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, without particular limitation. For example, there can be cited: (1) compounds having an epoxy group (referred to as "alicyclic epoxy group") formed by two adjacent carbon atoms and an oxygen atom constituting the alicyclic ring in the molecule; (2) compounds having an epoxy group directly bonded to the alicyclic ring via a single bond; (3) compounds having an alicyclic ring and an epoxypropyl ether group in the molecule (epoxypropyl ether type epoxy compound), etc.

Examples of the compound having an alicyclic oxy group in the molecule of the above-mentioned (1) include the compound represented by the following formula (i).

In formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a portion or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups formed by linking multiples of these groups.

Examples of the aforementioned divalent alkyl groups include linear or branched alkylene groups having 1 to 18 carbon atoms and divalent alicyclic alkyl groups. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of the aforementioned divalent alicyclic alkyl groups include divalent cycloalkylene groups (including cycloalkylene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylene.

Examples of the alkenylene group in the aforementioned alkenylene group in which a portion or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as an "epoxidized alkenylene group") include straight-chain or branched alkenylene groups having 2 to 8 carbon atoms, such as ethenylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, and octenylene. The epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

Representative examples of alicyclic epoxy compounds represented by formula (i) include (3,4,3',4'-bicyclooxy)bicyclohexane and compounds represented by formulas (i-1) to (i-10) below. Furthermore, in formulas (i-5) and (i-7) below, l and m each represent an integer from 1 to 30. In formula (i-5) below, R' represents an alkylene group having 1 to 8 carbon atoms, preferably a linear or branched alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group. In formulas (i-9) and (i-10) below, n1 to n6 each represent an integer from 1 to 30. Examples of the aliphatic epoxy compound represented by the above formula (i) include 2,2-bis(3,4-epoxyepoxyhexyl)propane, 1,2-bis(3,4-epoxyepoxyhexyl)ethane, 2,3-bis(3,4-epoxyepoxyhexyl)ethylene oxide, and bis(3,4-epoxyepoxyhexyl methyl)ether.

Examples of the compound (2) in which an epoxide group is directly bonded to the aliphatic ring via a single bond include the compound represented by the following formula (ii).

In formula (ii), R'' is a group (a p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol, and p and n each represent a natural number. Examples of the p-valent alcohol [R''(OH) _p ] include polyols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis(hydroxymethyl)-1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or greater, n in each group within (inside the parentheses) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol [e.g., trade name "EHPE3150" (manufactured by Daicel Co., Ltd.)].

Examples of the compound having alicyclic and glycidyl ether groups in the molecule of (3) above include glycidyl ethers of alicyclic alcohols (e.g. alicyclic polyols). More specifically, for example, compounds obtained by hydrogenating bisphenol A type epoxides such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxides); compounds obtained by hydrogenating bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane Compounds obtained by hydrogenating bisphenol F-type epoxides such as bis[3,5-dimethyl-4-(2,3-epoxypropoxy)epoxyhexyl]methane (hydrogenated bisphenol F-type epoxides); hydrogenated diphenol-type epoxides; hydrogenated phenol novolac-type epoxides; hydrogenated cresol novolac-type epoxides; hydrogenated cresol novolac-type epoxides of bisphenol A; hydrogenated naphthalene-type epoxides; hydrogenated epoxides of epoxides obtained from trisphenol methane; hydrogenated epoxides of the following aromatic epoxides, etc.

Examples of the aromatic epoxy compounds include: epi-bis-type epoxy resins obtained by the condensation reaction of diphenols and epihalogen alcohols; high molecular weight epi-bis-type epoxy resins obtained by further addition reaction of these epi-bis-type epoxy resins with the above-mentioned diphenols; and high molecular weight epi-bis-type epoxy resins obtained by further addition reaction of phenols with bisphenols. Novolac-alkyl type epoxy resins obtained by condensing aldehydes to obtain polyols, which are then condensed with epihalogen alcohols to obtain epoxy resins; epoxy compounds having two phenol skeletons bonded to the 9-position of the phenol ring and epoxypropyl groups bonded directly or via an alkoxy group to the oxygen atoms after removing the hydrogen atoms from the hydroxyl groups of the phenol skeletons.

Examples of the aforementioned aliphatic epoxy compounds include: epoxypropyl ethers of q-membered alcohols (q is a natural number) that do not have a cyclic structure; epoxypropyl esters of mono- or polycarboxylic acids; epoxides of oils and fats having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxides of polyolefins (including polydienes) such as epoxidized polybutadiene.

Examples of the aforementioned cyclohexane compounds include known or commonly used compounds having one or more cyclohexane rings in the molecule. Examples of the aforementioned vinyl ether compounds include known or commonly used compounds having one or more vinyl ether groups in the molecule.

As other radical-curing compounds, known or commonly used radical-curing compounds can be used without particular limitation. Examples include (meth)acrylic compounds other than the polyorganosilsesquioxane of the present invention. Examples of such (meth)acrylic compounds include known or commonly used compounds having one or more (meth)acrylic groups in the molecule.

The content (incorporation amount) of other cationic curing compounds and/or other radical curing compounds in the curable composition of the present invention is not particularly limited. However, relative to the total amount of the polyorganosilsesquioxane, other cationic curing compounds, and other radical curing compounds of the present invention (100 weight percent; the total amount of the cationic curing compounds and radical curing compounds), it is preferably 50 weight percent or less (e.g., 0-50 weight percent), more preferably 30 weight percent or less (e.g., 0-30 weight percent), and even more preferably 10 weight percent or less.

The curable composition of the present invention may further contain a polymerization stabilizer. A polymerization stabilizer is a compound that inhibits the progress of cationic polymerization by capturing cations. The cation-capturing capacity of the polymerization stabilizer is saturated, allowing polymerization to proceed during the deactivated phase. By including a polymerization stabilizer in the curable composition of the present invention, polymerization can be suppressed for a long period after coating and drying to form an adhesive layer. This allows heating at the desired adhesion point, resulting in an adhesive layer exhibiting excellent adhesion and maintaining excellent stability. When the curable composition of the present invention is a curable composition for adhesives, it preferably contains a polymerization stabilizer.

Examples of the polymerization stabilizer include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly([6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-trimethylol]- -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]), 1,2,3,4-butanetetracarboxylic acid tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, (mixed 2,2,6,6-tetramethyl-4-piperidinyl/tridecyl)-1,2,3, 4-Butane tetracarboxylate, 3,9-bis(2,3-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5.5]undecane, mixed (2,2,6,6-tetramethyl-4-piperidinyl/β,β,β',β'-tetramethyl-3-9-[2,4,8,10-tetraoxospiro[5.5]undecane]diethyl)-1,2,3,4-butane tetracarboxylate, poly([6-N- 1,3,5-triazine Hindered amine compounds such as [(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]propionamide, [N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)imino]propionamide, trade names "LA-77", "LA-67", "LA-57" (all manufactured by ADEKA Co., Ltd.), trade names "TINUVIN123", "TINUVIN152" (all manufactured by Ciba Japan Co., Ltd.); or (4-hydroxyphenyl)dimethylsulfonium methylsulfite (for example, trade name "San-Aid Copper sulfate compounds such as "SI Additive" (manufactured by San Hsin Chemical Industries, Ltd.) and phosphite compounds such as "Adekastab PEP-36" (manufactured by ADEKA Co., Ltd.) are preferred. Copper sulfate compounds and phosphite compounds are preferred because they are less likely to cause localized curing of the adhesive during drying, resulting in better adhesion of the cured product to the substrate.

The above-mentioned polymerization stabilizers may be used singly or in combination. In the curable adhesive composition of the present invention, it is particularly preferred to contain two or more polymerization stabilizers. This results in significantly improved storage stability of the curable adhesive composition, reduces the likelihood of localized curing of the adhesive during drying, and tends to further improve the adhesion of the cured product to the adherend. The two or more polymerization stabilizers preferably contain at least a cobalt sulfate compound and a phosphite compound.

When the curable composition of the present invention contains the aforementioned polymerization stabilizer, its content (incorporation amount) is not particularly limited. However, it is preferably 0.005 parts by weight or greater, more preferably 0.01 to 10 parts by weight, and even more preferably 0.02 to 1 part by weight, relative to 100 parts by weight of the polyorganosilsesquioxane of the present invention (or, if other cationic curing compounds are included, the total amount of the polyorganosilsesquioxane and other cationic curing compounds). A content of 0.005 parts by weight or greater reduces the likelihood of localized curing of the adhesive during drying, resulting in a tendency for the cured product to exhibit superior adhesion to the substrate. When two or more polymerization stabilizers are used, the total amount of the polymerization stabilizers is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the polyorganosilsesquioxane of the present invention (or the total amount of the polyorganosilsesquioxane and other cationic curable compounds when the polyorganosilsesquioxane contains other cationic curable compounds).

When the curable composition of the present invention contains the aforementioned polymerization stabilizer and a curing catalyst, the content (incorporation amount) of the polymerization stabilizer is not particularly limited. It is preferably 1 part by weight or greater, more preferably 3 to 200 parts by weight, and even more preferably 5 to 150 parts by weight, per 100 parts by weight of the curing catalyst. When the content is 1 part by weight or greater, localized curing of the adhesive during drying is less likely to occur, and the cured product tends to exhibit superior adhesion to the substrate. When two or more polymerization stabilizers are used, the total amount of the polymerization stabilizers is preferably 100 to 200 parts by weight, more preferably 110 to 150 parts by weight, per 100 parts by weight of the curing catalyst.

The curable composition of the present invention preferably further contains a solvent. Examples of the solvent include water and organic solvents. There are no particular limitations on the solvent as long as it can dissolve the polyorganosilsesquioxane of the present invention and any additives used as needed and does not inhibit polymerization.

The solvent is preferably one or more solvents having a boiling point (at 1 atmosphere) of 170°C or lower (e.g., toluene, butyl acetate, methyl isobutyl ketone, xylene, 1,3,5-trimethylbenzene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, etc.).

The solvent should be used in an appropriate amount depending on the intended use of the curable composition. The amount of solvent used is, for example, approximately 30-80% by weight, preferably 40-70% by weight, and even more preferably 50-60% by weight, based on the non-volatile content of the curable composition of the present invention. Excessive amounts of solvent can reduce the viscosity of the curable composition, making it difficult to form a film of appropriate thickness. On the other hand, insufficient amounts of solvent can increase the viscosity of the curable composition, making uniform coating difficult.

The curable composition of the present invention may further contain the following conventional additives as other optional components: inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, aluminum oxide, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, and boron nitride; inorganic fillers obtained by treating such fillers with organic silicon compounds such as halosilane, organic alkoxysilane, and organic silazane; organic resin fine powders such as polysiloxane, epoxy resin, and fluororesin; silver, copper, etc. Fillers such as conductive metal powder, hardening aids, stabilizers, flame retardants, flame retardant additives, reinforcing materials, nucleating agents, lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, transparent agents, rheology modifiers, processability modifiers, colorants, antistatic agents, dispersants, surface conditioners, surface modifiers, matting agents, defoamers, foam suppressants, antifoaming agents, antimicrobial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, and foaming agents. These additives may be used alone or in combination of two or more.

The curable composition of the present invention is not particularly limited and can be prepared by stirring and mixing the aforementioned components at room temperature or, if necessary, while heating. Furthermore, the curable composition of the present invention can be used as a single-liquid composition, where the components are pre-mixed and used directly, or as a multi-liquid (e.g., two-liquid) composition, where two or more components, stored separately, are mixed at a predetermined ratio before use.

The curable composition of the present invention is not particularly limited, but is preferably a liquid at room temperature (approximately 25°C). More specifically, the viscosity of the curable composition of the present invention, diluted to a 20% solvent (e.g., a curable composition (solution) containing 20% by weight of methyl isobutyl ketone), at 25°C is preferably 300 to 20,000 mPa·s, more preferably 500 to 10,000 mPa·s, and even more preferably 1,000 to 8,000 mPa·s. A viscosity of 300 mPa·s or greater tends to further improve the heat resistance of the cured product. On the other hand, setting the viscosity below 20,000 mPa·s makes the preparation and handling of the curable composition easier, and also reduces the likelihood of air bubbles remaining in the cured product. The viscosity of the curable composition of the present invention was measured using a viscometer (trade name "MCR301," manufactured by Anton Paar) at a swing angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25°C.

[Cured Product] The curable composition of the present invention can be cured by polymerizing the cationic curable compound or radical curable compound, thereby obtaining a cured product (sometimes referred to as the "cured product of the present invention"). The curing method can be appropriately selected from known methods and is not particularly limited. Examples include irradiation with active energy rays and/or heating. Examples of the active energy rays include infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, and γ-rays. Ultraviolet rays are preferred due to their superior workability.

The conditions for curing the curable composition of the present invention by irradiating it with active energy rays (active energy ray irradiation conditions, etc.) can be appropriately adjusted depending on the type and energy of the active energy rays irradiated, the shape and size of the cured product, and are not particularly limited. In the case of ultraviolet irradiation, for example, the irradiation intensity is preferably set to approximately 1 to 1000 mJ/ ^cm² . Furthermore, active energy ray irradiation can be performed using, for example, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arcs, metal halogen lamps, solar light, LED lamps, lasers, and the like. After irradiation with active energy rays, a heat treatment (annealing, aging) can be performed to further promote the curing reaction.

On the other hand, the conditions for curing the curable composition of the present invention by heating are not particularly limited, but are preferably 30 to 200° C., more preferably 50 to 190° C. The curing time can be appropriately set.

As described above, the curable composition of the present invention, upon curing, can form a cured product having high surface hardness and heat resistance, as well as excellent flex resistance and workability. Therefore, the curable composition of the present invention is suitable for use as a "hardcoat-forming curable composition" (sometimes referred to as a "hardcoat liquid" or "hardcoat agent") for forming a hardcoat layer in a hardcoat film, or as an adhesive for laminated semiconductors. Hardcoat films having a hardcoat layer formed using the curable composition of the present invention can maintain high hardness and heat resistance while maintaining flexibility, making them suitable for roll-to-roll production or processing. Furthermore, when the curable composition of the present invention is used as a curable adhesive composition, it can be cured at low temperatures, resulting in a cured product with excellent crack resistance, heat resistance, and adhesion and tightness to the adherend. Therefore, even when subjected to thermal shock, the adhesive layer will not crack or peel, resulting in a reliable device.

Furthermore, the curable composition of the present invention is applied to a release layer provided on a substrate and dried, resulting in an uncured or semi-cured hard coating layer with a non-stick surface and improved blocking resistance. This allows the hard coating to be rolled up for handling. Furthermore, by transferring this hard coating layer to the surface of a molded article and curing it, a hard coating layer with high surface hardness can be formed. Therefore, the curable composition of the present invention can also be suitably used as a hard coating composition for forming a hard coating layer with excellent flex resistance.

[Hard Coat] The hard coat of the present invention is composed of a substrate and a hard coat layer formed on at least one surface of the substrate. The hard coat layer is formed from the hardenable composition of the present invention (the hardenable composition for forming the hard coat) (the hardened layer of the hardenable composition of the present invention). Figure 9 is a schematic diagram (cross-sectional view) showing one embodiment of the hard coat of the present invention. Reference numeral 1 represents the hard coat, reference numeral 11 represents the hard coat layer, and reference numeral 12 represents the substrate.

Furthermore, the hard coating layer in the hard coating film of the present invention may be formed on only one surface (single surface) of the substrate or on both surfaces (double surfaces).

Furthermore, the hard coating layer in the hard coating film of the present invention may be formed on only a portion of each surface of the substrate or on the entire surface.

The substrate in the hard coat film of the present invention is the substrate of the hard coat film and refers to the portion other than the hard coat layer. Such substrates can be any known or commonly used substrate, including plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wooden substrates), and substrates with painted surfaces, without particular limitation. Among these, plastic substrates (substrates composed of plastic materials) are preferred.

The plastic material constituting the above-mentioned plastic substrate is not particularly limited, and examples thereof include: polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate; polyamide; polyacetal; polyphenylene ether; polyphenylene sulfide; polyether sulfone; polyether ether ketone; homopolymers of norbornene monomers (addition polymers or ring-opening polymers, etc.), copolymers of norbornene monomers and olefin monomers (cyclic olefins such as addition polymers or ring-opening polymers, etc.); Various plastic materials may be used, including cyclic polyolefins such as propylene glycol copolymers, and their derivatives; vinyl polymers (e.g., acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin)); vinylidene polymers (e.g., polyvinylidene chloride); cellulose resins such as triacetyl cellulose (TAC); epoxy resins; phenolic resins; melamine resins; urea resins; cis-butylene imide resins; and silicones. Furthermore, the plastic substrate may be composed of only one plastic material or two or more plastic materials.

Among them, when the purpose is to obtain a hard coating film with excellent transparency as the hard coating film of the present invention, it is preferred to use a substrate with excellent transparency (transparent substrate), and more preferably a polyester film (such as PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, or a PMMA film.

The plastic substrate may also contain other additives, such as antioxidants, UV absorbers, light stabilizers, heat stabilizers, crystallization nucleating agents, flame retardants, flame retardant additives, fillers, plasticizers, impact resistance improvers, reinforcing agents, dispersants, antistatic agents, foaming agents, and antimicrobial agents, as needed. These additives may be used singly or in combination.

The plastic substrate may have a single layer or a multilayer (laminated) structure, and its composition (structure) is not particularly limited. For example, the plastic substrate may have a layer other than the hard coat layer of the present invention formed on at least one surface of the plastic film (sometimes referred to as an "other layer"), i.e., a laminated structure such as "plastic film/other layer" or "other layer/plastic film/other layer." Examples of the other layer include hard coat layers other than the hard coat layer of the present invention. Furthermore, examples of the materials comprising the other layer include the aforementioned plastic materials.

The surface of the plastic substrate may be partially or entirely roughened, treated for adhesion, treated with an antistatic agent, sandblasted (sand matt treated), treated with a corona discharge treatment, treated with a plasma treatment, treated with a chemical etching treatment, treated with a water matt, flame treated, treated with an acid, treated with an alkali, oxidized, treated with ultraviolet light, or treated with a silane coupling agent, among other known or commonly used surface treatments. Furthermore, the plastic substrate may be either an unstretched film or a stretched film.

The plastic substrate can be manufactured by, for example, the following known or commonly used methods: forming the plastic material into a film to form a plastic substrate (plastic film); optionally forming appropriate layers (such as the aforementioned other layers) on the plastic film; or performing appropriate surface treatment on the plastic film. Commercially available plastic substrates may also be used.

The thickness of the substrate is not particularly limited and can be appropriately selected from the range of 0.01 to 10000 μm, for example.

The hard coat layer of the hard coat film of the present invention constitutes at least one surface layer of the hard coat film of the present invention. This layer (cured material layer) is formed by a curing material (cured resin material) obtained by curing the curable composition of the present invention (curable composition for forming the hard coat layer).

The thickness of the hard coat layer of the present invention (the thickness of each hard coat layer when the hard coat layer is provided on both surfaces of the substrate) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Even when the hard coat layer of the present invention is thin (e.g., 5 μm or less), it can maintain a high surface hardness (e.g., a pencil hardness of 3H or higher). Furthermore, even when the hard coat layer of the present invention is thick (e.g., 50 μm or greater), it is less susceptible to problems such as cracking caused by curing shrinkage. Therefore, by thickening the film, pencil hardness can be significantly improved (e.g., a pencil hardness of 9H or higher).

The haze of the hard coat layer is not particularly limited; however, at a thickness of 50 μm, it is preferably 1.5% or less, and more preferably 1.0% or less. Furthermore, the lower limit of the haze is not particularly limited, but may be, for example, 0.1%. By setting the haze to 1.0% or less, the hard coat layer may be suitable for applications requiring very high transparency, such as surface protection sheets for touch panels and other displays. The haze of the hard coat layer of the present invention can be measured in accordance with JIS K7136.

The total light transmittance of the hard coat layer is not particularly limited; however, at a thickness of 50 μm, it is preferably 85% or greater, and more preferably 90% or greater. Furthermore, the upper limit of the total light transmittance is not particularly limited, and may be, for example, 99%. A total light transmittance of 85% or greater may be suitable for applications requiring extremely high transparency, such as surface protection sheets for touch panels and other displays. The total light transmittance of the hard coat layer of the present invention can be measured in accordance with JIS K7361-1.

The hard coat film of the present invention may also have a surface protective film on its surface. This tends to further improve the hard coat film's punching processability. With this surface protective film, even if the hard coat layer is very hard and prone to peeling or cracking from the substrate during punching, this problem can be eliminated, allowing punching using a Thomson blade. The surface protective film can be any known or commonly used surface protective film.

The hard coat film of the present invention can be produced according to known or commonly used hard coat film production methods, and the production method is not particularly limited. For example, the hard coat film can be produced by applying the hardenable composition of the present invention (hardenable composition for forming a hard coat layer) to at least one surface of the substrate, optionally removing the solvent by drying, and then curing the hardenable composition (hardenable composition layer). The conditions for curing the hardenable composition are not particularly limited and can be appropriately selected from the conditions for forming the hardened material described above.

Because the hard coat layer of the hard coat film of the present invention is formed from the hardening composition of the present invention (hard coat layer-forming hardening composition) capable of forming a cured product with excellent flex resistance and workability, the hard coat film of the present invention can be manufactured using a roll-to-roll process. By using a roll-to-roll process to manufacture the hard coat film of the present invention, its productivity can be significantly improved. As a method for producing the hard coating film of the present invention in a roll-to-roll manner, a well-known or commonly used roll-to-roll manufacturing method can be adopted without particular limitation. For example, a method including the following steps (steps A to C) as necessary steps and performing these steps (steps A to C) continuously can be cited: step A, unwinding the rolled substrate; step B. Applying the hardenable composition of the present invention (hardenable composition for forming a hard coat layer) to at least one surface of the unrolled substrate. Subsequently, the solvent is optionally removed by drying, and the hardenable composition (hardenable composition layer) is cured to form the hard coat layer of the present invention. And C. The resulting hard coat film is then rewound into a roll. Furthermore, the method may include steps other than steps A-C.

The thickness of the hard coating film of the present invention is not particularly limited and can be appropriately selected from the range of 1 to 10,000 μm.

The pencil hardness of the hard coating layer of the hard coating film of the present invention is preferably 4H or higher, more preferably 5H or higher, and even more preferably 6H or higher. Furthermore, pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

The haze of the hard coat film of the present invention is not particularly limited, but is preferably 1.5% or less, and more preferably 1.0% or less. Furthermore, the lower limit of the haze is not particularly limited, but is, for example, 0.1%. By setting the haze to 1.0% or less, the hard coat film tends to be suitable for applications requiring very high transparency, such as surface protection sheets for touch panels and other displays. The haze of the hard coat film of the present invention can be easily controlled within the above range by using the aforementioned transparent substrate as the substrate. Furthermore, the haze can be measured in accordance with JIS K7136.

The total light transmittance of the hard coat film of the present invention is not particularly limited, but is preferably 85% or greater, and more preferably 90% or greater. Furthermore, the upper limit of the total light transmittance is not particularly limited, and may be, for example, 99%. By setting the total light transmittance to 90% or greater, it tends to be suitable for applications requiring very high transparency, such as surface protective sheets for displays such as touch panels. The total light transmittance of the hard coat film of the present invention can be easily controlled within the above range, for example, by using the above-mentioned transparent substrate as the substrate. Furthermore, the total light transmittance can be measured in accordance with JIS K7361-1.

The hard coat film of the present invention maintains high hardness and heat resistance while remaining flexible, enabling roll-to-roll manufacturing or processing. This results in high quality and excellent productivity. When a surface protective film is applied to the surface of the hard coat layer of the present invention, punching processability is also excellent. Therefore, it is ideally suited for all applications requiring these properties. For example, the hard coat film of the present invention can be used as a surface protective film for various products, as a surface protective film for components or parts of various products, and as a component material for various products or their components or parts. Examples of these products include: display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; various home appliances; various electrical and electronic products; various electrical and electronic products such as portable electronic terminals (e.g., game consoles, personal computers, tablets, smartphones, mobile phones); and various optical devices. Furthermore, examples of using the hard coat film of the present invention as a component material for various products or their components or parts include a laminate of a hard coat film and a transparent conductive film for use in touch panels.

[Transfer Film] The transfer film (transfer hard coat film) of the present invention comprises a substrate and an uncured or semi-cured hard coat layer formed on a release layer formed on at least one surface of the substrate. The uncured or semi-cured hard coat layer comprises the curable composition of the present invention (curable composition for forming a hard coat layer (hereinafter sometimes referred to as the "hard coat of the present invention"). Here, "uncured" refers to a state in which the polymerizable functional groups of the polyorganosilsesquioxane of the present invention contained in the curable composition for forming a hard coat layer (hard coat) of the present invention have not yet undergone polymerization. "Semi-cured" refers to a state in which a portion of the polymerizable functional groups have undergone polymerization. A state in which a polymerization reaction has occurred and unreacted polymerizable functional groups remain. Furthermore, in this specification, an uncured or semi-cured hard coat layer formed from the curable composition (hard coat) of the present invention is sometimes referred to simply as a "hard coat layer," while a hard coat layer transferred to a molded article and cured is referred to as a "cured hard coat layer." Figure 10 is a schematic diagram (cross-sectional view) showing one embodiment of the transfer film of the present invention. Reference numeral 2 denotes a transfer film, reference numeral 21 denotes a substrate, reference numeral 22 denotes a release layer, reference numeral 23 denotes a hard coat layer (uncured or semi-cured hard coat layer), reference numeral 24 denotes an adhesion promoter layer, reference numeral 25 denotes a coloring layer, and reference numeral 26 denotes an adhesive layer.

The substrate in the transfer film of the present invention is the base material of the transfer film and refers to the portion of the film other than the transfer layer comprising the hard coat layer of the present invention. Herein, the transfer layer refers to the layer of the transfer film of the present invention other than the base material on which the release layer is formed and refers to the portion that is transferred to the surface of the molded article.

The substrate mentioned above for the hard coat film can be used, with plastic substrates (plastic films) being particularly preferred. The thickness of the substrate can be appropriately selected from the range of 0.01 to 10,000 μm, with a preferred thickness of 2 to 250 μm, more preferably 5 to 100 μm, and even more preferably 20 to 100 μm, based on considerations such as formability, shape conformability, and operability.

The release layer in the transfer film of this invention forms at least one surface layer of the substrate in the transfer film and is provided to facilitate the release of the transfer layer from the substrate. The release layer ensures reliable and easy transfer of the transfer layer from the transfer film to the transfer target (molded article), allowing for reliable release of the substrate.

In the transfer film of the present invention, the peel strength between the release layer and the hard coat layer is not particularly limited, but is preferably 30 to 500 mN/24 mm, more preferably 40 to 300 mN/24 mm, and even more preferably 50 to 200 mN/24 mm. By maintaining the peel strength within this range, the hard coat layer does not peel during normal handling, and tends to be easily peeled during transfer to a molded article. The peel strength of the hard coat layer and the release layer of the present invention can be measured in accordance with JIS Z0237.

Furthermore, the release layer in the transfer film of the present invention may be formed on only one surface (single side) or both surfaces (double sides) of the substrate. Furthermore, the release layer in the transfer film of the present invention may be formed on only a portion of each surface of the substrate or on the entire surface.

As a component forming the release layer, a publicly known release agent can be used without particular limitation. For example, at least one selected from unsaturated ester resins, epoxy resins, epoxy-melamine resins, aminoalkyd resins, acrylic resins, melamine resins, silicone resins, fluororesins, cellulose resins, urea resins, polyolefin resins, wax resins, and cycloolefin resins can be used. From the perspective of the releasability of the hard coating layer of the present invention and the release layer in contact therewith in the transfer layer, the release layer is preferably a melamine-based resin or a cycloolefin-based resin, and more preferably a cycloolefin copolymer resin (COC resin) such as a 2-norbornene-ethylene copolymer.

The release layer can be formed on the substrate surface using any known release treatment method without particular limitation. For example, the aforementioned resin can be dispersed or dissolved in a solvent (e.g., alcohols such as methanol and butanol, aromatic hydrocarbons such as toluene and xylene, tetrahydrofuran, etc.), applied using a known coating method such as rod coating, Mayer bar coating, gravure coating, or roll coating, dried, and heated at 80-200°C to form the release layer. The thickness of the release layer is also not particularly limited, but can generally be selected from a range of 0.01-5 μm, preferably 0.1-3.0 μm.

The hard coat layer in the transfer film of the present invention constitutes at least one surface layer of the release layer and is an uncured layer obtained by drying the curable composition (hard coat) of the present invention, or a semi-cured layer obtained by partial curing. The semi-cured hard coat layer can be formed by irradiating the uncured hard coat layer with the aforementioned active energy rays or heating it to partially cure it. The uncured or semi-cured hard coat layer of the present invention has low viscosity, preventing the resin from sticking to the surface when touched by fingers, and has excellent anti-blocking properties, allowing it to be rolled up for easy handling.

Furthermore, the hard coating layer in the transfer film of the present invention may be formed on only one release layer (one side) of the substrate, or on both release layers (both sides). Furthermore, the hard coating layer in the transfer film of the present invention may be formed on only a portion of each surface of the release layer, or on the entire surface.

The method for depositing the hard coating layer on the release layer of the transfer film of the present invention is not particularly limited. Examples of such methods include coating the curable composition (hard coating agent) of the present invention on the release layer using a known method and drying the hard coating layer to form an uncured hard coating layer; or further irradiating the uncured hard coating layer with active energy rays or heating the hard coating layer to form a semi-cured hard coating layer. The curable composition (hard coat) of the present invention can be applied using any known coating method, including, without limitation, rod coater coating, Mayer bar coating, air knife coating, gravure coating, offset printing, flexographic printing, and screen printing. The heating temperature for forming the hard coat is not particularly limited but can be suitably selected from 50 to 200°C. The heating time is also not particularly limited but can be suitably selected from 1 to 60 minutes. The conditions for irradiating the hard coat with active energy rays are not particularly limited and can be suitably selected from the conditions for forming the cured product described above.

The thickness of the hard coat layer in the transfer film of the present invention (when a hard coat layer is provided on both sides of the substrate, the thickness of each hard coat layer) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 150 μm. Even with a thin hard coat layer (e.g., 5 μm or less), high surface hardness (e.g., a pencil hardness of 5H or higher) can be maintained. Furthermore, even with a thicker hard coat layer (e.g., 50 μm or greater), problems such as cracking caused by curing shrinkage are less likely to occur. Therefore, thicker films can significantly increase pencil hardness (e.g., a pencil hardness of 9H or higher).

The haze of the hard coat layer in the transfer film of the present invention is not particularly limited. At a thickness of 50 μm, it is preferably 1.5% or less, and more preferably 1.0% or less. Furthermore, the lower limit of the haze is not particularly limited, but is, for example, 0.1%. A haze of 1.0% or less is preferred, as it allows for clear transfer of patterns and designs, for example, when the transfer film of the present invention is used as a decorative film. The haze of the hard coat layer of the present invention can be measured in accordance with JIS K7136.

The total light transmittance of the hard coat layer in the transfer film of the present invention is not particularly limited. At a thickness of 50 μm, it is preferably 85% or greater, and more preferably 90% or greater. Furthermore, the upper limit of the total light transmittance is not particularly limited, but may be 99% for example. A total light transmittance of 85% or greater is preferred, for example, when the transfer film of the present invention is used as a decorative film, as it enables clear transfer of patterns and designs. The total light transmittance of the hard coat layer of the present invention can be measured in accordance with JIS K7361-1.

The transfer film of the present invention preferably has an adhesion-promoting coating layer and an adhesive layer sequentially deposited on a hard coat layer. Furthermore, when the transfer film of the present invention is used as a decorative film, at least one coloring layer is deposited. While the location of the coloring layer is not particularly limited, it is preferably deposited as one or two or more layers between the adhesion-promoting coating layer and the adhesive layer.

The adhesion-enhancing coating layer in the transfer film of the present invention is provided to enhance the adhesion between the hard coating layer and the adhesive layer or the coloring layer. The adhesion-enhancing coating layer is preferably a transparent or translucent layer so that the patterns and designs of the coloring layer can be transferred clearly. Phenolic resins, alkyd resins, melamine resins (such as methylated melamine resins, butylated melamine resins, methylated melamine resins, butylated melamine resins, methylbutyl mixed etherified melamine resins, etc.), epoxy resins (such as bisphenol A epoxy resins, bisphenol F epoxy resins, multifunctional epoxy resins) can be used. Resins, flexible epoxy resins, brominated epoxy resins, epoxy propyl type epoxy resins, high molecular weight epoxy resins, biphenyl type epoxy resins, etc.), urea resins, unsaturated polyester resins, urethane resins [for example, polyisocyanate compounds (O=C=NRN=C=O) with two or more isocyanate groups and polyol compounds (HO-R'-OH) with two or more hydroxyl groups, polyamines (H ₂ N-R''-NH ₂ ), or water and compounds having active hydrogen (-NH ₂ , -NH, -CONH-, etc.)], thermosetting resins such as thermosetting polyimide and polysilicone resins; or thermoplastic resins such as vinyl chloride-vinyl acetate copolymer resins, acrylic resins (such as acrylic polyol resins), chlorinated rubber, polyamide resins, nitrocellulose resins, cyclic polyolefin resins, etc., either alone or as a mixture of two or more thereof, preferably epoxy resins.

The above-mentioned adhesion-enhancing coating resin may further contain conventional additives such as wax, silica, plasticizer, leveling agent, surfactant, dispersant, defoaming agent, UV absorber, UV stabilizer, antioxidant, etc. as other optional ingredients within a range that does not impair the effectiveness of the present invention. These additives may be used alone or in combination of two or more.

The tackifying coating layer can be formed by applying a coating solution obtained by dissolving the above-mentioned resin in a solvent onto the hard coating layer of the present invention using a known coating method such as rod coating, Mayer bar coating, gravure coating, or roller coating, followed by drying and, if necessary, heating. The temperature for heating the tackifying coating layer is not particularly limited, but is preferably selected from 50 to 200°C. The heating time is also not particularly limited, but is preferably selected from 10 seconds to 60 minutes.

The thickness of the adhesion-promoting coating is usually around 0.1 to 20 μm, preferably in the range of 0.5 to 5 μm.

The adhesion-enhancing coating of the present invention can be formed using a commercially available adhesion-enhancing coating agent. Examples of commercially available adhesion-enhancing coating agents include K468HP Anchor (an epoxy resin-based adhesion-enhancing coating agent manufactured by Toyo Ink Co., Ltd.) and TM-VMAC (an acrylic polyol resin-based adhesion-enhancing coating agent manufactured by Dainichi Seika Co., Ltd.).

The adhesive layer in the transfer film of the present invention is used to ensure good adhesion between the transfer layer (including the hard coat layer, the optional adhesion-promoting coat layer, and the coloring layer) and the molded article. Examples of adhesive layers include those composed of heat-sensitive adhesives and pressurized adhesives. In the present invention, a heat sealant layer is preferred, which can achieve close adhesion to the molded article by applying heat and pressure, as required. As the resin used for the adhesive layer, for example, acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, polyester resin, polyamide resin, etc. can be used alone or as a mixture of two or more resins. Acrylic resin and vinyl chloride-vinyl acetate copolymer are preferred.

Examples of acrylic resins used in the adhesive layer of the present invention include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymers, and methyl (meth)acrylate-styrene copolymers. Modified acrylic resins modified with fluorine or the like may be used alone or as a mixture of two or more. Furthermore, acrylic polyol esters obtained by copolymerizing alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate with (meth)acrylates having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate may also be used. As the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of approximately 5 to 20% by mass and an average degree of polymerization of approximately 350 to 900 are generally used. Optionally, the vinyl chloride-vinyl acetate copolymer resin may be further copolymerized with a carboxylic acid such as maleic acid or fumaric acid. Furthermore, as auxiliary resin components, other resins, such as thermoplastic polyester resins, thermoplastic urethane resins, and chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene, may be appropriately blended as needed.

The adhesive layer can be formed by applying a solution or emulsion of one or more of the above-mentioned resins in a coatable form using a known coating method such as rod coating, Mayer bar coating, gravure coating, or roll coating, followed by drying and, if necessary, heating. The heating temperature for forming the adhesive layer is preferably selected from 50 to 200°C. The heating time is preferably selected from 10 seconds to 60 minutes.

In order to ensure good adhesion of the transfer film and efficient transfer to the molded article, the thickness of the adhesive layer is preferably about 0.1 to 10 μm, more preferably 0.5 to 5 μm.

The adhesive layer may contain organic UV absorbers such as benzophenone compounds, benzotriazole compounds, oxanilide compounds, cyanoacrylate compounds, and salicylate compounds; or inorganic UV-absorbing microparticle additives such as oxides of zinc, titanium, arsenic, tin, and iron. Additionally, additives such as coloring pigments, white pigments, textured pigments, fillers, antistatic agents, antioxidants, and fluorescent whitening agents may be used as needed.

Commercially available adhesives may also be used. Examples of commercially available adhesives include K588HP Adhesive Gloss A Varnish (a vinyl chloride-vinyl acetate copolymer adhesive manufactured by Toyo Ink Co., Ltd.) and PSHP780 (an acrylic resin adhesive manufactured by Toyo Ink Co., Ltd.).

The coloring layer in the transfer film of this invention is applied when creating a decorative film used to transfer a pattern layer and/or concealing layer to a molded article. Here, the pattern layer is used to express patterns, text, and other graphic designs, while the concealing layer is typically a solid layer used to mask the coloring of injection molding resins. The concealing layer is sometimes placed inside the pattern layer to highlight the pattern layer's design, and sometimes the decorative layer consists solely of the concealing layer.

The pattern layer of the present invention is provided for displaying patterns, text, and other graphic designs. The pattern layer can be any pattern, for example, patterns consisting of wood grain, stone grain, cloth grain, grain pattern, geometric patterns, text, etc.

The coloring layer is typically formed by printing ink onto the hardcoat or adhesion-enhancing layer using known printing methods such as gravure printing, offset printing, screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and inkjet printing. This layer can be formed between the hardcoat and adhesive layer, or between the adhesion-enhancing layer and adhesive layer. The thickness of the coloring layer is preferably 3-40 μm, more preferably 10-30 μm, based on design considerations.

Preferred binder resins for printing inks used to form the color layer include polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins. Preferred binders are those containing only acrylic resins as the main component, or mixtures of acrylic resins and vinyl chloride-vinyl acetate copolymer resins as the main component. Among these, blends of acrylic resins, vinyl chloride-vinyl acetate copolymer resins, and other acrylic resins are preferred because they offer improved printability and molding properties. Examples of acrylic resins include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymers, methyl (meth)acrylate-styrene copolymers, and modified acrylic resins modified with fluorine or the like. These resins may be used alone or as a mixture of two or more. Furthermore, acrylic polyol esters obtained by copolymerizing alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate with (meth)acrylates having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate may also be used. Furthermore, vinyl chloride-vinyl acetate copolymer resins generally have a vinyl acetate content of approximately 5-20% by mass and an average degree of polymerization of approximately 350-900. Optionally, vinyl chloride-vinyl acetate copolymer resins may be further copolymerized with carboxylic acids such as maleic acid and fumaric acid. The mixing ratio of acrylic resin to vinyl chloride-vinyl acetate copolymer resin is approximately 1/9 to 9/1 (mass ratio): acrylic resin/vinyl chloride-vinyl acetate copolymer resin. Furthermore, other resins may be mixed as auxiliary resins, such as thermoplastic polyester resins, thermoplastic urethane resins, and chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene.

As the coloring agent used for the coloring layer, metallic pigments can be used, which are composed of scaly foil powder of metals, alloys, or metal compounds such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, and brass; and pigments composed of mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, alkaline Pearlescent pigments made from lead carbonate and other foil powders; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, and calcium sulfide; white inorganic pigments such as titanium dioxide, zinc white, and antimony trioxide; inorganic pigments such as zinc white, red lead, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, and carbon black; and organic pigments (including dyes) such as isoindolinone yellow, Hansa Yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and aniline black, one or a mixture of two or more.

This coloring layer is used to add design to the transfer film of the present invention. To enhance design, a metal thin film layer may also be formed. Metal thin films can be formed using methods such as vacuum evaporation and sputtering using aluminum, chromium, gold, silver, and copper. The metal thin film layer can be applied across the entire surface or partially patterned.

In addition to the above ingredients, printing inks used to form the coloring layer may also contain appropriate additives such as anti-precipitants, curing catalysts, UV absorbers, antioxidants, leveling agents, thickeners, defoamers, and lubricants. Printing inks can be provided by dissolving or dispersing the above ingredients in a common solvent. Any solvent capable of dissolving or dispersing the binder resin can be used, and organic solvents and/or water can be used. Examples of organic solvents include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, celluloic acid, and butyl celluloic acid acetate, and alcohols.

The transfer film of the present invention is laminated with the aforementioned substrate, release layer, hard coat layer, adhesion promoter layer, adhesive layer, and coloring layer, and optionally further laminated with a low-reflection layer, antistatic layer, ultraviolet absorption layer, near-infrared blocking layer, and electromagnetic wave absorption layer in any order.

The thickness of the transfer film of the present invention is not particularly limited and can be appropriately selected from the range of 1 to 10,000 μm. Based on the viewpoints of formability, shape tracking, and operability, it is preferably 2 to 250 μm, more preferably 5 to 150 μm, and even more preferably 25 to 150 μm.

The hard coating layer of the transfer film of the present invention is non-sticky and has excellent adhesion resistance, allowing it to be rolled up for handling, making it suitable for use as a transfer film for in-mold injection molding. For example, within a mold consisting of a fixed mold and a movable mold, the transfer film of the present invention is continuously transported using a conveyor roller, etc., so that the substrate film side contacts the fixed mold surface. After appropriately adjusting the position, the movable mold is moved to lock the mold. Then, a pre-molded thermoplastic resin is injected from the transfer layer side of the transfer film under high temperature and high pressure to fill the mold. After rapid cooling, the mold is opened, and the molded product (in-mold molded product) with the hard coating layer of the present invention transferred to the outermost surface can be removed.

If the hard coat layer of the molded article of the present invention is uncured or semi-cured, the hard coat layer can be cured by irradiating the hard coat layer with active energy rays and/or heating the hard coat layer. The conditions for irradiating the hard coat layer with active energy rays and/or heating the hard coat layer are not particularly limited and can be appropriately selected from the conditions for forming a cured article described above.

After the transfer layer of the transfer film of the present invention is transferred to a molded article, a hardened hardcoat of the present invention is formed on the outermost surface of the molded article. This allows the surface of the molded article to have a very high pencil hardness, preferably 5H or higher, more preferably 6H or higher. Pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

Molded articles (in-mold molded articles) produced using the transfer film of this invention via in-mold injection molding exhibit exceptionally high surface hardness, allowing for vivid transfer of designs and patterns. This makes it ideal for all molded articles requiring these properties. For example, the transfer film of this invention is suitable for various exterior molded articles requiring high surface hardness, scratch resistance, design, and durability, such as automotive dashboards and other interior and exterior trims, and home appliance housings.

[Adhesive Sheet] Using the curable composition of the present invention (curable composition for adhesive, curable composition for laminated semiconductors) yields an adhesive sheet having an adhesive layer formed from the curable composition of the present invention on at least one side of a substrate. Figure 11 is a schematic diagram (cross-sectional view) of one embodiment of the adhesive sheet of the present invention. Reference numeral 3 represents the adhesive sheet, reference numeral 31 represents the adhesive layer, reference numeral 32 represents the substrate, and reference numeral 33 represents the adhesion-promoting coating layer.

The aforementioned adhesive sheet can be obtained, for example, by applying the curable composition of the present invention (curable composition for adhesives, curable composition for laminated semiconductors) to a substrate and then drying it as needed. The coating method is not particularly limited, and conventional methods can be used. Furthermore, the drying method and conditions are not particularly limited; the conditions can be set to remove volatile components such as solvents as much as possible, and conventional methods can be used. When the curable composition of the present invention contains a polymerization initiator whose curing time at 130°C is 3.5 minutes or longer when 1 part by weight of Celloxide 2021P (manufactured by Daicel Co., Ltd.) is added to 100 parts by weight, heat drying can suppress the progress of the curing reaction and rapidly remove volatile components such as solvents, thereby forming an adhesive layer. The adhesive layer thus obtained has the following characteristics: it has no adhesive properties below 50°C, exhibits adhesive properties by heating to a temperature that can suppress damage to electronic components such as semiconductor chips, and then rapidly cures. The above-mentioned adhesive sheet includes not only sheets but also sheet-like forms such as films, tapes, and plates.

The adhesive sheet may be a single-sided adhesive sheet having an adhesive layer on only one side of the substrate, or a double-sided adhesive sheet having adhesive layers on both sides of the substrate. In the case of a double-sided adhesive sheet, at least one adhesive layer may be an adhesive layer formed from the curable composition of the present invention; the other adhesive layer may be the aforementioned adhesive layer or an adhesive layer other than the aforementioned adhesive layer (an additional adhesive layer).

The substrate used in the adhesive sheet of the present invention can be any commonly used substrate (substrate used for adhesive sheets) without particular limitation. Examples include plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates, and substrates with painted surfaces. Furthermore, the substrate used in the adhesive sheet of the present invention can be a so-called peelable liner. Furthermore, the adhesive sheet of the present invention can have only one substrate layer or two or more layers. The thickness of the substrate is not particularly limited and can be appropriately selected from a range of 1 to 10,000 μm, for example.

The adhesive sheet may have only one adhesive layer formed from the curable composition of the present invention, or may have two or more adhesive layers. The thickness of the adhesive layer in the adhesive sheet is not particularly limited and can be appropriately selected, for example, from a range of 0.1 to 10,000 μm.

Another aspect of the aforementioned adhesive sheet is the use of a silane coupling agent and the polyorganosilsesquioxane of the present invention to achieve an adhesive sheet with excellent crack resistance, heat resistance, and excellent adhesion and tightness to the substrate. Specifically, the adhesive sheet comprises an adhesion-promoting coating layer containing a silane coupling agent and an adhesive layer formed from a curable composition containing the polyorganosilsesquioxane of the present invention on at least one side of a substrate, with the adhesive layer disposed on the surface of the adhesion-promoting coating. The adhesive sheet exhibits excellent crack resistance, heat resistance, and excellent adhesion and tightness to the substrate.

In another embodiment of the adhesive sheet, the adhesive sheet may have only one layer of the above-mentioned adhesion-promoting coating layer, or may have two or more layers of the adhesion-promoting coating layer. The thickness of the adhesion-promoting coating layer may be appropriately selected from the range of 0.001 to 10,000 μm, for example.

The adhesive sheet may also have other layers (such as an intermediate layer, a primer layer, etc.) in addition to the base material, the adhesive layer, and the adhesion-promoting coating layer.

By using the aforementioned bonding sheet, a laminate can be obtained in which a bonded layer (bond) is attached to an adhesive layer of the bonding sheet. Furthermore, when the laminate obtained using the aforementioned bonding sheet is a three-dimensional laminate of semiconductor chips, it is more highly integrated and more energy-efficient than conventional semiconductors. Therefore, the use of this laminate can increase packaging density and provide smaller, higher-performance electronic devices.

The various aspects disclosed in this specification may be combined with any other features disclosed in this specification. The various components and their combinations in the various embodiments are merely examples, and additions, omissions, substitutions, and other modifications may be made as appropriate without departing from the spirit of the present invention. The present invention is limited only by the scope of the patent application and not by the embodiments. [Examples]

The present invention is described in more detail below based on embodiments, but the present invention is not limited to these embodiments.

The number average molecular weight and molecular weight dispersion of the product were determined using the following GPC conditions. The content of monomeric cage-type silsesquioxane and condensed silsesquioxane in the product was determined based on the area ratio of the corresponding peaks in the GPC measurement. Furthermore, the ratio of the T2 isomer to the T3 isomer [T3 isomer/T2 isomer] in the product was determined using ²⁹ Si-NMR spectroscopy using a Brucker NMR (600 MHz).

[GPC Conditions] Measurement Apparatus: Trade Name "GPC Semi-Micro System" (Shimadzu Corporation) Detector: RI Detector (Shoko Scientific Co., Ltd.) Columns: KF-G4A (guard column), KF-602, and KF-603 (Shoko Scientific Co., Ltd.) Flow Rate: 0.6 mL/min Measurement Temperature: 40°C Measurement Time: 13 min Injection Volume: 20 μL Eluent: THF, Sample Concentration: 0.1-0.2 wt% Molecular Weight: Standard Polystyrene Equivalent

UPLC-MS was performed using the following apparatus and conditions. [UPLC Conditions] Analyzer: ACQUITY UPLC H-Class (Waters Corporation) Detector and Detection Conditions: MS conditions described below Column: ACQUITY UPLC HSS PFP 2.1 × 100 mm × 1.8 μm Mobile Phase A: 5 mM Ammonium Formate in Water Mobile Phase B: Acetonitrile/THF = 6/4 Washing Solvent: Acetonitrile/THF = 6/4 Flow Rate: 0.35 mL/min Sample Temperature: 10°C Column Temperature: 40°C Injection Volume: 2.0 μL

[MS Conditions] Measurement Apparatus: Xevo-G2XS QTOFMS (Waters Corporation) Ionization Mode: ESI+ (Sensitivity Mode) Measurement Method: MS Capillary Voltage: 3.2 kV Conical Voltage: 30 V Source Compensation Voltage: 80 V Desolvent Gas: 1000 L/hr (200°C) Conical Gas: 50 L/hr Ion Source Heater: 80°C Scan Range: m/z = 100–3000 Scan Time: 0.4 sec Collision Energy: 30–50 eV (MSE High Energy) Target Mass: Leucine Enkephalin

Example 1 : Preparation of the epoxy-containing polyorganosilsesquioxane of the present invention ( 1 ) In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a Dean-Stark tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were added under a nitrogen flow, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g (2.8 mmol as potassium carbonate) of a 5% aqueous solution was added over a period of 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over a period of 20 minutes. During the addition, the temperature was not allowed to rise significantly. The polycondensation reaction was then carried out for 5 hours, maintained at 50°C, under a nitrogen stream. 230.5 g of methyl isobutyl ketone was then added, and the temperature was raised from 50°C to 90°C under reduced pressure. Distillation was performed to remove acetone (0.0%), methyl isobutyl ketone (30.32%), and water (0.23%) from the system. The temperature was then maintained at 90°C with stirring for 11 hours. 273.2 g of methyl isobutyl ketone was then added, and the mixture was washed five times with 273.2 g of water until the conductivity was below 1.5 μS/cm. The mixture was then concentrated to obtain 61.1 g of a colorless, transparent liquid. Analysis of the product revealed a number-average molecular weight of 4736, a molecular weight dispersity of 2.54, a monomeric cage-type silsesquioxane content of 6.7% (retention time 7.6-8.3 minutes), a condensed cage-type silsesquioxane content of 93.3% (retention time 4.9-7.6 minutes), and a [T3 isomer/T2 isomer] ratio of 46.5. The ²⁹ Si-NMR spectrum is shown in Figure 1, and the GPC chart is shown in Figure 2.

The epoxy-containing polyorganosilsesquioxane obtained in Example 1 was analyzed using the aforementioned UPLC-MS conditions. The MS spectra detected at retention times of 3.86 minutes and 1.81 minutes are shown in Figures 3 and 4, respectively. According to the comparison of the MS simulation diagram of the molecular formula C ₁₄₄ H ₂₃₄ O ₄₅ Si ₁₈ (Z＝2) shown in FIG5 and the MS simulation diagram of the molecular formula C ₁₂₈ H ₂₁₀ O ₄₁ Si ₁₆ (Z＝2) shown in FIG6, it can be respectively identified that the silsesquioxane with the peak at the retention time of 3.86 minutes is the condensed silsesquioxane obtained by condensing two cage-type silsesquioxanes represented by the composition formula (1) (all R ¹ is 2-(3',4'-epoxycyclohexyl)ethyl), and the silsesquioxane with the peak at the retention time of 1.81 minutes is the composition formula (1) (all R Condensed silsesquioxane obtained by condensing a cage-type silsesquioxane represented by formula ( ^{1) (wherein R 2} is 2-(3',4'-epoxycyclohexyl)ethyl) with a cage-type silsesquioxane represented by formula (2) (wherein all R ² are 2-(3',4'-epoxycyclohexyl)ethyl). The following shows the estimated structure of the condensed silsesquioxane with peaks at retention times of 3.86 minutes and 1.81 minutes. Silsesquioxane with a peak at a retention time of 3.86 minutes

All ^R1 in the above formula is 2-(3',4'-epoxycyclohexyl)ethyl. ・Silsesquioxane with a peak retention time of 1.81 minutes In the above formula, all R ¹ and R ² are 2-(3',4'-epoxycyclohexyl)ethyl.

Example 2 : Preparation of the epoxy-containing polyorganosilsesquioxane of the present invention ( 2 ) In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, a nitrogen inlet tube, and a Dean-Stark tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were added under a nitrogen flow, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g (2.8 mmol as potassium carbonate) of a 5% aqueous solution was added over a period of 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over a period of 20 minutes. During the addition, the temperature was not allowed to rise significantly. The polycondensation reaction was then carried out for 5 hours, maintained at 50°C, under a nitrogen stream. 230.5 g of methyl isobutyl ketone was then added, and the temperature was raised from 50°C to 90°C under reduced pressure. Acetone (0.0%), methyl isobutyl ketone (20.58%), and water (0.35%) were removed by distillation until the system remained at 90°C with stirring for 42 hours. 273.2 g of methyl isobutyl ketone was then added, and the mixture was washed six times with 273.2 g of water until the conductivity was below 1.5 μS/cm. The mixture was then concentrated to obtain 50.0 g of a colorless, transparent liquid. Analysis of the product revealed a number-average molecular weight of 9843, a molecular weight dispersity of 2.89, a content of 1.9% for monomeric cage-type silsesquioxane (retention time 7.6-8.3 minutes), a content of 98.1% for condensed silsesquioxane (retention time 4.7-7.6 minutes), and a [T3 isomer/T2 isomer] ratio of 196.2. The ²⁹ Si-NMR spectrum is shown in Figure 7, and the GPC chart is shown in Figure 8.

Comparative Example 1 : Preparation of Epoxy-Group-Containing Polyorganosilsesquioxane: In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a Dean-Stark tube, 3.0 mmol (0.56 g) of phenyltrimethoxysilane and 275.4 g of acetone were added under a nitrogen flow, and the temperature was raised to 50°C. To the resulting mixture, 7.74 g (2.8 mmol as potassium carbonate) of a 5% aqueous solution of potassium carbonate was added over 5 minutes, followed by 2800.0 mmol (50.40 g) of water over 20 minutes. Simultaneously with the start of the dropwise addition of potassium carbonate, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added dropwise, and the addition was terminated after two hours. During the addition, the temperature was not allowed to rise significantly. Polycondensation was then carried out under a nitrogen stream at 50°C for five hours. Subsequently, 230.5 g of methyl isobutyl ketone was added, and the mixture was washed six times with water (273.2 g). Concentration was performed until the conductivity was below 1.5 μS/cm, yielding 50.0 g of a turbid white liquid.

[Evaluation of Solvent Solubility] Solvent solubility was evaluated by adding 2 L of acetone or chloroform to 50-60 g of the products obtained in the Examples and Comparative Examples above. Complete dissolution, resulting in a clear solution, was evaluated as "completely dissolved," while partial insolubility, resulting in a turbid solution, was evaluated as "turbid." The results are shown in Table 1.

[Table 1] (Table 1) Sample acetone Chloroform Example 1 Completely dissolved Completely dissolved Example 2 Completely dissolved Completely dissolved Comparative example 1 White turbidity White turbidity

Reference Example 1 : Preparation of a Hard Coat Film: A mixed solution of 100 parts by weight of the epoxy-containing polyorganosilsesquioxane obtained in Example 1, 20 parts by weight of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.), and 1 part by weight of curing catalyst 1 (diphenyl[4-(phenylthio)phenyl]aluminum tris(pentafluoroethyl)trifluorophosphate) was prepared to serve as a hard coating solution (curable composition). The hard coating liquid obtained above was cast onto a PET film (trade name "KEB03W", manufactured by DuPont Teijin Films) using a wire bar coater, achieving a 5 μm thick hard coating layer after curing. The film was then placed in a 70°C oven (pre-baked) for 10 minutes and then irradiated with UV light (irradiation conditions (dose): 312 mJ/ ^cm² , irradiation intensity: 80 W/ ^cm² ). Finally, the film was heat-treated (cured) at 80°C for 2 hours to cure the hard coating liquid, producing a hard coating film with a hard coating layer.

The hard coating film obtained above was evaluated in various ways using the following methods. (1) Haze and total light transmittance The haze and total light transmittance of the hard coating film obtained above were measured using a HAZE METER (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-300A).

(2) Surface hardness (pencil hardness) The pencil hardness of the hard coating layer surface of the hard coating film obtained above was evaluated in accordance with JIS K5600-5-4.

(3) Heat resistance (5% weight loss temperature ( _Td5 )) A sample of approximately 5 mg of the hard coat layer of the hard coat film obtained by the same method as above was cut using a cutter, except that a glass plate was used instead of the PET film. The sample was measured using a differential thermogravimetric analyzer (TG/DTA6300, manufactured by Seiko Instruments Co., Ltd.) under the following conditions to determine the 5% weight loss temperature of the sample. Measurement temperature range: 25-550°C Heating rate: 10°C/min Gas atmosphere: Nitrogen

(4) Abrasion resistance: A #0000 steel wool was moved back and forth 100 times on the hard coating surface of the hard coating film obtained above at a load of 1000 g/ ^cm2 . The presence and number of scratches on the hard coating surface were determined, and the abrasion resistance was evaluated according to the following criteria. ◎ (Excellent abrasion resistance): 0 scratches ○ (Good abrasion resistance): 1 to 10 scratches × (Poor abrasion resistance): More than 10 scratches

(5) Bending resistance (cylindrical mandrel method); mandrel test Using a cylindrical mandrel, the bending resistance of the hard coating film obtained above was evaluated in accordance with JIS K5600-5-1.

The following describes variations of the invention related to the present invention. [Supplementary Note 1] A polyorganosilsesquioxane comprising a silsesquioxane, wherein the silsesquioxane is a condensate obtained by condensing two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3), and composition formula (4), and has a molecular weight of 8000 or less.・Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (In formula (1), R ¹ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (In formula (2), R ² are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (In formula (3), R ³ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (In formula (4), R ⁴ each independently represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) [Supplementary Note 2] The polyorganosilsesquioxane as described in Supplementary Note 1, wherein the silsesquioxane is a condensate obtained by condensing at least one of the cage-type silsesquioxanes represented by the following composition formulas (5) to (8).・Formula (5): [R ⁵ SiO _3/2 ] ₆ [R ⁵ SiO _2/2 (OR ^c )] ₃ (In formula (5), R ⁵ is independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c is independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (6): [R ⁶ SiO _3/2 ] ₈ [R ⁶ SiO _2/2 (OR ^c )] ₃ (In formula (6), R ⁶ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (7): [R ⁷ SiO _3/2 ] ₁₀ [R ⁷ SiO _2/2 (OR ^c )] ₁ (In formula (7), R ⁷ are each independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (8): [R ⁸ SiO _3/2 ] ₁₂ [R ⁸ SiO _2/2 (OR ^c )] ₁ (In formula (8), R ⁸ are independently a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing a polymerizable functional group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) [Supplementary Note 3] The polyorganosilsesquioxane as described in Supplementary Note 1 or 2, wherein the group containing a polymerizable functional group is a cationic polymerizable functional group (preferably an epoxy group, an oxobutyl group, a vinyl ether group, or a vinylphenyl group). [Supplementary Note 4] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 3, wherein the group containing a polymerizable functional group is a free radical polymerizable functional group (preferably a (meth)acryloxy group, a (meth)acrylamide group, a vinyl group, or a vinylthio group). [Supplementary Note 5] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 4, wherein the polymerizable functional group is an epoxy group or a (meth)acryloxy group. [Supplementary Note 6] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 5, wherein the group containing a polymerizable functional group is of the following formula (1A): [In formula (1A), R ^1A represents a linear or branched alkylene group] A group represented by the following formula (1B) [In formula (1B), R ^1B represents a linear or branched alkylene group] A group represented by the following formula (1C): [In formula (1C), R ^1C represents a linear or branched alkylene group], or a group represented by the following formula (1D) [In formula (1D), R ^1D represents a linear or branched alkylene group] A group represented by [Supplementary Note 7] The polyorganosilsesquioxane described in Supplementary Note 6, wherein in the above formulas (1A), (1B), (1C), and (1D), R ^1A , R ^1B , R ^1C , and R ^1D are each a linear alkylene group having 1 to 4 carbon atoms, or a branched alkylene group having 3 or 4 carbon atoms (preferably an ethylene group, a trimethylene group, or a propylene group, more preferably an ethylene group or a trimethylene group). [Supplementary Note 8] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 7, wherein, in the above-mentioned composition formula (1), the number of groups containing polymerizable functional groups in R ¹ is 3 to 9 (preferably 5 to 9, more preferably 7 to 9, and further preferably 9). [Supplementary Note 9] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 8, wherein, in the above-mentioned composition formula (2), the number of groups containing polymerizable functional groups in R ² is 3 to 8 (preferably 5 to 8, more preferably 7 to 8, and further preferably 8). [Supplementary Note 10] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 9, wherein, in the above-mentioned composition formula (3), the number of groups containing polymerizable functional groups in R ³ is 3 to 10 (preferably 5 to 10, more preferably 7 to 10, and further preferably 10). [Supplementary Note 11] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 10, wherein, in the above-mentioned composition formula (4), the number of groups containing polymerizable functional groups in R ⁴ is preferably 3 to 12 (preferably 5 to 12, more preferably 7 to 12, and further preferably 12). [Supplementary Note 12] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 11, wherein the ratio of the group containing a polymerizable functional group relative to the total of R ¹ in the above-mentioned composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), and R ⁴ in the composition formula (4) is 30% or more (preferably 50% or more, and more preferably 80% or more). [Supplement 13] The polyorganosilsesquioxane according to any one of Supplements 1 to 12, wherein the molar ratio of the constitutional unit represented by the following formula (I) (T3 form) to the constitutional unit represented by the following formula (II) (T2 form) [constituent unit represented by formula (I)/constituent unit represented by formula (II); T3 form/T2 form] is 1 or more (preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 6 or more, more preferably 7 or more, more preferably 8 or more, more preferably 10 or more, more preferably 15 or more, and further preferably 20 or more). [R ^a SiO _3/2 ] (I) [In formula (I), R ^a represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom] [R ^b SiO _2/2 (OR ^c )] (II) [In formula (II), R ^b represents a group containing a polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group; R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] [Supplement 14] The polyorganosilsesquioxane as described in Supplement 13, wherein the molar ratio of the (T3 form) to the (T2 form) [T3 form/T2 form] is 500 or less (preferably 400 or less, more preferably 300 or less, more preferably 100 or less, more preferably 50 or less, more preferably 40 or less, more preferably 30 or less, and further preferably 25 or less). [Supplement 15] The polyorganosilsesquioxane as described in any one of Supplements 1 to 14, which is obtained by condensing 2 to 5 (preferably 2 to 3, more preferably 2) of one of the cage-type silsesquioxanes represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3), and composition formula (4) or condensing 2 to 5 (preferably 2 to 3, more preferably 2) of two or more of the cage-type silsesquioxanes represented by the above-mentioned composition formula (1), composition formula (2), composition formula (3), and composition formula (4). [Supplementary Note 16] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 15, comprising a cage-type silsesquioxane monomer. [Supplementary Note 17] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 16, wherein the content of the cage-type silsesquioxane monomer is 5% by weight or greater (preferably 10% by weight or greater, more preferably 20% by weight or greater) relative to the total weight of the polyorganosilsesquioxane. [Supplementary Note 18] The polyorganosilsesquioxane according to Supplementary Note 17, wherein the content of the cage-type silsesquioxane monomer is 50% by weight or less (preferably 40% by weight or less, more preferably 20% by weight or less) relative to the total weight of the polyorganosilsesquioxane. [Supplementary Note 19] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 18, wherein the content of the condensed silsesquioxane in the polyorganosilsesquioxane is 20% by weight or greater (preferably 25 to 90% by weight, more preferably 30 to 80% by weight, and even more preferably 40 to 70% by weight) relative to the total weight of the polyorganosilsesquioxane. [Supplementary Note 20] The polyorganosilsesquioxane according to Supplementary Note 19, wherein the condensed silsesquioxane has a number average molecular weight (Mn) of 2,000 to 50,000 (preferably 2,500 to 40,000, and even more preferably 3,000 to 30,000) based on standard polystyrene as determined by gel permeation chromatography. [Supplementary Note 21] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 20, wherein the number average molecular weight (Mn) is 2,000 to 50,000 (preferably 2,500 to 40,000, more preferably 3,000 to 30,000) based on standard polystyrene conversion by gel permeation chromatography. [Supplementary Note 22] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 21, wherein the molecular weight dispersion (Mw/Mn) is 1.0 to 4.0 (preferably 1.1 to 3.0, more preferably 1.2 to 2.5) based on standard polystyrene conversion by gel permeation chromatography. [Supplementary Note 23] The polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 22, wherein the 5% weight loss temperature ( _Td5 ) in an air environment is 330°C or higher (e.g., 330-450°C, preferably 340°C or higher, and more preferably 350°C or higher). [Supplementary Note 24] A curable composition comprising the polyorganosilsesquioxane according to any one of Supplementary Notes 1 to 23. [Supplementary Note 25] The curable composition according to Supplementary Note 24, wherein the content of the polyorganosilsesquioxane is 70% by weight to 100% by weight (preferably 80% by weight to 99.8% by weight, and more preferably 90% by weight to 99.5% by weight) relative to the total weight of the curable composition excluding the solvent (100% by weight). [Supplementary Note 26] The curable composition according to Supplementary Note 22 or 23, wherein the ratio of the polyorganosilsesquioxane is 70-100% by weight (preferably 75-98% by weight, more preferably 80-95% by weight) relative to the total amount of the cationic curable compound or the radical curable compound (100% by weight). [Supplementary Note 27] The curable composition according to any one of Supplementary Notes 24 to 26, comprising a curing catalyst. [Supplementary Note 28] The curable composition according to Supplementary Note 27, comprising a photopolymerization initiator or a thermal polymerization initiator as the curing catalyst. [Supplementary Note 29] The curable composition according to Supplementary Note 27 or 28, comprising a cationic polymerization initiator or a radical polymerization initiator as the curing catalyst. [Supplementary Note 30] The curable composition according to Supplementary Note 29, wherein the cationic polymerization initiator is a photo-catalytic polymerization initiator or a thermal-catalytic polymerization initiator. [Supplementary Note 31] The curable composition according to Supplementary Note 30, wherein the photo-catalytic polymerization initiator is one or more selected from the group consisting of salts of coronium, iodonium, selenium, ammonium, phosphonium, and salts of transition metal complex ions and anions. [Note 32] The curable composition as described in Note 30, wherein the thermal cationic polymerization initiator is one or more compounds selected from the group consisting of aryl stibnium salts, aryl iodonium salts, aromatic hydrocarbon-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes. [Note 33] The curable composition as described in Note 29, wherein the free radical polymerization initiator is a photo-free radical polymerization initiator or a thermal free radical polymerization initiator. [Note 34] The curable composition as described in Note 33, wherein the photo-free radical polymerization initiator is selected from the group consisting of 2-amino-2-benzoyl-1-phenylalkane compounds, imidazole compounds, halogenated trimethylol compounds, Compounds, and halogenated methyl One or more photoradical polymerization initiators selected from the group consisting of oxadiazole compounds. [Supplementary Note 35] The curable composition according to Supplementary Note 33, wherein the thermal radical polymerization initiator is an organic peroxide. [Supplementary Note 36] The curable composition according to any one of Supplementary Notes 27 to 35, comprising a cationic curable compound other than the polyorganosilsesquioxane and/or a radical curable compound other than the polyorganosilsesquioxane. [Supplementary Note 37] The curable composition according to Supplementary Note 36, wherein the content of the curing catalyst is 0.01 to 3.0 parts by weight (preferably 0.05 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, and even more preferably 0.3 to 1.0 parts by weight) based on 100 parts by weight of the total amount of the polyorganosilsesquioxane and the other cationic curable compound. [Supplementary Note 38] The curable composition according to Supplementary Note 36 or 37, wherein the other cationic curable compound comprises an epoxy compound, an oxetane compound, or a vinyl ether compound other than the polyorganosilsesquioxane. [Supplementary Note 39] The curable composition according to Supplementary Note 38, wherein the epoxy compound is an aliphatic epoxy compound, an aromatic epoxy compound, or an aliphatic epoxy compound. [Supplementary Note 40] The curable composition according to any one of Supplementary Notes 36 to 39, comprising a (meth)acrylic compound other than the polyorganosilsesquioxane as the other radical-curable compound. [Supplementary Note 41] The curable composition according to any one of Supplementary Notes 36 to 40, wherein the content (blend amount) of the other cationic curable compound and/or the other radical-curable compound is 50% by weight or less (preferably 30% by weight or less, and more preferably 10% by weight or less) relative to the total amount of the polyorganosilsesquioxane, the other cationic curable compound, and the other radical-curable compound. [Supplement 42] The curable composition according to any one of Supplements 24 to 41, comprising a polymerization stabilizer. [Supplement 43] The curable composition according to Supplement 42, wherein the polymerization stabilizer is one or more selected from the group consisting of hindered amine compounds, cobalt sulfate compounds, and phosphite compounds. [Supplement 44] The curable composition according to Supplement 42 or 43, wherein the content of the polymerization stabilizer is 0.005 parts by weight or more (preferably 0.01 to 10 parts by weight, and more preferably 0.02 to 1 part by weight) per 100 parts by weight of the polyorganosilsesquioxane. [Supplementary Note 45] The curable composition according to any one of Supplementary Notes 42 to 44, comprising the aforementioned polymerization stabilizer and a curing catalyst, wherein the content of the polymerization stabilizer is at least 1 part by weight (preferably 3 to 200 parts by weight, more preferably 5 to 150 parts by weight) per 100 parts by weight of the curing catalyst. [Supplementary Note 44] The curable composition according to any one of Supplementary Notes 24 to 45, comprising a solvent. [Supplementary Note 45] The curable composition according to Supplementary Note 44, wherein the boiling point of the solvent is 170°C or less. [Supplementary Note 46] The curable composition according to Supplementary Note 44 or 45, wherein the amount of the solvent used is 30 to 80% by weight (preferably 40 to 70% by weight, more preferably 50 to 60% by weight), based on the concentration of the non-volatile matter in the curable composition. [Supplementary Note 47] The curable composition according to any one of Supplementary Notes 24 to 46, which is a liquid at room temperature (approximately 25°C). [Supplementary Note 48] The curable composition according to any one of Supplementary Notes 24 to 47, which has a viscosity at 25°C of 300 to 20,000 mPa·s (preferably 500 to 10,000 mPa·s, more preferably 1,000 to 8,000 mPa·s). [Supplement 49] The curable composition according to any one of Supplements 24 to 48, which is a curable composition for forming a hard coat layer. [Supplement 50] The curable composition according to any one of Supplements 24 to 48, which is a curable composition for use as an adhesive. [Supplement 51] A cured product, which is a cured product of the curable composition according to any one of Supplements 24 to 50. [Supplement 52] A hard coat film comprising a substrate and a hard coat layer comprising the cured product according to Supplement 51. [Supplement 53] The hard coat film according to Supplement 52, wherein the substrate is a plastic substrate, a metal substrate, a ceramic substrate, a semiconductor substrate, a glass substrate, a paper substrate, a wood substrate, or a substrate having a painted surface. [Supplementary Note 54] The hard coat film according to Supplementary Note 52 or 53, wherein the thickness of the substrate is 0.01 to 10,000 μm. [Supplementary Note 55] The hard coat film according to any one of Supplementary Notes 52 to 54, wherein the thickness of the hard coat layer is 1 to 200 μm (preferably 3 to 150 μm). [Supplementary Note 56] The hard coat film according to any one of Supplementary Notes 52 to 55, wherein the haze value when the hard coat layer has a thickness of 50 μm is 1.5% or less (preferably 1.0% or less). [Supplementary Note 57] The hard coat film according to any one of Supplementary Notes 52 to 56, wherein the haze value when the hard coat layer has a thickness of 50 μm is 0.1% or more. [Supplementary Note 58] The hard coat film according to any one of Supplementary Notes 52 to 57, wherein the total light transmittance of the hard coat layer is 85% or greater (preferably 90% or greater) when the thickness is 50 μm. [Supplementary Note 59] The hard coat film according to any one of Supplementary Notes 52 to 58, wherein the hard coat layer has a surface protective film on the surface. [Supplementary Note 60] The hard coat film according to any one of Supplementary Notes 52 to 59, wherein the thickness is 1 to 10,000 μm. [Supplementary Note 61] A transfer film comprising a substrate and a hard coat layer formed on at least one surface of the substrate, the hard coat layer being a layer containing the curable composition according to Supplementary Note 49. [Supplementary Note 62] The transfer film according to Supplementary Note 61, wherein the peel strength between the release layer and the hard coat layer is 30 to 500 mN/24 mm (preferably 40 to 300 mN/24 mm, more preferably 50 to 200 mN/24 mm). [Supplementary Note 63] The transfer film according to Supplementary Note 61 or 62, further comprising an adhesion-enhancing coating layer and an adhesive layer sequentially deposited on the hard coat layer. [Supplementary Note 64] The transfer film according to Supplementary Note 63, wherein the adhesion-enhancing coating layer has a thickness in the range of 0.1 to 20 μm (preferably 0.5 to 5 μm). [Supplementary Note 65] The transfer film according to any one of Supplementary Notes 61 to 64, wherein the thickness of the adhesive layer is 0.1 to 10 μm (preferably 0.5 to 5 μm). [Supplementary Note 66] The transfer film according to any one of Supplementary Notes 61 to 65, further comprising at least one coloring layer. [Supplementary Note 67] The transfer film according to Supplementary Note 66, wherein the coloring layer is provided when forming a decorative film for transferring a pattern layer and/or a concealing layer to a molded article. [Supplementary Note 68] An adhesive sheet comprising a substrate and an adhesive layer, wherein the adhesive layer is located on at least one side of the substrate and is a layer comprising the curable composition according to Supplementary Note 50. [Supplementary Note 69] Use of the curable composition according to Supplementary Note 50, wherein the adhesive layer is used in an adhesive sheet comprising a substrate and an adhesive layer located on at least one side of the substrate. [Supplementary Note 70] A adhesive sheet comprising a substrate, an adhesion-promoting coating layer, and an adhesive layer, wherein the adhesion-promoting coating layer and the adhesive layer are located on at least one side of the substrate, the adhesion-promoting coating layer containing a silane coupling agent, and the adhesive layer being a layer containing the curable composition according to Supplementary Note 50; the adhesive layer is disposed on the surface of the adhesion-promoting coating layer. [Supplementary Note 71] Use of the curable composition according to any one of Supplementary Notes 22 to 48, wherein the curable composition is used as a curable composition for forming a hard coat layer. [Supplementary Note 72] Use of the curable composition according to any one of Supplementary Notes 22 to 48 as a curable adhesive composition. [Supplementary Note 73] Use of the cured product according to Supplementary Note 51 as a hard coat layer in a hard coat film comprising a substrate and a hard coat layer. [Supplementary Note 74] Use of the curable composition according to Supplementary Note 49 as a hard coat layer in a transfer film comprising a substrate and a hard coat layer formed on a release layer formed on at least one surface of the substrate. [Supplement 75] A use of the curable composition according to Supplement 50, wherein the adhesive layer is used in an adhesive sheet comprising a substrate, an adhesion-promoting coating, and an adhesive layer, wherein the adhesion-promoting coating and the adhesive layer are located on at least one side of the substrate, the adhesion-promoting coating contains a silane coupling agent, and the adhesive layer is disposed on a surface of the adhesion-promoting coating. [Industrial Applicability]

The polyorganosilsesquioxane of the present invention can be used as a hard coating film or adhesive sheet material.

1: Hardcoat 11: Hardcoat 12: Substrate 2: Transfer film 21: Substrate 22: Release layer 23: Hardcoat (uncured or semi-cured) 24: Adhesion-enhancing layer 25: Coloring layer 26: Adhesive layer 3: Adhesive sheet 31: Adhesive layer 32: Substrate 33: Adhesion-enhancing layer

[Figure 1] is a ^29Si -NMR spectrum of the epoxy-containing condensed silsesquioxane of the present invention obtained in Example 1. [Figure 2] is a GPC chart of the epoxy-containing condensed silsesquioxane of the present invention obtained in Example 1. [Figure 3] is a UPLC-MS chart of the epoxy-containing condensed silsesquioxane of the present invention obtained in Example 1. [Figure 4] is a UPLC-MS chart of the epoxy-containing condensed silsesquioxane of the present invention obtained in Example 1. [Figure 5] is a MS simulation chart of the molecular formula C ₁₄₄ H ₂₃₄ O ₄₅ Si ₁₈ (Z=2). Figure 6 is a MS simulation chart of the molecular formula _{C₁₂₈H₁₁₀O₄₁₁₁₁₁₁₁} (Z= ₂ ). Figure 7 is ^{a 29Si} _{- NMR} spectrum of the epoxy-containing condensed silsesquioxane of the present invention obtained in Example 2. Figure 8 is a GPC chart of the epoxy-containing condensed silsesquioxane of the present invention obtained in Example 2. Figure 9 is a schematic diagram (cross-sectional view) showing one embodiment of the hard coat film of the present invention. Figure 10 is a schematic diagram (cross-sectional view) showing one embodiment of the transfer film of the present invention. Figure 11 is a schematic diagram (cross-sectional view) showing one embodiment of the adhesive sheet of the present invention.

Claims (20)

A polyorganosilsesquioxane comprising a condensed silsesquioxane, wherein the condensed silsesquioxane is a condensate obtained by condensing two or more cage-type silsesquioxanes selected from the group consisting of cage-type silsesquioxanes represented by the following composition formula (1), composition formula (2), composition formula (3), and composition formula (4), and has a molecular weight of 8000 or less, wherein the content of the monomer cage-type silsesquioxane is 5% by weight or more relative to the total amount of the polyorganosilsesquioxane, and the content of the condensed silsesquioxane is 20% by weight or more relative to the total amount of the polyorganosilsesquioxane; Formula (1): [R ¹ SiO _3/2 ] ₈ [R ¹ SiO _2/2 (OR ^c )] ₁ (In formula (1), R ¹ is independently a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing an epoxy group; R ^c represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (2): [R ² SiO _3/2 ] ₆ [R ² SiO _2/2 (OR ^c )] ₂ (In formula (2), R ² is independently a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is a group containing an epoxy group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (3): [R ³ SiO _3/2 ] ₈ [R ³ SiO _2/2 (OR ^c )] ₂ (In formula (3), R ³ each independently represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is an epoxy group-containing group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom) ・Formula (4): [R ⁴ SiO _3/2 ] ₁₀ [R ⁴ SiO _2/2 (OR ^c )] ₂ (In formula (4), R ⁴ are each independently an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and at least one of them is an epoxy-containing group; R ^c each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom). The polyorganosilsesquioxane of claim 1, wherein the epoxy group is represented by the following formula (1A): [In formula (1A), R ^1A represents a linear or branched alkylene group] A group represented by the following formula (1B) [In formula (1B), R ^1B represents a linear or branched alkylene group] A group represented by the following formula (1C): [In formula (1C), R ^1C represents a linear or branched alkylene group], or a group represented by the following formula (1D) [In the formula (1D), R ^1D represents a linear or branched alkylene group] The polyorganosilsesquioxane of claim 1 or 2, wherein the ratio of the groups containing epoxy groups relative to the total of R ¹ in the above-mentioned composition formula (1), R ² in the composition formula (2), R ³ in the composition formula (3), and R ⁴ in the composition formula (4) is 30% or more. The polyorganosilsesquioxane of claim 1 or 2, wherein the constituent unit represented by the following formula (I) [ ^RaSiO3 _/2 ] (I) [in formula (I), ^Ra represents an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom] and the following formula (II) [ ^RbSiO2 _/2 ( ^ORc )] (II) [in formula (II), ^Rb represents an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom; ^Rc represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] The molar ratio of the constituent units represented by formula (I)/constituent units represented by formula (II)] is 1 or more and 500 or less. The polyorganosilsesquioxane of claim 1 or 2, wherein the number average molecular weight is 2,000 to 50,000. For the polyorganosilsesquioxane of claim 1 or 2, its molecular weight dispersion (weight average molecular weight/number average molecular weight) is 1.0 to 4.0. A curable composition comprising the polyorganosilsesquioxane according to any one of claims 1 to 6. The hardening composition of claim 7 further comprises a hardening catalyst. The curable composition of claim 8, wherein the curing catalyst is a photo- or thermal-polymerization initiator. The hardening composition of claim 7 further comprises a polymeric stabilizer. The hardening composition of claim 7 is a hardening composition for forming a hard coating layer. The hardening composition of claim 7, which is a hardening composition for adhesives. A cured product, which is a cured product of the curable composition according to any one of claims 7 to 12. A hard coating film comprises a substrate and a hard coating layer which is a cured product according to claim 13. A transfer film comprises a substrate and a hard coating layer formed on a release layer formed on at least one surface of the substrate, wherein the hard coating layer is a layer containing the curable composition of claim 11. The transfer film of claim 15 further comprises an anchor coat layer and an adhesive layer sequentially deposited on the hard coat layer. The transfer film of claim 15 further comprises at least one colored layer. The transfer film of claim 15, wherein the thickness of the hard coating layer is 3 to 150 μm. A bonding sheet comprises a substrate and an adhesive layer, wherein the adhesive layer is located on at least one side of the substrate and is a layer containing the curable composition of claim 12. A bonding sheet comprising a substrate, an adhesion-promoting coating layer, and an adhesive layer, wherein the adhesion-promoting coating layer and the adhesive layer are located on at least one side of the substrate, the adhesion-promoting coating layer contains a silane coupling agent, and the adhesive layer is a layer containing the curable composition of claim 12; the adhesive layer is disposed on a surface of the adhesion-promoting coating layer.