TWI774893B - Organopolysiloxane compound and active energy ray curable composition containing the same - Google Patents

Abstract

(式中，R¹ 及R⁵ 相互獨立表示氫原子、甲基、乙基、n-丙基、或i-丙基，R² 、R³ 及R⁶ 相互獨立表示碳原子數1~10之2價之烴基，R⁴ 表示氫原子或甲基，n表示滿足0≦n≦2之整數，m表示滿足0≦m≦2之整數)。The present invention provides an organopolysiloxane that satisfies both hardness and toughness, and provides an alkali-developable cured film, and an active energy ray curability containing the organopolysiloxane, which can be used as a negative resist material. composition. The organopolysiloxane compound of the present invention has structural units represented by the following formulae (I) and (II).

(In the formula, R ¹ and R ⁵ independently represent a hydrogen atom, methyl group, ethyl group, n-propyl group, or i-propyl group, and R ² , R ³ and R ⁶ independently represent a carbon atom having 1 to 10 carbon atoms. A divalent hydrocarbon group, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer satisfying 0≦n≦2, and m represents an integer satisfying 0≦m≦2).

Description

Organopolysiloxane compound and active energy ray curable composition containing the same

The present invention relates to an organopolysiloxane compound and an active energy ray curable composition containing the same, more specifically, the present invention relates to an organopolysiloxane compound having an alkali-soluble portion and an active energy containing the compound Linear hardening composition.

Along with the high integration and high speed of LSI, miniaturization of resist patterns is required in the manufacturing process of semiconductor devices. In addition, in the manufacture of flexible devices represented by organic EL, a resist material having bending resistance or toughness is required. Generally speaking, the resist pattern often uses a positive photoresist whose solubility in an alkaline developer becomes high by exposure, and a positive photoresist has naphthoquinonediazide sulfonic acid used as a photosensitizer to generate sulfonic acid. Acid, corrosion of metal wiring parts.

In addition, the negative photoresist using a mixture of a photocurable resin and an alkali-soluble resin does not have this problem, but the strength of the cured product is weak, and the light stability and thermal stability are insufficient, so it is not suitable for fine patterning.

The organopolysiloxane compound containing an organofunctional group is excellent in characteristics such as weather resistance, heat resistance, shock resistance, crack resistance, and workability, and thus is also suitable as a photoresist material. For example, in Patent Document 1, methyltrimethoxysilane, 3-(trimethoxymethylsilyl)propylsuccinic anhydride, and 3-acryloyloxypropyltrimethoxysilane are hydrolyzed and condensed to synthesize organopolysilicon Oxane compounds, check developability and corrosiveness. Patent Document 2 hydrolyzes and condenses tetraethoxysilane, 3-(trimethoxymethylsilyl)propylsuccinic anhydride, and 3-(meth)acryloyloxypropyltrimethoxysilane to synthesize an organic polymer. The siloxane compound is mixed with a compound having two or more ethylenically unsaturated groups and a photo-radical polymerization initiator, and the heat-resistant transparency, pencil hardness, and developability of the cured product are examined.

Moreover, it is widely used as a (meth)acrylate which has a radically polymerizable unsaturated compound. In general, however, hard (meth)acrylates have problems of being brittle and prone to cracks, while soft (meth)acrylates have problems that they are poor in curability and tend to swell with solvents. Therefore, by including a urethane bond in the constituent elements of the (meth)acrylate compound, the molecules are agglomerated by the hydrogen bond derived from the urethane bond, and the improvement of the toughness of the cured product has been examined. . For example, Patent Document 3 discloses an example of synthesizing a silsesquioxane by subjecting a trifunctional alkoxysilane having a urethane acrylate structure to hydrolysis and condensation.

However, an organopolysiloxane compound that satisfies both the hardness and toughness of the cured product and provides an active energy ray-curable composition of an alkali-developable cured film has not been known. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-39052 [Patent Document 2] Japanese Patent Laid-Open No. 2012-212114 [Patent Document 3] Japanese Patent No. 5579072

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an organopolysiloxane that satisfies both hardness and toughness, and provides an alkali-developable cured film, and the organopolysiloxane containing the organopolysiloxane, which can Active energy ray curable composition used as a negative resist material.

The inventors of the present invention, as a result of careful examination in order to achieve the above object, found that the silicon atom contains an organic group having a (meth)acryloyloxy group and a urethane bond and an organic group having an acid anhydride group. The composition of the organopolysiloxane compound is irradiated with an active energy ray to provide a cured film having excellent hardness and ductility, which can be developed by alkali, thereby completing the present invention. Moreover, in this invention, a (meth)acryloyloxy group means an acryloxy group or a methacryloyloxy group.

(式中，R¹ 及R⁵ 相互獨立表示氫原子、甲基、乙基、n-丙基、或i-丙基，R² 、R³ 及R⁶ 相互獨立表示碳原子數1~10之2價之烴基，R⁴ 表示氫原子或甲基，n表示滿足0≦n≦2之整數，m表示滿足0≦m≦2之整數)。 2.如前述1之有機聚矽氧烷化合物，其係進一步具有下述式(III)表示之構成單位，且相對於矽原子數，直接鍵結於矽原子的烷氧基數及羥基數之合計之比為0.3以下，

(式中，R⁷ 相互獨立表示氫原子、可經鹵素原子取代之碳原子數1~8之烷基、苯基、(甲基)丙烯醯氧基丙基、或環氧丙氧基丙基)。 3.一種活性能量線硬化性組成物，其係含有如前述1或2之有機聚矽氧烷化合物及光聚合起始劑。 4.如前述3之活性能量線硬化性組成物，其係進一步含有前述有機聚矽氧烷化合物以外的聚合性不飽和化合物。 5.如前述3或4之活性能量線硬化性組成物，其係進一步含有溶劑。 6.一種硬化物，其係使如前述3~5中任一項之活性能量線硬化性組成物硬化而成。 7.一種阻劑膜，其係由如前述6之硬化物所成。That is, the present invention provides the following: 1. An organopolysiloxane compound having structural units represented by the following formulae (I) and (II),

(In the formula, R ¹ and R ⁵ independently represent hydrogen atom, methyl group, ethyl group, n-propyl group, or i-propyl group, and R ² , R ³ and R ⁶ independently represent a carbon atom having 1 to 10 carbon atoms. A divalent hydrocarbon group, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer satisfying 0≦n≦2, and m represents an integer satisfying 0≦m≦2). 2. The organopolysiloxane compound according to the above 1, which further has a structural unit represented by the following formula (III), and the sum of the number of alkoxy groups and the number of hydroxyl groups directly bonded to silicon atoms relative to the number of silicon atoms The ratio is below 0.3,

(in the formula, R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted by a halogen atom, a phenyl group, a (meth)acryloyloxypropyl group, or a glycidoxypropyl group ). 3. An active energy ray-curable composition comprising the organopolysiloxane compound described in 1 or 2 above and a photopolymerization initiator. 4. The active energy ray-curable composition according to the above-mentioned 3, which further contains a polymerizable unsaturated compound other than the above-mentioned organopolysiloxane compound. 5. The active energy ray-curable composition according to 3 or 4 above, which further contains a solvent. 6. A cured product obtained by curing the active energy ray-curable composition according to any one of 3 to 5 above. 7. A resist film, which is formed from the cured product of the above-mentioned 6.

Since the organopolysiloxane compound of the present invention contains an organic group having a (meth)acryloyloxy group and a urethane bond and an organic group having an acid anhydride group on the silicon atom, various active energy It exhibits free radical hardening properties, and at the same time, by free radical hardening, a cured film excellent in hardness and hardness is provided. Moreover, since the obtained cured film has alkali solubility and can be easily developed, the curable composition containing the organopolysiloxane compound of the present invention can also be used as a negative photoresist. [Form of implementing the invention]

The present invention will be specifically described below. (1) Organopolysiloxane compounds The organopolysiloxane compound of the present invention is characterized by having structural units represented by the following formulae (I) and (II).

In the above formulas, R ¹ and R ⁵ independently represent hydrogen atom, methyl group, ethyl group, n-propyl group or i-propyl group, and R ² , R ³ and R ⁶ independently represent a carbon atom having 1 to 10 carbon atoms. A divalent hydrocarbon group, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer satisfying 0≦n≦2, and m represents an integer satisfying 0≦m≦2. In addition, when there are two R ¹ , they may be the same or different from each other, and when there are two R ⁵ , they may be the same or different from each other.

R ² , R ³ and R ⁶ are divalent hydrocarbon groups having 1 to 10 carbon atoms, which may be linear, branched or cyclic, and specific examples thereof include methylene, ethylidene and trimethylene. straight-chain, branched or cyclic alkylene such as base, propylidene, tetramethylene, hexylene, decylidene, cyclohexylene, etc.; arylidene such as phenylene, xylylene, etc. . Among these, an alkylene group having 1 to 5 carbon atoms is preferable, and an ethylene group and a trimethylene group are more preferable.

In particular, the alkali solubility of the organopolysiloxane compound having the constituent units of the general formulae (I) and (II), the curability of the curable composition comprising the organopolysiloxane compound, and the sclerosing properties obtained from the composition From the viewpoint of hardness, crack resistance, bending resistance and water resistance of the cured product, in the general formulae (I) and (II), R ¹ is a methyl group, R ² is a trimethylene group, and R ³ is an ethylidene group , R ⁴ is a hydrogen atom, R ⁵ is a methyl group, and R ⁶ is preferably a trimethylene group.

In addition, the organopolysiloxane compound of the present invention has the following general features from the viewpoint of effectively suppressing the condensation reaction due to the condensable functional group or the crack resistance, water resistance and weather resistance of the obtained cured product. In the constituent unit represented by the formula (III), the ratio of the total of the number of alkoxy groups directly bonded to silicon atoms and the number of hydroxyl groups is preferably 0.3 or less, more preferably 0.2 or less, relative to the number of silicon atoms.

In formula (III), R ⁷ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted by a halogen atom, a phenyl group, a (meth)acryloyloxypropyl group, or a glycidoxy group propyl.

The alkyl group having 1 to 8 carbon atoms in R ⁷ may be any of linear, branched and cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n -Butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, etc., such alkyl groups, part or all of one of their hydrogen atoms It can also be substituted by halogen atoms. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.

In the present invention, the organopolysiloxane compound having the constituent units represented by the above formulae (I) to (III) is preferably a compound represented by the following average formula (IV).

In formula (IV), R ² to R ⁴ , R ⁶ and R ⁷ represent the same meanings as above, R ⁸ represents a hydrogen atom, methyl, ethyl, n-propyl, or i-propyl, a, b , c, d, e, and f indicate that 0.1≦a≦0.5, 0.1≦b≦0.5, 0≦c≦0.03, 0≦d≦0.4, 0≦e≦0.4, 0≦f≦0.7, a+b The number of +c+d+e+f=1, and g represents the number that satisfies 0≦g≦0.3.

The above a is preferably a number satisfying 0.05≦a≦0.6, and from the viewpoints of the curability of the composition containing the organopolysiloxane compound and the hardness, scratch resistance and crack resistance of the cured product, it is more preferably 0.1≦ a≦0.5. The above-mentioned b is preferably a number satisfying 0.05≦b≦0.6, and more preferably 0.1≦b≦0.5 from the viewpoint of alkali developability and viscosity (workability) of the organopolysiloxane compound. The above-mentioned c is preferably a number satisfying 0≦c≦0.03, and from the viewpoint of the viscosity (workability) of the organopolysiloxane compound, it is more preferably 0≦c≦0.01. The above-mentioned d is preferably a number satisfying 0≦d≦0.4, and more preferably 0≦d≦0.2 from the viewpoint of crack resistance and bending resistance of the cured product obtained. The above-mentioned e is preferably a number satisfying 0≦e≦0.4, and more preferably 0≦e≦0.3 from the viewpoint of the hardness of the obtained cured product. The above f is preferably a number satisfying 0≦f≦0.7, and from the viewpoint of the viscosity (workability) of the organopolysiloxane compound and the hardness of the obtained cured product, it is more preferably 0.2≦f≦0.6. The above g is preferably a number satisfying 0≦g≦0.3, but from the viewpoint of effectively suppressing the condensation reaction due to the condensable functional group, or the crack resistance, water resistance and weather resistance of the resulting cured product, The number satisfying 0≦g≦0.2 is better.

The organopolysiloxane compound of the present invention may have a single composition or a mixture of plural compounds with different compositions.

The average molecular weight of the organopolysiloxane compound of the present invention is not particularly limited, and the weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 200-100,000, more preferably 500-5,000. In such a range, condensation proceeds sufficiently, and the organopolysiloxane compound has excellent storability and can be quickly removed by alkali development.

The viscosity of the organopolysiloxane compound of the present invention is not particularly limited. From the viewpoint of workability and processability, the viscosity at 25°C measured by a rotational viscometer is preferably 50 to 100,000 mPa･s, more preferably 100~20,000mPa･s. Moreover, it is preferable that the organic polysiloxane compound of this invention does not contain the nonvolatile matter, such as an organic solvent, in 90 mass % or more. When the amount of volatile matter is reduced, voids occur when the composition is hardened, resulting in deterioration of appearance and reduction of mechanical properties.

The organopolysiloxane compound of the present invention can be manufactured according to a general organopolysiloxane manufacturing method. For example, the organic compound of the present invention can be obtained by condensing a hydrolyzable silane containing an organic group having a urethane bond and a (meth)acryloyloxy group, and a hydrolyzable silane containing an organic group having an acid anhydride group. Polysiloxane compounds. Specifically, a method of producing an organopolysiloxane compound by hydrolyzing and condensing the hydrolyzable silane represented by the following formula (V) and, if necessary, other hydrolyzable silane in the presence of a catalyst, can be mentioned.

(式中，R⁹ 表示具有胺基甲酸酯鍵結及(甲基)丙烯醯氧基之有機基、或具有酸酐基之有機基，X相互獨立表示氯原子或碳原子數1~6之烷氧基。)

(in the formula, R ⁹ represents an organic group having a urethane bond and a (meth)acryloyloxy group, or an organic group having an acid anhydride group, and X independently represents a chlorine atom or a carbon atom having 1 to 6 carbon atoms. alkoxy.)

X is an alkoxy group having 1 to 6 carbon atoms, wherein the alkyl group can be any one of straight chain, branched or cyclic, and specific examples thereof include methoxy, ethoxy, and n-propoxy , isopropoxy, n-butoxy, t-butoxy, pentoxy, etc. The organic group having a urethane bond and a (meth)acryloyloxy group as R ⁹ includes the groups shown below which are bonded to the silicon atom in the above formula (I).

(式中，R² ~R⁴ 係表示與上述相同意義。)

(In the formula, R ² to R ⁴ represent the same meanings as above.)

Specific examples of the hydrolyzable silane represented by the formula (V) include the hydrolyzable silanes represented by the following general formulae (V') and (V").

(In the formula, R ² to R ⁴ , R ⁶ and X have the same meanings as described above.)

In addition, if necessary, other hydrolyzable silanes that can be used, and those that can produce organopolysiloxane compounds by hydrolysis condensation together with the hydrolyzable silane represented by the general formula (V), are not particularly limited.

Specific examples of this include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. , p-styryltrimethoxysilane, p-styryltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-cyclohexyl) Oxycyclohexyl)ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methylpropene Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Trialkoxysilanes such as triethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiethoxysilane Phenyldimethoxysilane, Diphenyldiethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-Methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, etc. The dialkoxysilane; trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, 3-glycidoxypropyl dimethyl methoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyl Monoalkoxysilanes such as dimethylethoxysilane, 3-propenyloxypropyldimethylmethoxysilane, 3-propenyloxypropyldimethylethoxysilane, or the like Hexamethyldisiloxane, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyl) oxypropyl) tetramethyldisiloxane, 1,3-bis(3-propenyloxypropyl)tetramethyldisiloxane, etc.

The catalyst used for the condensation is not particularly limited, but is preferably an acidic catalyst, and specific examples thereof include hydrochloric acid, formic acid, acetic acid, sulfuric acid, fluoric acid, p-toluenesulfonic acid, benzoic acid, lactic acid, carbonic acid, methanesulfonic acid, Fluoromethanesulfonic acid, etc.

The amount of the catalyst to be used is not particularly limited, but considering the rapidity of the reaction and the ease of removal of the catalyst after the reaction, it is preferably in the range of 0.0002 to 0.5 mol relative to 1 mol of the hydrolyzable silane.

The amount ratio of the hydrolyzable silane to the water required for the hydrolytic condensation reaction is not particularly limited, but in consideration of preventing the deactivation of the catalyst, allowing the reaction to proceed sufficiently, and the ease of removal of the water after the reaction, the amount of the hydrolyzable silane The ratio of 1 mol of silane, preferably 0.1 to 10 mol of water, is preferred.

The reaction temperature during the hydrolysis condensation is not particularly limited, but it is preferably -10 to 150° C. in consideration of improving the reaction rate and preventing the decomposition of the organic functional group possessed by the hydrolyzable silane.

In addition, in the case of hydrolytic condensation, an organic solvent can be used. Specific examples of the organic solvent include methanol, ethanol, propanol, acetone, methyl isobutyl ketone, tetrahydrofuran, toluene, and xylene.

(2) Active energy ray curable composition The active energy ray-curable composition of the present invention contains the organopolysiloxane compound of the present invention and a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is an initiator that generates radical species by active energy rays, and acetophenone-based, benzoin-based, acylphosphine oxide-based, and diphenylene can be appropriately selected and used. Well-known photopolymerization initiators such as ketone-based and thioxanthone-based ones. Specific examples of the photopolymerization initiator include benzophenone, diphenyl ethylenedione, Michler's ketone, thioxanthone derivatives, phenyl diethyl ether, diethoxyacetophenone, benzyl diethyl ether. Methyl acetal, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, acylphosphine oxide derivatives, 2-methyl-1-{4-(methylthio)benzene yl}-2-morpholinopropan-1 ketone, 4-benzyl-4'-methyldiphenyl sulfide (Sulfide), 2,4,6-trimethylbenzyldiphenyl Phosphine and the like may be used alone or in combination of two or more.

The photopolymerization initiator can be obtained as a commercial product, for example, DAROCUR1173, DAROCURMBF, IRGACURE127, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE379EG, IRGACURE651, IRGACURE754, IRGACURE784, IRGACURE819, IRGACURE819DW, IRGACURE1807, IRGACURE379, IRGACURE784, IRGACURE819, IRGACURE819DW, IRGACURE1807, IRGACURE55 manufactured by BASF Japan) etc.

The amount of the photopolymerization initiator to be used is considered relative to the organopolysiloxane compound of the present invention and, if necessary, the polymerizable unsaturated compound to be used in order to improve the curability of the composition and prevent the surface hardness of the cured product from decreasing. The total amount is 100 parts by mass, preferably 0.1 to 20 parts by mass.

The active energy ray-curable composition of the present invention may contain a polymerizable unsaturated compound other than the organopolysiloxane compound of the present invention. Specific examples of the polymerizable unsaturated compound include 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, and ethylene oxide-modified bisphenol A di(meth)acrylate. base) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylol)propane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate Acrylates, pentaerythritol tri(meth)acrylates, 3-(meth)acrylooxyglycerol mono(meth)acrylates, urethane acrylates, epoxy acrylates, ester acrylates, etc. . When a polymerizable unsaturated compound is used, the content thereof is preferably 1 to 1,000 parts by mass relative to 100 parts by mass of the organopolysiloxane compound of the present invention.

In addition, the active energy ray-curable composition of the present invention may contain metal oxide fine particles, polysiloxane resin, silane coupling agent, diluent solvent, plasticizer, filler within the range that does not impair the object of the present invention. , sensitizers, light absorbers, light stabilizers, polymerization inhibitors, heat ray reflectors, antistatic agents, antioxidants, antifouling imparting agents, water repellency imparting agents, defoaming agents, colorants, tackifiers, Various additives such as leveling agents.

The active energy ray-curable composition of the present invention can be obtained by uniformly mixing the above-mentioned components according to an ordinary method.

The viscosity of the active energy ray-curable composition of the present invention is not particularly limited, but in consideration of improving the forming or coating workability and suppressing the occurrence of band-like unevenness, the viscosity at 25°C measured by a rotational viscometer, Preferably it is 100,000mPa. s or less, more preferably 20,000mPa. s or less. Also, the lower limit of the viscosity at 25°C is preferably 10mPa. s or more.

The above-mentioned active energy ray-curable composition of the present invention can also be suitably used as a coating agent, especially a resist. This is cured to obtain a coated article having a film formed thereon.

The above-mentioned base material is not particularly limited, and examples thereof include silicon wafers, metals, plastic moldings, ceramics, glass, and composites thereof.

In addition, the surface of these substrates can also be chemically treated, corona discharge treatment, plasma treatment, acid or alkali treated substrates, or cosmetic plywood coated with different types of paint on the substrate body and the surface layer. Wait.

The coating method of the coating agent can be appropriately selected from known methods, for example, spin coating, coating bar, brush coating, spraying, dipping, curtain coating, roll coating, curtain coating, doctor blade can be used Various coatings such as coating cloth method.

The light source for curing the active energy ray-curable composition generally includes a light source with a wavelength in the range of 200 to 450 nm, and examples thereof include high pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, xenon lamps, and carbon arc lamps.

The irradiation dose is not particularly limited, but is preferably 10 to 5,000 mJ/cm ² , more preferably 20 to 1,000 mJ/cm ² .

The hardening time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

[Example]

The following examples and comparative examples are shown to describe the present invention more specifically, but the present invention is not limited to the following examples.

In addition, in the following, the volatile content is the value measured according to JIS C2133, and the weight average molecular weight is measured using GPC (gel permeation chromatography, HLC-8220 manufactured by Tosoh Corporation), and tetrahydrofuran (THF) is used as a developing solvent. value.

In addition, the values of a to g in the average formula (IV) were calculated from the measurement results of ¹ H-NMR and ²⁹ Si-NMR.

[1] Synthesis of organopolysiloxane compound containing acid anhydride group and acryloxy group bound via urethane bond [Example 1-1]

While stirring 348.3 g (3.0 mol) of hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) in the reactor, 3-isocyanate propyl trimethoxy was added. Silane (KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 615.9 g (3.0 mol) was stirred at 25° C. for 1 hour to obtain 964.2 g (3.0 mol) of a compound represented by the following formula (VI).

Here, 262.3 g (1.0 mol) of 3-(trimethoxymethylsilyl)propyl succinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane, and 7.2 g of methanesulfonic acid were added to make it uniform, and then added 147.6 g of ion-exchanged water was stirred at 25°C for 4 hours. 35.9 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was put in and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 4,500 mPa at 25°C. s, 1.3 mass % of volatile matter, and a viscous liquid at 25°C of a weight average molecular weight of 1,350. The values of a to g in the average formula (IV) calculated from the NMR results were a=0.35, b=0.14, c=0, d=0, e=0, f=0.51, and g=0.04, respectively.

[Example 1-2]

642.8 g (2.0 mol) of the compound represented by the above formula (VI), 524.7 g (2.0 mol) of 3-(trimethoxymethylsilyl)propyl succinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane , 6.9 g of methanesulfonic acid was added to the reactor, and when it became a uniform state, 165.6 g of ion-exchanged water was added, and the mixture was stirred at 25° C. for 2 hours. 34.5 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was put in and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 3,200 mPa at 25°C. s, 2.5 mass % of volatile matter, and a weight average molecular weight of 1,530 - viscous liquid at 25°C. The values of a to g in the average formula (IV) calculated from the NMR results were a=0.22, b=0.23, c=0, d=0, e=0, f=0.55, and g=0.02, respectively.

[Example 1-3]

642.8 g (2.0 mol) of the compound represented by the above formula (VI), 262.3 g (1.0 mol) of 3-(trimethoxymethylsilyl)propylsuccinic anhydride, 136.2 g (1.0 mol) of methyltrimethoxysilane, 487.1 g (3.0 mol) of hexamethyldisiloxane and 6.3 g of methanesulfonic acid were put into the reactor, and when it became a uniform state, 147.6 g of ion-exchanged water was added, and the mixture was stirred at 25° C. for 2 hours. 31.3 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was put in and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 2,990 mPa at 25°C. s, 2.1 mass % of volatile matter, and a weight average molecular weight of 1,770 - viscous liquid at 25°C. The values of a to g in the average formula (IV) calculated from the NMR results were a=0.26, b=0.09, c=0, d=0.10, e=0, f=0.55, and g=0.08, respectively.

[Example 1-4]

964.2 g (3.0 mol) of the compound represented by the above formula (VI), 262.3 g (1.0 mol) of 3-(trimethoxymethylsilyl)propyl succinic anhydride, dimethyldimethoxy 240.4 g (2.0 mol) of siloxane, 487.1 g (3.0 mol) of hexamethyldisiloxane, and 7.9 g of methanesulfonic acid were added to the reactor, and when a uniform state was obtained, 190.8 g of ion-exchanged water was added, and the mixture was stirred at 25°C 2 hours. 39.6 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was put in, and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 7,200 mPa at 25°C. s, 3.1 mass % of volatile matter, and a viscous liquid at 25°C of a weight average molecular weight of 1,620. The values of a to g in the average formula (IV) calculated from the NMR results were a=0.32, b=0.10, c=0, d=0, e=0.14, f=0.44, and g=0.09, respectively.

[Example 1-5]

642.8 g (2.0 mol) of the compound represented by the above formula (VI), 262.3 g (1.0 mol) of 3-(trimethoxymethylsilyl)propyl succinic anhydride, 480.8 g (4.0 mol) of dimethyldimethoxysilane ) and 5.0 g of methanesulfonic acid were added to the reactor, and when a uniform state was obtained, 324.0 g of ion-exchanged water was added, and the mixture was stirred at 25° C. for 4 hours. 24.9 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged, and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 23,000 mPa at 25°C. s, a liquid having a volatile content of 4.5% by mass and a weight average molecular weight of 3,200. The values of a to g in the average formula (IV) calculated from the NMR results were a=0.32, b=0.17, c=0, d=0, e=0.51, f=0, and g=0.9, respectively.

[2] Those containing acryloxy group and acid anhydride group without urethane bond Synthesis of organopolysiloxane compounds [Comparative Example 1-1]

702.9 g (3.0 mol) of 3-propenyloxypropyltrimethoxysilane, 262.3 g (1.0 mol) of 3-(trimethoxysilyl)propyl succinic anhydride, 487.1 g of hexamethyldisiloxane (3.0 mol) and 5.1 g of methanesulfonic acid were put into the reactor, and when it became a uniform state, 147.6 g of ion-exchanged water was added, and the mixture was stirred at 25° C. for 4 hours. 25.3 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was put in and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 190mPa at 25°C. s, a liquid having a volatile content of 4.1% by mass and a weight average molecular weight of 1,210. The values of a to g in the average formula (IV) calculated from the NMR results were a=0, b=0.14, c=0, d=0.42, e=0, f=0.44, and g=0.08, respectively.

[3] Synthesis of an organopolysiloxane compound having an acryloxy group bonded via a urethane bond and not containing an acid anhydride group [Comparative Example 1-2]

1,285.6 g (4.0 mol) of the compound represented by the above formula (VI), 487.13 g (3.0 mol) of hexamethyldisiloxane, and 7.5 g of methanesulfonic acid were charged into the reactor, and when a uniform state was obtained, 129.6 g of ion-exchanged water was added. g, stirred at 25°C for 4 hours. 37.4 g of Kyowaad 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged, and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, followed by pressure filtration.

The resulting reactant had a viscosity of 1,290 mPa at 25°C. s, a liquid having a volatile content of 2.5% by mass and a weight average molecular weight of 1,350. The values of a to g in the average formula (VI) calculated from the NMR results were a=0.42, b=0, c=0, d=0, e=0, f=0.58, and g=0.13, respectively.

[4] Manufacture of active energy ray curable composition and its cured product [Examples 2-1 to 2-5, Comparative Examples 2-1, 2-2] The above Examples 1-1 to 1-5 were mixed and compared 10 parts by mass of each of the organopolysiloxane compounds obtained in Examples 1-1 and 1-2 and 0.5 parts by mass of DAROCUR1173 (radical photopolymerization initiator, manufactured by BASF Corporation) were poured into a mold to which a release film was attached, The thickness was set to 0.2 mm, the cumulative irradiation amount was 600 mJ/cm ² using a high pressure mercury lamp, and the film was irradiated with light to cure the film. For the resulting film, pencil hardness and flex resistance were measured. The results are shown in Table 1. (1) Pencil hardness was measured with a load of 750 g in accordance with JIS K5600-5-4. (2) Bending resistance is measured using a cylindrical mandrel (Mandrel) (TYPE1) in accordance with JIS K5600-5-1, and about bending resistance, for a film with cracks in the 8 mmφ test, it was set to >8 mmφ.

As shown in Table 1, the curing of Examples 2-1 to 2-5 and Comparative Example 2-2 of the organopolysiloxane compounds containing acryloxy groups bonded via urethane bonds were found. The cured product of Comparative Example 2-1, which has no urethane bond, is good in both properties of pencil hardness and flex resistance, and has no flex resistance.

[5] Manufacture of coating composition and coated article [Examples 3-1 to 3-5, Comparative Examples 3-1, 3-2] The above Examples 1-1 to 1-5 and Comparative Example 1-1 were mixed, 10 parts by mass of each organopolysiloxane compound obtained in 1-2, and 0.5 part by mass of DAROCUR1173 (radical photopolymerization initiator, manufactured by BASF Corporation), the coating composition was spin-coated on silicon at a rotation speed of 1,500 rpm. On the wafer, through a mask with a specific pattern, a high-pressure mercury lamp is used with a cumulative irradiation dose of 600 mJ/cm ² , the coating film is irradiated with light so that the coating film has an exposed portion and an unexposed portion, and a coating is formed by curing to produce a coated article. Then, the coated article was immersed in a 0.1 mass % KOH aqueous solution, and developed to remove the unexposed coating composition. After washing with water, the film residue remaining on the substrate was observed with an optical microscope, and when the residue did not remain, the KOH developability was evaluated as OK, and when the residue remained, it was evaluated as NG. The results are shown in Table 2.

As shown in Table 2, only the coating compositions of Examples 3-1 to 3-5 and Comparative Example 3-1 containing 3-(trimethoxymethylsilyl)propylsuccinic anhydride as constituent components were coated The KOH developability can be seen in the coated articles of the present invention, showing the excellent performance of the organopolysiloxane compound having the polymerizable functional group of the present invention.

Claims (7)

An organopolysiloxane compound having structural units represented by the following formulae (I) and (II),

(In the formula, R ¹ and R ⁵ independently represent a hydrogen atom, methyl group, ethyl group, n-propyl group, or i-propyl group, and R ² , R ³ and R ⁶ independently represent a carbon atom having 1 to 10 carbon atoms. A divalent hydrocarbon group, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer satisfying 0≦n≦2, and m represents an integer satisfying 0≦m≦2). The organopolysiloxane compound of claim 1 further has a structural unit represented by the following formula (III), and the sum of the number of alkoxy groups directly bonded to silicon atoms and the number of hydroxyl groups relative to the number of silicon atoms ratio is less than 0.3,

(in the formula, R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted by a halogen atom, a phenyl group, a (meth)acryloyloxypropyl group, or a glycidoxypropyl group ). An active energy ray curable composition containing the organopolysiloxane compound of claim 1 or 2 and a photopolymerization initiator. The active energy ray-curable composition according to claim 3, further comprising a polymerizable unsaturated compound other than the aforementioned organopolysiloxane compound. The active energy ray curable composition according to claim 3 or 4, which further contains a solvent. A hardened product obtained by hardening the active energy ray hardening composition according to any one of Claims 3 to 5. A resist film, which is made of the cured product as claimed in claim 6.