TW201429982A - Cage-like silsesquioxane compound, curable resin composition and resin cured article using the same - Google Patents

Abstract

The object of the present invention is to provide a cage-like silsesquioxane compound capable of obtaining curable resin compostion with excellent formability, and a resin cured article with excellent transparency, low water absorbability and antiweatherability. The present invention provides a cage-like silsesquioxane compound comprising the following compounds represented by the general formula (1): [R1SiO3/2]n[R2SiO3/2]m[R3SiO3/2j...(1) {in formula (1), R1 represents a reactive organic functional group comoprising a (meth)acryloyl group and an alkyl chain with a carbon number of 4 to 10. R2 represents a reactive organic functional group comoprising a (meth)acryloyl group and an alkyl chain with a carbon number of 1 to 3, and the likes. R3 represents a hydrogen atom, an alkyl group with 1 to 6 carbons, a phenyl group and an aryl group and the likes. n', m and j reprensets a number satisfying the condition represented by the following formulae (i) to (iv): n ≥ 2...(i), m ≥ 1...(ii), j ≥ O...(iii), n+m+j=h...(iv) [in formula (iv), h reprensets any one integer selected from the group consisting of 8, 10, 12 and 14.]. While n, m and j are separately 2 or more, R1, R2 and R3 may be the same or different.}.

Description

Cage sesquioxane compound, curable resin composition using the same, and resin cured product

The present invention relates to a cage sesquioxane compound, a curable resin composition using the compound, and a cured resin.

In general, a glass plate is widely used as a transparent substrate such as a liquid crystal display element substrate, a color filter substrate, an organic EL display element substrate, an electronic paper substrate, a TFT substrate, or a solar cell substrate. However, in recent years, a transparent plastic plate has been reviewed as a substitute for the reason that the glass plate is easily broken, is not easily bent, and is not suitable for weight reduction.

On the other hand, a sesquioxane having a cage structure exhibits a specific function by utilizing its characteristic structure, and is attracting attention in various fields. In particular, since the cured product of the cage sesquioxane resin has excellent heat resistance, weather resistance, optical properties, dimensional stability, and the like, it is expected to be a material for a transparent plastic sheet instead of a glass plate.

In the case of the hardened material of the above-mentioned cage sesquioxane resin, for example, in JP-A-2006-89685 (Patent Document 1), a description will be given of [RSiO _3/2 ] _n to A radical copolymerization of a fluorinated resin copolymer obtained by a cage-type polyorganosilsesquioxane having a (meth)acryl fluorenyl group as a functional group, an oligomer, and a oxirane resin composition of an unsaturated compound.

In JP-A-2004-143449 (Patent Document 2), any one of (meth)acryl fluorenyl group, epoxy propyl group, and vinyl group represented by [RSiO _3/2 ] _{n is} described. Cage sesquioxane resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2006-89685

[Patent Document 2] JP-A-2004-143449

The oxime resin copolymer described in the above Patent Document 1 has a certain small linear expansion coefficient in a non-absorbent state, but the inventors have found that hydrophilicity is present on all of the ruthenium atoms in the skeleton. a compound of a (meth)acrylonitrile-based cage type sesquiterpoxide compound (cage polyorganosilsesquioxane), which has high water absorption and, due to water absorption, a linear expansion coefficient Bigger problem.

Further, the cage type polyorganosilsesquioxane described in Patent Document 1 and the cage sesquioxane resin described in Patent Document 2 use a cage type sesquiterpene of (meth) acrylonitrile group. In the oxyalkylene resin, a cured resin having excellent transparency is obtained. However, the inventors of the present invention have found that the cured resin obtained has insufficient weather resistance, and ultraviolet rays which are exposed to a wavelength of about 300 nm for a long period of time become yellow. A problem of reduced transparency is produced.

The present invention has been made in view of all the problems of the prior art described above, and an object of the invention is to provide a curable resin composition having excellent moldability, and excellent transparency and low water absorbability, and excellent weather resistance. The tree refers to a cage type sesquiterpene oxide compound of a cured product, and a curable resin composition using the compound and a cured resin obtained by curing the same.

The inventors of the present invention have carefully studied the results of the above studies in order to achieve the above object, and found that a novel cage sesquiterpoxide compound using a reactive organic functional group containing a (meth) acrylonitrile group and a specific hydrocarbon chain is found. Further, a curable resin composition having excellent moldability can be obtained, and the cured resin obtained by curing the resin can have excellent transparency and low water absorbability, and also has excellent weather resistance, and can attain the present invention. carry out.

That is, the characteristic of the cage sesquioxane compound of the present invention is

A compound represented by the following formula (1): [R ¹ SiO _3/2 ] _n [R ² SiO _3/2 ] _m [R ³ SiO _3/2 ] _j . . . (1)

In the formula (1), R ¹ is a group represented by the following formula (2):

[In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, p represents an integer of 4 to 10], and R ² is a group consisting of groups selected from the following general formulas (3) to (6). Any group of the group: a group represented by the formula (3):

In the formula (3), R ⁵ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 3. ], a group represented by the formula (4):

[In the formula (4), r represents an integer of 1 to 3], and the group represented by the formula (5):

[In the formula (5), s represents an integer of 1 to 3. ], and the group represented by the formula (6):

R ³ represents a group of any one selected from the group consisting of a free hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an aryl group, and n, m, and j are represented by the following formulas (i) to (iv). The integer of the condition indicated: n≧2. . . (i), m≧1. . . (ii), j≧O. . . (iii), n+m+j=h. . . (iv)

[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]

When n, m and j are each 2 or more, R ¹ , R ² and R ³ may be the same or different. }.

Further, the curable resin composition of the present invention contains the cage sesquiterpene oxide compound of the present invention and a radical polymerization initiator, and the content of the cage sesquioxane compound is 10 to 80% by mass. .

It is preferable that the curable resin composition further contains a (meth)acryl fluorenyl unsaturated compound other than the cage sesquiterpene oxide compound, the ladder type siloxane, and the random siloxane. Further, the curable resin composition was cast to have a thickness of 0.2 mm, and a high-pressure mercury lamp having an illuminance of 30 W/cm was used to irradiate light at a temperature of 2000 mJ/cm ² at room temperature to cause radical polymerization. The reaction rate of the (meth) acrylonitrile group measured by the spectrophotometry is preferably 70% or more. Further, in the curable resin composition, the content of the radical polymerization initiator is preferably 0.01 to 10% by mass.

The resin cured product of the present invention is characterized in that the curable resin composition of the present invention is obtained by radical polymerization.

Here, the reason for achieving the above object by the constitution of the present invention is not It is determined, but the inventors and the like presume as follows. In other words, a compound having a (meth) acrylonitrile group is generally excellent in radical polymerizability, and is conventionally known. However, when a resin cured product is produced using a resin composition containing a cage sesquioxane compound of the (meth) acrylonitrile group described in Patent Documents 1 and 2, a part of the above compound is (meth) propylene. The fluorenyl group may remain as an unreacted group. The present inventors have speculated that when such an unreacted group (residual double bond) has a large amount of residual in the cured resin, when it is exposed to high temperature in the presence of oxygen or exposed to ultraviolet rays in the outside for a long period of time, the bond is broken or The cause of recondensation, cracking or yellowing.

Compared with this, the cage type sesquioxane compound of the present invention is The propylene group contains a reactive organic functional group having a specific hydrocarbon chain, so that the adaptability is sufficiently large and the radical polymerizability is excellent. Therefore, the inventors of the present invention have estimated that the resin-cured material of the present invention obtained by using the compound has a reduced unreacted group and exhibits excellent transparency and excellent weather resistance.

Furthermore, the inventors of the present invention presumed that there is a specific one as described above. In the curable resin composition of the cage sesquiterpoxide compound of the present invention having a reactive organic functional group, the content of the (meth)acryl fluorenyl group of the hydrophilic group is sufficiently reduced, and the obtained resin cured product is sufficiently reduced. Excellent low water absorption.

Here, in the present invention, the (meth)acryl fluorenyl group means an acryl fluorenyl group and a methacryl fluorenyl group. In the present invention, the reaction rate of the (meth) acrylonitrile group means the double bond of the (meth) acryl oxime group when the curable resin composition containing the (meth) acryl fluorenyl group is cured. In terms of rate of change, according to Ohara, "Material design of hard coating film with plastic substrate as the center. Improvement of coating technology and hardness", Technical Information Association, April 28, 2005, p136-139 The method is ascertained. More specifically, first, the resin composition is extended to a thickness of 0.2 mm, and a high-pressure mercury lamp having an illuminance of 30 W/cm is used, and a light having an exposure amount of 2000 mJ/cm ² is irradiated at room temperature to cause radical polymerization. Maximum absorbance of stretching vibration derived from a carbon-oxygen double bond (C=O) in a (meth) acrylonitrile group in the range of 1723 to 1735 cm ^-1 (ideally 1728 cm ^-1 ) (A _C=O And, the maximum absorbance (A _{C = C} ) of the stretching vibration derived from the carbon-carbon double bond (C=C) in the (meth) acrylonitrile group from 1627 to 1638 cm ^-1 (ideally 1635 cm ^-1 ) They were each measured using a microscopic infrared spectroscopic device.

Then, the _ratio of A _C=O (AW _C=O ) to A _C=C (AW _C=C ) of the resin composition before the aforementioned radical polymerization (AW=AW _C=O /AW _C=C ) And the _ratio of A _C=O (AF _C=O ) to A _C=C (AF _C=C ) of the cured resin after the polymerization (AF=AF _C=O /AF _C=C ), according to The following formula: double bond change rate (AR) = (1-AW/AF) × 100, the double bond change rate (AR (%), ie (meth) propylene oxime of the above (meth) propylene fluorenyl group can be obtained. The reaction rate of the base.

According to the present invention, it is possible to provide a curable resin composition which can have excellent moldability, and a cage sesquiterpene oxide compound having a resin cured product which is excellent in transparency and low water absorbability and excellent in weather resistance. A curable resin composition of the compound and a cured resin obtained by curing the compound are used.

Fig. 1 is a graph showing the results of GPC of the resin mixture 1 obtained in Synthesis Example 1.

Fig. 2 is a graph showing the mass analysis of the resin mixture 1 obtained in Synthesis Example 1. The figure of the fruit.

Fig. 3 is a graph showing the results of GPC of the resin mixture 2 obtained in Synthesis Example 2.

Fig. 4 is a graph showing the results of GPC of the resin mixture 3 obtained in Synthesis Example 8.

Fig. 5 is a graph showing the results of GPC of the resin mixture 4 obtained in Synthesis Example 4.

Fig. 6 is a graph showing the results of GPC of the resin mixture 5 obtained in Synthesis Example 5.

Fig. 7 is a graph showing the results of GPC of the resin mixture 6 obtained in Synthesis Example 6.

Fig. 8 is a graph showing the results of GPC of the resin mixture 7 obtained in Synthesis Example 7.

Fig. 9 is a graph showing the results of GPC of the resin mixture 8 obtained in Synthesis Example 8.

Hereinafter, the present invention will be described in detail in a suitable embodiment.

First, the cage sesquiterpene oxide compound of the present invention will be described. The characteristic of the cage sesquiterpoxide compound of the present invention is represented by the following formula (1): [R ¹ SiO _3/2 ] _n [R ² SiO _3/2 ] _m [R ³ SiO _3/2 ] _j . . . (1)

In the above formula (1), R ¹ is a (meth) acrylonitrile group and a hydrocarbon chain reactive organic functional group containing a radical polymerizable functional group, and represents a group represented by the following formula (2):

In the above formula (2), R ⁴ represents a hydrogen atom or a methyl group. The above R ⁴ is particularly preferably a methyl group from the viewpoint of the repelling effect of the three-dimensional structure and the water absorption of the obtained cured resin.

In the above formula (2), p represents an integer of 4 to 10, and the hydrocarbon chain represented by (CH ₂ ) _p may be linear or branched, but the linear shape is ideal from the viewpoint of easy starting of the raw material. . When the value of p is less than the lower limit, the number of (meth) acrylonitrile groups per unit weight is increased, and as a result, the water absorption rate of the obtained cured product is deteriorated. On the other hand, when the above-mentioned upper limit is exceeded, the hydrocarbon chain length becomes When it is too long, the obtained cured product is decomposed or yellowed when exposed to ultraviolet rays for a long period of time. In the case of p, it is easy to start with raw materials, and the adaptability of the cage sesquiterpene oxide compound (the degree of freedom is larger and the radical polymerizability is improved), the integer of 6 to 10 is ideal, and 8 is more desirable. Desirably, the aforementioned hydrocarbon chain is particularly preferred as an octenyl group.

In the above formula (1), R ² represents a group selected from any group consisting of groups represented by the following general formulae (3) to (6).

In the above formula (3), R ⁵ is a hydrogen atom or a methyl group, and a methyl group is particularly preferable from the viewpoint of reducing the water absorption of the obtained resin cured product due to the repellency effect of the three-dimensional structure. Further, in the above formulae (3) to (5), each of q, r and s is an integer of 1 to 3, and 3 is more preferable. When the values of q, r, and s are less than the lower limit, the raw material tends to be difficult to obtain. On the other hand, if the value exceeds the upper limit, the hydrocarbon chain represented by (CH ₂ ) _t (t is q, r or s) becomes When it is too long, when the obtained hardened material is exposed to ultraviolet rays for a long period of time, there is a tendency to cause deterioration such as deterioration or yellowing. Further, the hydrocarbon chain represented by (CH ₂ ) _t may be linear or branched, but is preferably linear.

Among these, R ² is advantageous in a process which can be photo-radically polymerized in a short time and the time required for the curing process can be shortened, and the group represented by the above formula (3) or (6) is preferable.

In the above formula (1), R ³ represents any one selected from the group consisting of a free hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a group consisting of a phenyl group and an aryl group. When R ³ is an alkyl group, when the carbon number exceeds the above upper limit, the hydrocarbon chain length becomes too long, and the obtained cured product tends to cause decomposition or yellowing when exposed to ultraviolet rays for a long period of time. Among them, in the case of R ³ , a hydrogen atom, a methyl group, an ethyl group or a phenyl group is preferred.

Further, in the above formula (1), n, m and j represent integers satisfying the conditions of the following formulas (i) to (iv): n ≧ 2. . . (i), m≧1. . . (ii), j≧0. . . (iii), n+m+j=h. . . (iv)

[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]

When n in the above formula (1) satisfies the condition represented by the above formula (i), the cage sesquiterpene oxide compound of the present invention contains two or more (meth) acrylonitrile groups and a carbon number of 4 to 10. The reactive organic functional group of the hydrocarbon chain (the group represented by the above formula (2)) is sufficiently adaptable and superior to the radical polymerizable property, and can sufficiently reduce the unreacted group remaining in the obtained cured resin (residual double The key) suppresses decomposition and yellowing when exposed to ultraviolet light for a long period of time.

Further, when m in the above formula (1) satisfies the condition represented by the above formula (ii), a reactive functional group capable of forming a compact three-dimensional network structure having a short cross-linking distance (the above formulas (3) to (6) Any of the groups shown in the formula) is imparted to the cage type sesquiterpene oxide compound, and thus excellent rigidity and toughness can be imparted to the obtained resin cured product.

Further, all of n, m and j in the above formula (1) satisfy the conditions represented by the above formulas (i) to (iv), and the cage sesquioxaxane compound of the present invention can be a cage which is almost completely condensed. Since the structure is obtained, the obtained cured resin composition can achieve more excellent formability, and further excellent transparency, low water absorption and weather resistance can be achieved in the obtained cured resin. Here, when each of n, m, and j is 2 or more, R ¹ , R ^{2 ,} and R ³ may be the same or different.

The cage sesquioxane compound of the present invention is preferably, for example, a compound represented by the following formula (7) to formula (18): Formula (7) represents R in the above formula (1). ² is a group represented by the formula (3), R ⁴ and R ⁵ are a methyl group, n is 2, m is 6, and j is 0 of the following compounds:

In the formula (7), p represents an integer of 4 to 10, q represents an integer of 1 to 3, and the formula (8) represents a group represented by the formula (4) in the above formula (1), and R ² is a group represented by the formula (4). A compound represented by the following formula wherein R ⁴ is a methyl group, n is 2, m is 6, and j is 0:

In the formula (8), p represents an integer of 4 to 10, and r represents an integer of 1 to 3. In the above formula (1), R ² is a group represented by the formula (3), R ⁴ and R ⁵ are a methyl group, n is 4, m is 4, and j is 0. Compound represented by the formula:

[In the formula (9), p represents an integer of 4 to 10, and q represents an integer of 1 to 3. In the above formula (1), R ² is a group represented by the formula (3), R ⁴ and R ⁵ are a methyl group, n is 3, m is 7, and j is 0. Compound represented by the formula:

In the formula (10), p represents an integer of 4 to 10, q represents an integer of 1 to 3, and the formula (11) represents the above formula (1), and in the above formula (1), R ² is a formula (3) A group represented by the following formula: wherein R ⁴ and R ⁵ are a methyl group, n is 5, m is 5, and i is 0:

[In the formula (11), p represents an integer of 4 to 10, and represents an integer of 1 to 3. In the above formula (1), R ² is a group represented by the formula (3), R ³ is a vinyl group (CH ₃ -CH ₂ -), and R ⁴ and R ⁵ are a methyl group. , n is 3, m is 5, and j is a compound represented by the following formula:

In the formula (12), p represents an integer of 4 to 10, and q represents an integer of 1 to 3. In the above formula (1), R ² is a group represented by the formula (6), R ⁴ is a methyl group, n is 5, m is 5, and j is 0. compound of:

In the formula (13), p represents an integer of 4 to 10. In the above formula (1), R ² is a group represented by the formula (6), R ³ is a vinyl group (CH ₃ -CH ₂ -), R ⁴ is a methyl group, and n is 5, m is 3, and j is a compound represented by the following formula:

[In the formula (14), p represents an integer of 4 to 10], of formula (15) is a group represented by the above general formula (1), R ² is of formula (3), R ⁴ and R ⁵ is methyl , n is 4, m is 8, and j is a compound represented by the following formula:

[In the formula (15), p represents an integer of 4 to 10, and q represents an integer of 1 to 3. In the above formula (1), R ² is a group represented by the formula (3), R ⁴ and R ⁵ are a methyl group, n is 7, m is 5, and j is 0. Compound represented by the formula:

[In the formula (16), p represents an integer of 4 to 10, and q represents an integer of 1 to 3. In the above formula (1), R ² is a group represented by the formula (6), R ⁴ is a methyl group, n is 10, m is 2, and j is 0. compound of:

In the formula (17), p represents an integer of 4 to 10. In the above formula (1), R ² is a group represented by the formula (6), R ³ is a vinyl group (CH ₃ -CH ₂ -), R ⁴ is a methyl group, and n is 4, m is 2, and j is a compound represented by the following formula:

In the formula (18), p represents an integer of 4 to 10. ].

In the method for producing a cage sesquioxane compound, for example, first, an anthracene compound (A) represented by the following formula (19): R ¹ SiX ₃ . . . (19)

[In the formula (19), R ¹ is ^a synonymous R (1) in the formula, X represents an alkoxy group the freedom to choose any one of the group of hydrolyzable groups consisting of acetyl group, a halogen atom and a hydroxyl group . ], an anthracene compound (B) represented by the following formula (20): R ² SiY ₃ . . . (20)

In the formula (20), R ² is synonymous with R ² in the above formula (1), and Y is a hydrolyzable property indicating any one selected from the group consisting of a free alkoxy group, an ethenyloxy group, a halogen atom and a hydroxyl group. Base], and if necessary, an anthracene compound (C) represented by the following formula (21): R ³ SiZ ₃ . . . (twenty one)

In the formula (21), R ³ is synonymous with R ³ in the above formula (1), and Z is a hydrolyzable property of any one selected from the group consisting of a free alkoxy group, an ethenyloxy group, a halogen atom and a hydroxyl group. base. The mixture is mixed and hydrolyzed in water in the presence of a basic catalyst to partially condense, and then the resulting hydrolysis reaction product is recondensed in the presence of a basic catalyst and a non-polar solvent.

The above hydrazine compound (A) may, for example, be 4-methylpropoxy butyl trimethoxy decane, 4-methyl propylene oxy triethoxy decane or 5-methyl propylene oxide. Pentyl trimethoxy decane, 5-methyl propylene oxy pentyl triethoxy decane, 6-methyl propylene oxy hexyl trimethoxy decane, 6-methyl propylene oxy hexyl triethoxy decane, 7-Methylacryloxyheptyltrimethoxydecane, 7-methylpropenyloxyheptyltriethoxydecane, 8-methylpropoxyoctyltrimethoxydecane, 8-methylpropenyloxy Octyltriethoxydecane, 8-propoxyoctyltrimethoxydecane, 8-propenyloxyoctyltriethoxydecane, 9-methylpropenyloxydecyltrimethoxydecane, 9-A These may be used alone or in combination of two kinds of acryloxymethyl triethoxy decane, 10-methyl acryloxy decyl trimethoxy decane, 10-methyl acryloxy decyl triethoxy decane, and the like. The above combination is used, and among them, 8-(meth) propylene hexyl hexyl methoxy decane is preferable from the viewpoint of easy starting of the raw material.

The above hydrazine compound (B) is exemplified by (meth) acryloxymethyl three Methoxydecane, (meth) propyleneoxymethyl triethyl decane, 3-(meth) propylene oxy propyl trimethoxy decane, 3-(methyl) propylene oxy propyl triethoxy Decane, 3-propoxypropyltrimethoxydecane, 3-propoxypropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxy These may be used alone or in combination of two or more kinds, such as cyclohexyl)ethyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, or vinyltrichloromethane. Among them, from the viewpoint of easy starting of the raw materials, 3-(meth)acryloxypropyltrimethoxydecane, 3-oxopropoxypropyltrimethoxydecane, 2-(3,4-epoxy) are used. Cyclohexyl)ethyltrimethoxydecane and vinyltrimethoxydecane are preferred.

The hydrazine compound (C) may, for example, be phenyltrimethoxydecane or benzene. Triethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethyl Oxydecane, butyltrimethoxydecane, butyltriethoxydecane, pentyl Trimethoxy decane, pentyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, p-styryl trimethoxy decane, p-styryl triethoxy decane, etc. These may be used alone or in combination of two or more.

The hydrazine compound (A), the hydrazine compound (B) and the hydrazine compound The mixing ratio of (C) is a molar ratio (the molar number of B: the molar number of A) of the ruthenium compound (A) and the ruthenium compound (B) is 1:4 to 13:1, The molar ratio (the molar number of A+B: the molar number of C) of the aforementioned hydrazine compound (C) in which the total hydrazone compound (A) and the hydrazine compound (B) are combined is 1:0 to 2: 5 is ideal, and mixing is preferably 1:0 to 2:3.

The alkaline catalyst may, for example, be potassium hydroxide, sodium hydroxide or hydrogen. An alkali metal hydroxide such as cerium oxide; tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide or the like Ammonium hydroxide salt. Among them, tetramethylammonium hydroxide is preferably used from the viewpoint of high catalytic activity in the hydrolysis reaction. The amount of the basic catalyst is preferably 0.01 to 20% by mass based on the total mass of the above-mentioned ruthenium compounds (A) to (C). Here, the above basic catalyst is usually an aqueous solution.

There must be water in the aforementioned hydrolysis reaction, but this can be as described above. The aqueous solution of the alkaline catalyst may be supplied with water. The amount of water may be preferably from 1.0 to 1.5 times the theoretical amount (mass) of the hydrolyzable group calculated from the mass of the deuterated oxygen species (A) to (C) as long as it is sufficient to hydrolyze the hydrolyzable group.

Further, in the hydrolysis reaction, a non-polar solvent and/or a polarity is used. Solvents are ideal. In such a solvent, when the non-polar solvent is used only, the reaction system is not uniform, the hydrolysis reaction does not proceed sufficiently, and the unreacted hydrolyzable group tends to remain, and both the non-polar solvent and the polar solvent are used, or Use only polar solvents miss you.

As the polar solvent, an alcohol such as methanol, ethanol or 2-propanol or another polar solvent can be used. Among them, a lower alcohol having a carbon number of 1 to 6 which is soluble in water is preferred, and 2-propanol is more preferred. The amount of the nonpolar solvent and/or the polar solvent to be used is preferably in the range of 0.01 to 10 M in terms of the total molar concentration (mol/liter: M) of the above-mentioned cerium compounds (A) to (C).

In the reaction conditions of the foregoing hydrolysis, the reaction temperature is preferably from 0 to 60 ° C, more preferably from 20 to 40 ° C. When the reaction temperature is less than the lower limit, the reaction rate is slow, and the hydrolyzable group remains in an unreacted state, and the reaction time tends to be long. On the other hand, when the reaction temperature exceeds the above upper limit, the reaction rate is too fast and a complicated condensation reaction proceeds, and as a result, the polymerization of the hydrolysis reaction product tends to be promoted. Further, in the reaction conditions for the hydrolysis, the reaction time is preferably 2 hours or longer. When the reaction time is less than the above lower limit, the hydrolysis reaction does not proceed sufficiently, and the hydrolyzable group tends to remain in an unreacted state.

After the completion of the hydrolysis reaction, a method of recovering the hydrolysis reaction product is a method in which a weakly acidic solution is first used to make the reaction solution neutral or acidic, and then water or an aqueous reaction solvent is separated. Examples of the weakly acidic solution include a sulfuric acid dilution solution, a hydrochloric acid dilution solution, a citric acid solution, acetic acid, an ammonium chloride aqueous solution, a malic acid solution, a phosphoric acid solution, an oxalic acid solution, and the like. In addition, the method of separating the water or the aqueous reaction solvent may be a method in which the reaction solution is washed with saline or the like to sufficiently remove water and other impurities, and then dried with a desiccant such as anhydrous magnesium sulfate.

Further, the solvent may be used as a method for recovering a hydrolysis reaction product when a polar solvent is used. First, the polar solvent is removed by evaporation under reduced pressure or the like, and then, A method of washing and drying in the same manner as described above after adding a non-polar solvent to dissolve the hydrolysis reaction product. Further, when the solvent is a non-polar solvent, the non-polar solvent can be separated by means of evaporation or the like to recover the hydrolysis reaction product. However, if the non-polar solvent can be used as a non-polar solvent in the next recondensation reaction, , there is no need to separate it.

Since in the aforementioned hydrolysis reaction, hydrolyzate occurs simultaneously with hydrolysis a condensation reaction, so that most of the hydrolyzable groups in the above ruthenium compounds (A) to (C) in the hydrolysis reaction are desirably almost entirely substituted by an OH group, and further, the OH group is formed by the aforementioned condensation reaction. Most, ideally more than 80% are condensed. Therefore, the hydrolysis reaction product contains a polycondensate produced by the condensation described above, and the polymerization condensate differs depending on the reaction conditions, but is a resin (or oligomer) having a number average molecular weight of 500 to 10,000. The mixture is composed of a plurality of types of cages, incomplete cages, ladder type (ladder type), and a random type of oxime, and the cage of the present invention is contained in the above-mentioned cage-structured siloxane. A type of sesquioxane compound.

In the method for producing a cage sesquioxane compound of the present invention, The hydrolysis reaction product is heated in the presence of a non-polar solvent and a basic catalyst to condense a helium-oxygen bond (referred to as recondensation) to selectively produce a recondensate (carotate of a cage structure). ideal.

In the case of the aforementioned non-polar solvent, it has no solubility with water, or almost no However, a hydrocarbon solvent is preferred. The hydrocarbon-based solvent may, for example, be a non-polar solvent having a low melting point such as toluene, benzene or xylene. Among them, toluene is particularly preferred. The amount of the non-polar melt solvent to be used is preferably an amount sufficient to dissolve the hydrolysis reaction product, and is preferably 0.1 to 20 times the total mass of the hydrolysis reaction product.

In the foregoing alkaline catalyst, it can be used in the aforementioned hydrolysis reaction. The alkaline catalyst is preferably a catalyst which is soluble in a non-polar solvent such as tetraalkylammonium. The amount of the basic catalyst is preferably from 0.01 to 20% by mass based on the hydrolysis reaction product.

In the reaction conditions of the foregoing recondensation reaction, the reaction temperature is 90 to 200 ° C is ideal, and 100 to 140 ° C is more desirable. When the reaction temperature is less than the above lower limit, a sufficient driving force for causing the recondensation reaction cannot be obtained, and the reaction tends not to proceed. On the other hand, when the reaction temperature exceeds the above upper limit, the reactive organic functional group such as a vinyl group or a (meth) acrylonitrile group may cause an autopolymerization reaction. Therefore, it is necessary to suppress the reaction temperature or to add a polymerization inhibitor. The tendency of the agent or the like. Further, in the reaction conditions of the above recondensation reaction, the reaction time is preferably from 2 to 12 hours.

Further, in the case of the hydrolysis reaction product used for recondensation, the use of The product which has been washed and dried as described above and re-concentrated is preferable, but it can be used without these treatments. Further, in the recondensation reaction, water may be present, but it is not necessary to actively add it, and it is preferable to stop the moisture supplied from the alkaline catalyst solution. However, when the hydrolysis is not sufficiently carried out, it is preferred to add water in an amount necessary to hydrolyze the remaining hydrolyzable group.

In the method for producing a cage sesquioxane compound of the present invention, The above-mentioned recondensation reaction solution is washed to remove the catalyst, and the recondensation product obtained by concentration in a rotary evaporator or the like can be obtained depending on the type of the functional group, the reaction conditions, and the state of the hydrolysis reaction product. A mixture of the cage sesquiterpoxide compounds of the present invention represented by the formula (1) (ideally, the formulae (7) to (18)). When the cage sesquioxaperane compound of the present invention contains 40% by mass or more of the reaction product, the reaction will occur. When the product is directly formulated in a curable resin composition to be described later, the effect of the cage type sesquioxaperane compound of the present invention can be sufficiently obtained.

Next, the curable resin composition of the present invention will be described. The invention The curable resin composition contains the above-described cage sesquiterpene oxide compound and a radical polymerization initiator of the present invention, and the cage sesquioxane compound has a characteristic content of 10 to 80% by mass.

In the curable resin composition of the present invention, the aforementioned cage type sesquiterpene The oxane compound may be contained alone or in combination of two or more kinds, and the reaction product may be used as it is. The content of the above-mentioned cage type sesquiterpene oxide compound is required to be 10 to 80% by mass based on the total amount of the curable resin composition of the present invention. When the content of the cage sesquioxane compound is less than the above lower limit, the compatibility between the curable resin composition and the physical properties such as transparency and low water absorbability of the obtained cured resin are lowered. On the other hand, when the above upper limit is exceeded, the viscosity of the curable resin composition increases to make the production of the molded article difficult. In addition, the content of the cage sesquioxane compound is preferably from 15 to 80% by mass in view of the fact that the transparency and the low water absorbability are better. In the present invention, when the curable resin composition contains a volatile solvent, the amount of each component such as the cage sesquioxane compound in the curable resin composition means removing the volatile matter. The content of the mass of the curable resin composition of the mass of the solvent is in terms of the mass.

In the curable resin composition of the present invention, the ratio of the number of R ^{1 to the} number of R ² of the reactive functional group in the general formula (1) in the entire cage sesquiterpene oxide compound (R ² : R ¹ ) is ideal from 1:6 to 13:1. When the content of R ¹ is less than the lower limit, the adaptability of the cage sesquioxane compound is lowered, and the radical polymerizability tends to be lowered. On the other hand, when the content exceeds the upper limit, the hydrocarbon chain content is large. The cage type sesquiterpene oxide compound tends to have a lower polarity and a lower compatibility with other resins. Further, from the viewpoint of the moldability of the resin composition, the transparency of the obtained cured resin, the low water absorbability and the weather resistance, the ratio (R ² : R ¹ ) is 1:4 to 13 :1 is more ideal.

The above-mentioned radical polymerization initiator may be a thermal polymerization initiator and Photopolymerization initiator. In the curable resin composition of the present invention, the radical polymerization of the cage sesquioxane compound is promoted by the radical polymerization initiator, and a cured resin having excellent strength and rigidity can be obtained.

The aforementioned thermal polymerization initiator is a curable resin composition of the present invention Used when heat hardening. An organic peroxide is preferred for such a thermal polymerization meeting agent, and examples of the organic peroxide include ketone peroxides, dimercapto peroxides, hydroperoxides, and dialkyl peroxy groups. Substances, peroxy ketals, alkyl peroxyesters, percarbonates, and the like. Among them, dialkyl peroxide is preferred from the viewpoint of high catalytic activity. Specific examples of the dialkyl peroxide include cyclohexanone peroxide, 1,1-bis(tri-hexylperoxy)cyclohexanone, and cumene hydroperoxide. ), dicumyl peroxide, dibenzoyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tertiary hexylperoxydiisopropyl monocarbonate, third Base peroxy-2 ethylhexanoate and the like. One type of the above-mentioned thermal polymerization initiator may be used singly or in combination of two or more types.

The aforementioned photopolymerization initiator is composed of the curable resin of the present invention. Use when the material is hardened by light. For the photopolymerization initiator, acetophenones, benzoin, benzophenones, thioxanthones, mercaptophosphine oxides are used. Compounds such as (acylphosphine oxide) are preferred. Specifically, trichloroacetophenone, diethylacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl 1-(4-methylthienyl)-2-morpholinylpropan-1-one, benzoin methyl ether, dimethylbenzyl ketone, benzophenone, thioxanthone, 2,4,6 - 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, Methyl phenylglyoxylate, camphorquinone, benzyl alcohol, hydrazine, Michler ( Michler's ketone) and so on. The photopolymerization initiator may be used alone or in combination of two or more.

In the radical polymerization initiator of the present invention, the aforementioned heat polymerization can be carried out The initiator or the photopolymerization initiator may be used singly or in combination. The content of the radical polymerization initiator is preferably from 0.01 to 10% by mass, more preferably from 0.05 to 5% by mass, in the curable resin composition of the present invention. When the content is less than the lower limit, the hardness of the composition is insufficient, and the strength and rigidity of the obtained cured product (molded body) tend to be low. On the other hand, when the content exceeds the upper limit, the molded article tends to cause coloring.

The curable resin composition of the present invention further comprises the aforementioned cage An unsaturated compound having a (meth)acryl fluorenyl group other than the sesquioxane compound, the ladder siloxane, and the random siloxane is preferable. When such an unsaturated compound is contained, the viscosity of the curable resin composition and the physical properties such as rigidity and strength of the obtained resin hard substance can be adjusted within a desired range.

The above (meth)acryl fluorenyl unsaturated compound (hereinafter, sometimes Referred to as an unsaturated compound. In the above, the cage sesquioxane compound of the present invention, a compound other than a ladder type siloxane and a random siloxane, and the above-described caged sesquitained siloxane compound of the present invention may be used. Free radical copolymerized (meth) acrylonitrile However, there is no particular limitation. However, when the viscosity of the curable resin composition is high, the production of the cured resin tends to be difficult, and the reactivity of the polymer having a repeat number of the structural unit of 2 to 20 is low. Polymers, low molecular weight and/or low viscosity reactive monomers and the like are preferred.

The aforementioned reactive oligomers include epoxy acrylates and rings. Oxidized acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene/thiol, decyl acrylate, polystyrene methacrylate, etc. . Further, examples of the reactive monomer include butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isodecyl acrylate, dicyclopentenyl acrylate. a monofunctional monomer such as ethyl ester, phenoxyethyl acrylate or trifluoroethyl acrylate; dicyclopentane diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1 , 9-decanediol acrylate, dimethylol tricyclodecane diacrylate, bisphenyl A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxytrimethyl acetic acid A polyfunctional monomer such as pentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or the like. One type of the above-mentioned unsaturated compound may be used alone or two or more types may be used in combination.

When the curable resin composition of the present invention contains such an unsaturated compound, the mass ratio of the cage type sesquiterpene oxide compound of the present invention in terms of the content thereof (cage sesquioxane compound: unsaturated) The compound) is ideal in a mass of from 10:90 to 80:20. When the content is less than the lower limit, the viscosity of the curable resin composition tends to increase, and the moldability tends to decrease. On the other hand, when the content exceeds the upper limit, the compatibility of the curable resin composition and the obtained cured resin are obtained. Transparency, low heat expansion, Physical properties such as low water absorption tend to decrease.

Moreover, the curable resin composition of the present invention does not lose the present Further, in the range of the effects of the invention, a ladder-type siloxane and/or a random siloxane may be further contained, and the oxime may be a side reaction in the production of the above-mentioned cage sesquioxane resin. a he formed alkane.

The curable resin composition of the present invention contains such a ladder type siloxane and In the case of a random type of decane, the total content (mass) of the cage sesquioxane compound of the present invention is a, and the content (mass) of the unsaturated compound is In the case where b, the content (mass) of the ladder-type siloxane and the random siloxane is c, it is desirable to satisfy the following formula: 10/90 ≦a/(b+c) ≦ 80/20, It is more desirable to satisfy the condition expressed by the following formula: 20/80≦a/(b+c)≦75/25.

When the content of the cage sesquioxane compound is less than the lower limit, the compatibility of the curable resin composition and the transparency of the obtained cured resin, the low thermal expansion property, and the low water property tend to be lowered. . On the other hand, when it exceeds the above upper limit, the viscosity of the curable resin composition increases, and the formability tends to decrease. Therefore, when the reaction product of the above-described cage-type sesquiterpene oxide is used as it is, the product which satisfies the above conditions is preferably added as needed.

Moreover, the curable resin composition of the present invention does not lose the present In the range of the effect of improving the physical properties of the cured resin, and/or radical polymerization, etc., it is possible to further contain a thermal polymerization accelerator, a photo-starting adjuvant, a sharpening agent, and the like. Further, the curable resin composition of the present invention may further contain organic/ Inorganic filler, inorganic filler, plasticizer, flame retardant, thermal stabilizer, antioxidant, light stabilizer, ultraviolet absorber, lubricant, antistatic agent, release agent, foaming agent, colorant, cross-linking Various additives such as a dispersing agent, a dispersing aid, and a resin component.

In addition, the curable resin composition of the present invention has a thickness of 0.2 mm, and is irradiated with a high-pressure mercury lamp having an illuminance of 30 W/cm at room temperature to accumulate light having an exposure amount of 2000 mJ/cm ² to cause radical polymerization. The reaction rate of the (meth) acrylonitrile group measured by infrared spectroscopy is preferably 70% or more, and more preferably 85% or more. The reaction rate of the aforementioned (meth) acrylonitrile group is as described above.

The conventional curable resin composition is also made to contain the aforementioned The saturated compound can increase the reaction rate of the (meth) acrylonitrile group. However, the water absorbing property of the cured resin obtained by increasing the content of the (meth) acrylonitrile group increases, and the water absorbing property is deteriorated. In addition, when the content of the unsaturated compound is increased, the weather resistance of the obtained resin cured product to ultraviolet rays or the like is lowered. On the other hand, since the curable resin composition of the present invention contains the above-described cage type sesquiterpoxysilane compound of the present invention, the reaction rate of the (meth) acrylonitrile group is also sufficient when the unsaturated compound is not contained. When the residual amount of the unreacted group of the obtained cured resin is sufficiently reduced, a cured resin having excellent weather resistance and low water absorbability can be obtained.

Next, the cured resin of the present invention will be described. The resin of the invention is hard The compound is obtained by radical polymerization of the curable resin composition of the present invention. The method of the radical polymerization described above may be a method of heat curing by heating or a method of curing by light irradiation. In the present invention, any of the above-described thermosetting and photocuring may be used singly, or a combination of both may be used.

In the case of the above-mentioned thermal curing, the thermal polymerization initiator and, if necessary, a thermal polymerization accelerator may be appropriately selected, and the reaction temperature may be from room temperature (25 ° C) to At a temperature of 200 ° C, the reaction time is a wide range of choices ranging from 0.5 to 10 hours. Moreover, in the present invention, the curable resin composition can be polymerized and cured in a metal mold or a steel conveyor belt to have a desired shape. In the method of obtaining such a molded body, all of the general molding processing methods such as injection molding, extrusion molding, compression molding, transfer molding, calender molding, and injection molding can be applied.

The method of photohardening described above may, for example, be a wavelength of 10 to A method of irradiating the curable resin composition to the ultraviolet light of 400 nm or the visible light of the wavelength of 400 to 700 nm for about 1 to 1200 seconds. The aforementioned wavelength is not particularly limited, and a near ultraviolet light having a wavelength of 200 to 400 nm is desirable. As the lamp used as the source of the ultraviolet rays, for example, a low-pressure mercury lamp (output: 0.4 to 4 W/cm), a high-pressure mercury lamp (40 to 160 W/cm), and an ultra-high pressure mercury lamp (173 to 435 W/cm) can be mentioned. A metal halide lamp (80 to 160 W/cm) or the like can be appropriately selected depending on the kind of the photopolymerization initiator to be used, the kind of the light-starting adjuvant and the type of the sharpening agent. In the present invention, for example, a method in which the curable resin composition is injected into a mold made of a transparent material such as quartz glass, and is cured by radical polymerization, and a molded body having a desired shape is produced by demolding the mold. A molded body having a desired shape can be obtained by a method of hardening the steel belt as described above or the like.

[Examples]

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the following examples. Further, in each of the synthesis examples, GPC and mass analysis were carried out by the methods described below.

(GPC (colloidal osmosis chromatography))

Using a colloidal permeation chromatography (GPC) (device name: HLC-8320GPC (manufactured by Tosoh Corporation), solvent: THF, column: ultra-high-speed semi-micro SEC column SuperH system, Temperature: 40 ° C, speed: 0.6 ml / min). The number average molecular weight (Mn) and the molecular weight distribution (weight average molecular weight/number average molecular weight (Mw/Mn)) were determined as converted values of standard polystyrene (trade name: TSK-GEL, manufactured by Tosoh Corporation).

(quality analysis)

Electrospray ionization mass spectrometry (ESI-MS) apparatus (device name: LC apparatus; separation module 2690 Waters Co., Ltd.), MS apparatus; ZMD4000 (manufactured by Micromass Co., Ltd.), measurement conditions: electrospray ionization Method, capillary voltage: 3.5 kV, cone voltage: +30 V).

(Synthesis Example 1)

First, in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 120 ml of 2-propanol (IPA) as a solvent, 150 ml of toluene, and 5% tetramethylammonium hydroxide aqueous solution of an alkaline catalyst (TMAH aqueous solution) were charged. ) 30.0ml. Then, 8-methylpropenyloctyltrimethoxydecane (KBM-5 803, manufactured by Shin-Etsu Chemical Co., Ltd.) 66.87 g (0.21 mol) and 3-methacryloxypropyltrimethoxydecane (SZ-6300, manufactured by Toray. Dow Croning. Silicone Co., Ltd.) 52.15 g (0.21 mol) was mixed and added to a dropping funnel, and it was dropped into the above reaction vessel for 30 minutes while stirring at room temperature (about 25 ° C). . After the completion of the dropwise addition, the mixture was stirred without heating for 2 hours. The solution (reaction solution) in the stirred reaction vessel was adjusted to neutral (pH 7) with a citric acid aqueous solution, and then the organic phase and the aqueous phase were separated by adding pure water, and 10.0 g of anhydrous magnesium sulfate was added to the organic phase to be dehydrated. . The above anhydrous magnesium sulfate was removed by filtration, and concentrated by a rotary evaporator to obtain a hydrolysis reaction product (sesquioxane) 81.03 g. This hydrolysis reaction product is a colorless viscous liquid which is soluble in various organic solvents.

Then, in a reaction vessel equipped with a mixer, a Dean Stark separator, and a cooling tube, the hydrolysis reaction obtained above is charged. 45.0 g of a product, 270 ml of toluene, and 6.5 ml of a 10% aqueous solution of TMAH were slowly heated to distill off water. The recondensation reaction was carried out by heating to 130 ° C at the reflux temperature of toluene. The temperature at this time was 106 °C. After refluxing of toluene, the mixture was stirred for 2 hours, and the reaction was terminated. The solution (reaction solution) in the reaction vessel after the stirring was adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water was added to separate the organic phase and the aqueous phase, and 10.0 g of anhydrous magnesium sulfate was added to the organic phase to be dehydrated. The above anhydrous magnesium sulfate was removed by filtration and concentrated on a rotary evaporator to yield 69.68 g of the resin mixture 1. The obtained resin mixture 1 is a colorless viscous liquid which is soluble in various organic solvents.

The GPC and mass analysis results of the obtained resin mixture 1 are shown in Fig. 1 and Fig. 2, respectively. In the result of GPC (chromatogram), a cage type sesquiterpene oxide resin containing a formula (1) (n+m) larger than 14 was detected, a ladder type siloxane, and a random type of argon gas were detected. Peak 1 of the alkane (Mw = 4,501, Mw / Mn = 1.06), and spike 2 containing the above (n + m) of the cage sesquiterpene oxide resin of 14 or less (Mw = 2,012, Mw / Mn = 1.03) From the results of the results and the mass analysis, it was confirmed that the obtained resin mixture 1 was a resin mixture containing the cage sesquioxaxane resin represented by the following formula (I): [CH ₂ =C(CH ₃ )COOC ₈ H ₁₆ SiO _3/2 ] _n [CH ₂ =C(CH ₃ )COOC ₃ H ₆ SiO _3/2 ] _m . . . (I).

Here, in the obtained resin mixture 1, the content of the cage sesquioxane resin represented by the above formula (I) is 81% by mass.

(Synthesis Example 2)

2-propanol (IPA) was set to 70 ml, toluene was 170 ml, and 8-(meth)acryloxyoctyltrimethoxydecane was 92.7 g (0.29 mol), 3-methylpropoxypropyltrimethoxy In the same manner as in Synthesis Example 1, except that the decane was 24.1 g (0.097 mol), 82.30 g of a hydrolysis reaction product (sesquioxane) was obtained. This hydrolysis reaction product is a variety of organic Solvent-soluble, colorless, viscous liquid. Then, the resin mixture 2 of 36.55 g was obtained in the same manner as in Synthesis Example 1 except that 40.0 g of the hydrolysis reaction product was used and the toluene was changed to 130 ml. The obtained resin mixture 2 is a colorless viscous liquid which is soluble in various organic solvents.

A graph (chromatogram) of the result of GPC of the obtained resin mixture 2 Shown in Figure 3. In the chromatogram, the peak 1 (Mw) of the cage sesquioxane resin, the ladder type siloxane, and the random siloxane having the formula (I) (n+m) larger than 14 was detected. =4,460, Mw/Mn=1.03), and the peak 2 (Mw=2,140, Mw/Mn=1.03) of the cage sesquioxane resin containing the above (n+m) of 14 or less, thereby obtaining results and quality As a result of the analysis, it was confirmed that the obtained resin mixture 2 was a resin mixture containing the cage type sesquiterpene oxide resin represented by the above formula (I). In the resin mixture 2 obtained here, the content of the cage sesquioxane resin represented by the above formula (I) is 83% by mass.

(Synthesis Example 3)

In addition to setting 2-propanol (IPA) to be 90 ml, 8-methylpropoxy octyltrimethoxydecane to be 28.32 g (0.089 mol), and 3-methylpropoxypropyltrimethoxydecane to be 66.26 g ( In the same manner as in Synthesis Example 1, a hydrolysis reaction product (62.30 g of sesquiterpene oxide) was obtained in the same manner as in Synthesis Example 1. The hydrolysis reaction product was a colorless viscous liquid which was soluble in various organic solvents. 34.80 g of the resin mixture 3 was obtained in the same manner as in Synthesis Example 1 except for 43.0 g of the hydrolysis reaction product. The obtained resin mixture 2 was a colorless viscous liquid which was soluble in various organic solvents.

The GPC result chart (chromatogram) of the obtained resin mixture 3 is shown in Figure 4. In the chromatogram, the peak of the cage sesquioxane resin, the ladder-type siloxane, and the random siloxane having the formula (I) (n+m) larger than 14 was detected ( Mw=4,012, Mw/Mn to 1.10), and cage type sesquiterpene oxide resin containing the above (n+m) of 14 or less The peak 2 (Mw = 1,640, Mw / Mn = 1.41), and the result of the mass analysis, confirmed that the obtained resin mixture 3 was a resin mixture containing the cage type sesquiterpene oxide resin represented by the above formula (I). In the resin mixture 3 obtained here, the content of the cage sesquioxane resin represented by the above formula (I) is 68% by mass.

(Synthesis Example 4)

In place of 2-propanol (IPA) of 60 ml, toluene of 100 ml, and 8-methylpropenyl octyloctyltrimethoxydecane of 87.25 g (0.27 mol) instead of 3-methylpropoxypropyltrimethoxy In the same manner as in Synthesis Example 1, except that 40.61 g (0.27 mol) of vinyl trimethoxydecane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the decane, a hydrolysis reaction product (sesquioxane) 65.94 g was obtained. . This hydrolysis reaction product is a colorless viscous liquid which is soluble in various organic solvents. Then, the hydrolysis reaction product was used, and 38.20 g of a resin mixture 4 was obtained in the same manner as in Synthesis Example 1 except that the reflux temperature of toluene was 108 °C. The obtained resin mixture 4 is a colorless viscous liquid which is soluble in various organic solvents.

The GPC result chart (chromatogram) of the obtained resin mixture 4 is shown in Fig. 5. In the chromatogram, the peak of the cage sesquioxane resin, the ladder-type siloxane, and the random siloxane having the formula (I) (n+m) larger than 14 was detected ( Mw=3.528, Mw/Mn=1.21), and the peak 2 (Mw=1, 306, Mw/Mn=1.03) of the cage sesquioxane resin containing (n+m) of 14 or less, and the result thereof As a result of the mass spectrometry, it was confirmed that the obtained resin mixture 4 was a resin mixture containing the cage sesquiterpene oxide resin represented by the following formula (II): [CH ₂ = C(CH ₃ )COOC ₈ H ₁₆ SiO _3/2 ] _n [CH ₂ =CHSi0 _3/2 ] _m . . . (II).

In the resin mixture 4 obtained here, the cage type sesquiterpenes represented by the above formula (II) The content of the oxyalkylene resin was 75% by mass.

(Synthesis Example 5)

In addition to 2-propanol (IPA) 100 ml, toluene 240 ml, 8-methylpropenyloctyltrimethoxydecane 38.16 g (0.12 mol), 3-methylpropoxypropyltrimethoxydecane 9.92 g ( 0.04 mol), and further, 24.00 g (0.16 mol) of ethyl methoxy decane (LS-890, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the dropping funnel, and the hydrolysis reaction product was obtained in the same manner as in Synthesis Example 1. (sesquioxane) 45.20g. This hydrolysis reaction product is a colorless viscous liquid which is soluble in various organic solvents. Then, 40.0 g of the hydrolysis reaction product was used, and 36.05 g of a resin mixture 5 was obtained in the same manner as in Synthesis Example 1 except that the reflux temperature of toluene was 108 °C. The obtained resin mixture 4 is a colorless viscous liquid which is soluble in various organic solvents.

The GPC result chart (chromatogram) of the obtained resin mixture 4 is shown in Fig. 5. In the chromatogram, the peak of the cage sesquioxane resin, the ladder-type siloxane, and the random siloxane having the formula (I) (n+m) larger than 14 was detected ( Mw=31,652, Mw/Mn=1.21), and the peak 2 (Mw=1,295, Mw/Mn=1.03) of the cage sesquioxane resin containing the above (n+m) of 14 or less, and the result As a result of mass spectrometry, it was confirmed that the obtained resin mixture 5 was a resin mixture containing a cage sesquioxane resin represented by the following formula (III): Formula (III): [CH ₂ =C(CH ₃ )COOC ₈ H ₁₆ Si0 _3/2 ] _n [CH ₂ =C(CH ₃ )COOC ₃ H ₆ Si0 _3/2 ] _m [CH ₃ CH ₂ Si0 _3/2 ] _j . . . (III).

In the resin mixture 5 obtained here, the content of the cage sesquioxane resin represented by the above formula (III) is 43% by mass.

(Synthesis Example 6)

Except that 2-propanol (IPA) was set to 60 ml, toluene was 120 ml, 3-methylpropoxypropyltrimethoxydecane was 69.27 g (0.28 mol), and 8-methylpropenyl octyltrimethoxy was not used. In the same manner as in Synthesis Example 1, except for the decane, 48.36 g of a hydrolysis reaction product (sesquioxane) was obtained. This hydrolysis reaction product is a colorless viscous liquid which is soluble in various organic solvents. Then, 41.40 g of the resin mixture 6 was obtained in the same manner as in Synthesis Example 1 except that the toluene reaction product was used. The obtained resin mixture 6 is a colorless viscous liquid which is soluble in various organic solvents.

The GPC result chart (chromatogram) of the obtained resin mixture 6 is shown in Fig. 7. In the chromatogram, a spike 1 (Mw = 1,769, Mw/Mn = 1.08) containing a permethacryloxy-cage sesquioxane resin was detected, and the results and mass analysis results confirmed the obtained resin. Mixture 6 is represented by the following formula (IV): [CH ₂ =C(CH ₃ )COOC ₃ H ₆ Si0 _3/2 ] _m . . . (IV)

m is a resin mixture of 10 cage sesquioxane resins. In the resin mixture 6 obtained here, the content of the cage sesquioxane resin represented by the above formula (IV) is 84% by mass.

(Synthesis Example 7)

In addition to setting 2-propanol (IPA) to 80 ml, toluene to 160 ml, 3-methylpropoxypropyltrimethoxydecane to 48.06 g (0.19 mol) instead of 8-methylpropenyloctyltrimethoxy In the same manner as in Synthesis Example 1, except that 28.68 g (0.19 mol) of ethylene trimethoxy decane was used as the decane, 48.68 g of a hydrolysis reaction product (sesquioxane) was obtained, and the hydrolysis reaction product was referred to as a resin mixture 7.

The GPC result chart (chromatogram) of the obtained resin mixture 7 is shown in Fig. 8. In the chromatogram, a cage type sesquiterpene oxide resin having a larger (m'+m'') of the following formula (V) than 14 is detected, a ladder type siloxane, and a random type of oxygen is detected. The peak of the alkane 1 (Mw = 6,047, Mw / Mn = 1.05), and the peak 2 of the cage sesquiterpene oxide resin containing the above (m' + m'') of 14 or less (Mw = 1,891, Mw / Mn) =1.41) From the results and the results of the mass analysis, it was confirmed that the obtained resin mixture 7 was a resin mixture containing the cage sesquioxaxane resin represented by the following formula (V): [CH ₂ = C(CH ₃ )COOC ₃ H ₆ SiO _3/2 ] _m' [CH ₂ =CHSiO _3/2 ]m _'' . . . (V).

In the resin mixture 7 obtained here, the content of the cage sesquioxane resin represented by the above formula (V) is 40% by mass. .

(Synthesis Example 8)

In addition to setting 2-propanol (IPA) to 130 ml, toluene to 260 ml, not using 8-methylpropenyl octyltrimethoxydecane, instead of 3-methylpropoxypropyltrimethoxydecane, vinyl was used. The hydrolysis reaction product (sesquioxane) 44.03 g was obtained in the same manner as in Synthesis Example 1 except for trifluoromethane (93.65 g, 0.632 mol). This hydrolysis reaction product is a colorless viscous liquid which is soluble in various organic solvents. Then, 42.0 g of the hydrolysis reaction product was used, and 38.24 g of a resin mixture 8 was obtained in the same manner as in Synthesis Example 1 except that toluene was 260 ml. The obtained resin mixture 8 is a colorless viscous liquid which is soluble in various organic solvents.

The GPC result chart (chromatogram) of the obtained resin mixture 8 is shown in Fig. 9. In the chromatogram, a spike 1 containing a cage sesquioxane resin, a ladder type siloxane, and a random siloxane having a formula n (I) of 0, a ratio of m larger than 14 was detected ( Mw=3,229, Mw/Mn=1.40), and the peak 2 (Mw=797, Mw/Mn=1.41) of the all-vinyl cage sesquiterpene oxide resin having the above m of 14 or less, and the result and mass analysis As a result, it was confirmed that the obtained resin mixture 8 was a resin mixture containing a cage type sesquiterpene oxide resin represented by the following formula (VI): [CH ₂ =CHSi0 _3/2 ] _m . . . (VI).

In the resin mixture 8 obtained here, the content of the cage sesquioxane resin represented by the above formula (VI) is 83% by mass.

(Example 1)

First, 100 parts by mass of the resin mixture 1 containing the sesquioxaxane compound obtained in Synthesis Example 1 and 1-hydroxycyclohexyl phenyl ketone (Irg 184, Ciba. Japan) as a polymerization initiator Co., Ltd.) 2.5 mass parts are mixed to obtain a curable resin composition. Then, 2 g of the obtained curable resin composition was applied on a glass plate, a metal separator having a height of 0.2 mm was placed, and then a glass plate was placed thereon, and the resin composition was cast to a thickness of 0.2 mm by the weight of the glass plate itself, and then used. A 30 W/cm high-pressure mercury lamp was hardened at a cumulative exposure amount of 2000 mJ/cm ² to obtain a film-shaped resin cured product.

(Example 2)

First, a resin mixture 1 containing 70 parts by mass of the cage sesquioxane compound obtained in Synthesis Example 1 and 30 parts of dicyclopentyl diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) The mixture was mixed, and 1-hydroxycyclohexyl phenyl ketone (Irg 184, manufactured by Ciba. Japan Co., Ltd.) of the polymerization initiator was 1.5 parts by mass and dicumyl peroxide (dicumyl D). The grease is made of 1.0 mass parts, and a curable resin composition is obtained. Then, a film-like cured resin was obtained in the same manner as in Example 1 except that the obtained curable resin composition was used.

(Example 3)

A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 2 obtained in Synthesis Example 2 was used instead of the resin mixture 1.

(Example 4)

A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 2 obtained in Synthesis Example 2 was used instead of the resin mixture 1.

(Example 5)

A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 3 obtained in Synthesis Example 3 was used instead of the resin mixture 1.

(Example 6)

A curable resin composition and a barium compound were obtained in the same manner as in Example 2, except that the resin mixture 3 obtained in Synthesis Example 3 was used instead of the resin mixture 1.

(Example 7)

The same procedure as in Example 1 was carried out, except that the resin mixture 4 obtained in Synthesis Example 4 was used instead of the resin mixture 1 and the mass portion of 1.2 parts of dicyclopentyl diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) was further mixed. A curable resin composition is obtained. Then, the obtained curable resin composition was subjected to the same operation as in Example 1 except that the obtained curable resin composition was cured by a high pressure mercury lamp and then heated at 200 ° C for 1 hour in a nitrogen atmosphere to obtain a cured resin.

(Example 8)

A curable resin composition was obtained in the same manner as in Example 2 except that the resin mixture 4 obtained in Synthesis Example 4 was used instead of the resin mixture 1. Then, the cured resin composition obtained was cured in the same manner as in Example 2 except that the obtained curable resin composition was cured by a high pressure mercury lamp and then heated at 200 ° C for 1 hour in a nitrogen atmosphere.

(Example 9)

A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 5 obtained in Synthesis Example 5 was used instead of the resin mixture 1.

(Embodiment 10)

A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 5 obtained in Synthesis Example 5 was used instead of the resin mixture 1.

(Comparative Example 1)

A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 6 obtained in Synthesis Example 6 was used instead of the resin mixture 1.

(Comparative Example 2)

A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 6 obtained in Synthesis Example 6 was used instead of the resin mixture 1.

(Comparative Example 3)

The same procedure as in Example 1 was carried out except that the resin mixture 7 obtained in Synthesis Example 7 was used instead of the resin mixture 1 and the mass portion of dicyclopentyl diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) was further mixed. A curable resin composition. Then, in the same manner as in Example 2 except that the obtained curable resin composition was cured by a high-pressure mercury lamp and then heated at 200 ° C for 1 hour in a nitrogen atmosphere, a resin cured product was obtained in the same manner as in Example 1. Hardened resin.

(Comparative Example 4)

A curable resin composition was obtained in the same manner as in Example 2 except that the resin mixture 7 obtained in Synthesis Example 7 was used instead of the resin mixture 1. Then, the obtained cured resin composition was cured in the same manner as in Example 2 except that the obtained curable resin composition was cured by a high pressure mercury lamp and then heated at 200 ° C for 1 hour in a nitrogen atmosphere.

(Comparative Example 5)

The resin mixture 8 obtained in Synthesis Example 8 was used instead of the resin mixture 1, and dicyclopentyl diacrylate (DCP-A, Kyoeisha Chemical Co., Ltd.) was further mixed. In the same manner as in Example 1, except for the 1.0 mass portion, a curable resin composition was obtained. Then, the obtained cured resin composition was cured in the same manner as in Example 2 except that the obtained curable resin composition was cured by a high pressure mercury lamp and then heated at 200 ° C for 1 hour in a nitrogen atmosphere.

(Comparative Example 6)

A curable resin composition was obtained in the same manner as in Example 2 except that the resin mixture 8 obtained in Synthesis Example 8 was used instead of the resin mixture 1. Then, the obtained cured resin composition was cured in the same manner as in Example 2 except that the obtained curable resin composition was cured by a high pressure mercury lamp and then heated at 200 ° C for 1 hour in a nitrogen atmosphere.

The curable resin composition and the cured resin obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were measured for the reaction rate by the following methods, the measurement of the water absorption rate, the total light transmittance, and the weather resistance.

(Measurement of reaction rate)

First, the conspicuous resin composition obtained in each of the examples and the comparative examples was measured by using a microscopic infrared spectroscopic device (trade name: FT-IR6100, manufactured by JASCO Corporation) at 1728 cm ^-1 (methyl group). ) Bing Xixi carbon group - maximum absorbance (AW _{C = O)} stretching vibration oxygen double bonds (C = O) of and, from 1635cm ^-1 in the (meth) Bing Xixi group of a carbon - carbon double The maximum absorbance (AW _C=C ) of the stretching vibration of the key (C _=C ). Then, after the radical polymerization of the curable resin composition, the maximum absorbance (AF _C=O ) of the resin cured product obtained in each of the examples and the comparative examples at 1728 cm ^-1 and at 1635 cm ^-1 were measured in the same manner as above. Maximum absorbance (AF _C=C ). The ratio of AW _C=O to AW _C=C (AW=(AW _C=O /AW _C=C ), and the ratio of AF _C=O to AF _C=C (AF=AF _C=O /AF _{C =C} ), according to the following formula: double bond change rate (AR) = (1-AW/AF) × 100 to determine the double bond change rate (AR (%)) of the (meth) acryl fluorenyl group, which is taken as The reaction rate of (meth) acrylonitrile group. The results are shown in Table 1.

(Measurement of water absorption rate)

First, the obtained cured resin was kept at 50 ° C for 24 hours, and preliminary drying was carried out. Then, the water absorption rate was measured according to the method of plastic-water absorption (JISK7209). The results obtained are shown in Table 1.

(Measurement of total light transmittance)

The obtained resin cured product (thickness: 0.2 mm) was measured for transmitted light intensity and incident light intensity using NDH2000 (manufactured by Nippon Denshoku Co., Ltd.) according to the following formula: total light transmittance (%) = transmitted light intensity / incident light intensity

Calculate the total light transmittance. The results obtained are shown in Table 1.

(weatherability assessment)

The obtained resin cured product (having a thickness of 0.2 mm) was irradiated with ultraviolet rays for 72 hours using a QUV-accelerated Weathering Tester (light lamp rUVB-313J) manufactured by Q-Lab Co., Ltd. under the condition of a lamp distance of 5 cm. For the cured resin of the resin before and after exposure to ultraviolet light, the yellowness (YI) was determined according to the method of plastic-yellowness and yellowness (JISK7373). The results are shown in Table 1.

As is clear from the results shown in Table 1, it was confirmed that the cured resin obtained in Examples 1 to 10 had excellent transparency and low water absorbability, and was sufficiently excellent in weather resistance.

Further, the cracks of the cured resin obtained in Examples 1 to 10 were visually observed, and cracks and cracks were not observed in any of the cured products (films), and it was confirmed that the curable resin composition of the present invention has excellent formability. . On the other hand, in Comparative Examples 1 to 6, a cured product having a high transmittance was also obtained, but the yellowness of all the cured products after exposure to ultraviolet rays was high, and it was confirmed that the weather resistance was poor. Further, it was confirmed that the water-reducing ratio of the cured resin obtained in Comparative Examples 1 to 2 was particularly high. Here, the cured product of Comparative Example 5 was cracked, and a cured test piece of a size that can be measured could not be obtained.

[Industry use possibility]

As described above, according to the present invention, excellent forming can be provided A curable resin composition, a cage sesquiterpene compound having a resin cured product having excellent transparency and low water absorbability and excellent weather resistance, a curable resin composition using the compound, and a curable resin composition thereof Hardened resin cured product.

The resin cured product can be used as a substrate for a liquid crystal display element, and color a color filter substrate, an organic EL display element substrate, an electronic paper substrate, a TFT substrate, a transparent substrate such as a solar cell substrate, and a touch panel, a transparent electrode attachment film, a light guide plate, a protective film, a polarizing film, An optical film such as a phase difference film or a lens sheet, a glass substitute material such as various transportation machines, and a window material for a house can be used in a wide range of applications, and is extremely valuable in industrial use.

Claims (6)

A cage type sesquiterpene oxide compound which is a compound represented by the following formula (1): [R ¹ SiO _3/2 ] _n [R ² SiO _3/2 ] _m [R ³ SiO _3/2 ] _j . . . (1) In the formula (1), R ¹ is a group represented by the following formula (2): [In the formula (2), R ⁴ represents a hydrogen atom or a methyl group, p represents an integer of 4 to 10], and R ² is a group selected from groups represented by the following general formulae (3) to (6). Any of the groups: a group represented by the formula (3): [In the formula (3), R ⁵ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 3], and a group represented by the formula (4): [In the formula (4), r represents an integer of 1 to 3], and the group represented by the formula (5): [In the formula (5), s represents an integer of 1 to 3], and a group represented by the formula (6): R ³ represents a group of any one selected from the group consisting of a free hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an aryl group, and n, m, and j are represented by the following formulas (i) to (iv). The integer of the condition indicated: n≧2. . . (i), m≧1. . . (ii), j≧O. . . (iii), n+m+j=h. . . (iv) [in the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14] n, and m and j are each 2 or more, respectively, and R ¹ , R ^{2 ,} and R ³ Can be the same or not the same}. A curable resin composition containing the cage sesquiterpoxide compound and the radical polymerization initiator according to the first aspect of the invention, wherein the cage sesquioxane compound has a content of 10 to 80% by mass. The curable resin composition according to claim 2, which is further comprising the above-mentioned cage sesquioxanes, ladder-type siloxanes, and random siloxanes. There are (meth)acrylonyl unsaturated compounds. The curable resin composition according to the second or third aspect of the invention is characterized in that the casting has a thickness of 0.2 mm, and the integrated exposure is 2000 mJ at room temperature by using a high-pressure mercury lamp having an illuminance of 30 W/cm. When the light is radically polymerized by /cm ² , the reaction rate of the (meth) acrylonitrile group measured by infrared spectroscopy is 70% or more. The curable resin composition according to any one of claims 2 to 4, wherein the content of the radical polymerization initiator is from 0.01 to 10% by mass. A cured resin obtained by radical polymerization of a curable resin composition according to any one of claims 2 to 5.