JP6958313B2 - Organopolysiloxane compound and active energy ray-curable composition containing it - Google Patents

Description

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

With the increasing integration and speed of LSI, miniaturization of resist patterns in the manufacturing process of semiconductor devices is required. Further, in the production of flexible devices typified by organic EL, a resist material having bending resistance and toughness is required.
Generally, as a resist pattern, a positive photoresist whose solubility in an alkaline developer is increased by exposure is often used, but in a positive photoresist, naphthoquinonediazide sulfonic acid used as a photosensitizer is used. Has a problem that it generates sulfonic acid and corrodes the metal wiring part.

On the other hand, a negative photoresist using a mixture of a photocurable resin and an alkali-soluble resin does not cause such a problem, but the strength of the cured product is brittle and the photostability and thermostability are insufficient. , It is said that it is not suitable for fine patterning.

The organopolysiloxane compound containing an organic functional group is also suitable as a photoresist material because it has excellent properties such as weather resistance, heat resistance, impact resistance, crack resistance, and processability.
For example, in Patent Document 1, methyltrimethoxysilane, 3- (trimethoxysilyl) propyl anhydride succinic acid, and 3-acryloxypropyltrimethoxysilane are hydrolyzed and condensed to synthesize an organopolysiloxane compound, which is developable. Corrosiveness is being investigated.
In Patent Document 2, tetraethoxysilane, 3- (trimethoxysilyl) propyl anhydride succinic acid, and 3- (meth) acryloxypropyltrimethoxysilane are hydrolyzed and condensed to synthesize an organopolysiloxane compound, which is not ethylenic. A compound having two or more saturated groups and a photoradical polymerization initiator are mixed, and the heat-resistant transparency, pencil hardness, developability, etc. of the cured product have been investigated.

Further, (meth) acrylate is widely used as an unsaturated compound having radical polymerization property.
However, in general, hard (meth) acrylate has a problem that it is brittle and easily cracked, while soft (meth) acrylate has a problem that it has poor curability and easily swells with a solvent.
Therefore, studies have been conducted to improve the toughness of the cured product by incorporating urethane bonds into the components of the (meth) acrylate compound to agglomerate the molecules by hydrogen bonds derived from the urethane bonds.
For example, Patent Document 3 discloses an example in which silsesquioxane is synthesized by hydrolyzing and condensing a trifunctional alkoxysilane having a urethane acrylate structure.

However, there is no known active energy ray-curable organopolysiloxane compound that satisfies both the hardness and toughness of the cured product and provides a cured film that can be developed with alkali.

Japanese Unexamined Patent Publication No. 2010-39052 Japanese Unexamined Patent Publication No. 2012-212114 Japanese Patent No. 5579072

The present invention has been made in view of the above circumstances, and contains an organopolysiloxane that satisfies both hardness and toughness and provides a cured film that can be developed with alkali, and a negative resist containing this organopolysiloxane. An object of the present invention is to provide an active energy ray-curable composition that can be used as a material.

As a result of diligent studies to achieve the above object, the present inventors have an organic group having an organic group having a (meth) acryloyloxy group and a urethane bond and an organic group having an acid anhydride group on a silicon atom. The present invention has been completed by finding that a composition containing a polysiloxane compound provides a cured film having excellent hardness and toughness and being alkaline-developable by irradiation with active energy rays. In the present invention, the (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.

（式中、Ｒ¹およびＲ⁵は、互いに独立して、水素原子、メチル基、エチル基、ｎ−プロピル基、またはｉ−プロピル基を表し、Ｒ²、Ｒ³およびＲ⁶は、互いに独立して、炭素原子数１〜１０の２価の炭化水素基を表し、Ｒ⁴は、水素原子またはメチル基を表し、ｎは０≦ｎ≦２を満たす整数を表し、ｍは０≦ｍ≦２を満たす整数を表す。）
２． さらに下記式（ＩＩＩ）で表される構成単位を有し、かつ、ケイ素原子数に対するケイ素原子に直接結合したアルコキシ基数および水酸基数の合計の比が０．３以下である１のオルガノポリシロキサン化合物、

（式中、Ｒ⁷は、互いに独立して、水素原子、ハロゲン原子で置換されていてもよい炭素原子数１〜８のアルキル基、フェニル基、（メタ）アクリロイルオキシプロピル基、またはグリシドキシプロピル基を表す。）
３． １または２のオルガノポリシロキサン化合物、および光重合開始剤を含有する活性エネルギー線硬化性組成物、
４． 前記オルガノポリシロキサン化合物以外の重合性不飽和化合物をさらに含有する３の活性エネルギー線硬化性組成物、
５． 溶剤をさらに含有する３または４の活性エネルギー線硬化性組成物、
６． ３〜５のいずれかの活性エネルギー線硬化性組成物を硬化させてなる硬化物、
７． ６の硬化物からなるレジスト膜
を提供する。 That is, the present invention
1. 1. An organopolysiloxane compound, characterized by having a structural unit represented by the following formulas (I) and (II).

(In the formula, R ¹ and R ⁵ represent hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, or i-propyl groups independently of each other, and R ² , R ^{3 and R 6} are independent of each other. Then, it represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer satisfying 0 ≦ n ≦ 2, and m represents 0 ≦ m ≦. Represents an integer that satisfies 2.)
2. Further, an organopolysiloxane compound having a structural unit represented by the following formula (III) and having a total ratio of the number of alkoxy groups and the number of hydroxyl groups directly bonded to the silicon atom to the number of silicon atoms of 0.3 or less. ,

(In the formula, R ⁷ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxy, which may be substituted with a hydrogen atom or a halogen atom independently of each other. Represents a propyl group.)
3. 3. An active energy ray-curable composition containing 1 or 2 organopolysiloxane compounds and a photopolymerization initiator.
4. 3. The active energy ray-curable composition, which further contains a polymerizable unsaturated compound other than the organopolysiloxane compound.
5. 3 or 4 active energy ray-curable compositions further containing a solvent,
6. A cured product obtained by curing any of 3 to 5 active energy ray-curable compositions,
7. A resist film composed of the cured product of No. 6 is provided.

Since the organopolysiloxane compound of the present invention has 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, it is radically curable by various active energy rays. In addition to being shown, radical curing gives a cured film with excellent hardness and toughness. Further, 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 material. It is useful.

Hereinafter, the present invention will be specifically described.
(1) Organopolysiloxane compound The organopolysiloxane compound according to the present invention is characterized by having a structural unit represented by the following formulas (I) and (II).

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

The ^{divalent hydrocarbon group having 1 to 10 carbon atoms of R 2} , R ³ and R ⁶ may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, trimethylene, propylene and tetra. Linear, branched or cyclic alkylene groups such as methylene, hexylene, decylene and cyclohexylene groups; arylene groups such as phenylene and xylylene groups and the like can be mentioned.
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 formulas (I) and (II), the curability of the curable composition containing the organopolysiloxane compound, and the hardness of the cured product obtained from the composition. From the viewpoint of crack resistance, bending resistance, and water resistance, in the general formulas (I) and (II), R ¹ is a methyl group, R ² is a trimethylene group, and R ³ is an ethylene group. , R ⁴ is a hydrogen atom, R ⁵ is a methyl group, and R ⁶ is a trimethylene group.

Further, the organopolysiloxane compound of the present invention is effective in suppressing the condensation reaction due to the condensing functional group, and from the viewpoints of crack resistance, water resistance, and weather resistance of the obtained cured product, the following general formula is used. It preferably has the structural unit represented by (III), and the ratio of the total number of alkoxy groups and hydroxyl groups directly bonded to the silicon atom to the number of silicon atoms is 0.3 or less, preferably 0.2 or less. More preferably.

In formula (III), R ⁷ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a (meth) acryloyloxypropyl group, or a grease, which may be substituted with a hydrogen atom or a halogen atom independently of each other. Represents a sidoxylpropyl group.

The alkyl group having 1 to 8 carbon atoms of R ⁷ may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl and i-. Butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl groups and the like can be mentioned, and some or all of the hydrogen atoms of these alkyl groups are replaced with halogen atoms. May be.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among them, as R ⁷ , an alkyl group or a phenyl group having 1 to 4 carbon atoms is preferable, and a methyl group or a phenyl group is more preferable.

In the present invention, as the organopolysiloxane compound having the structural units represented by the above formulas (I) to (III), the compound represented by the following average formula (IV) is particularly preferable.

In formula (IV), R ^{2 to} R ⁴ , R ⁶ and R ⁷ have the same meanings as above, and R ⁸ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. Represented by a, b, c, d, e, and f, 0.1 ≦ a ≦ 0.5, 0.1 ≦ b ≦ 0.5, 0 ≦ c ≦ 0.03, 0 ≦ d ≦ 0. 4. Represents a number satisfying 0 ≦ e ≦ 0.4, 0 ≦ f ≦ 0.7, a + b + c + d + e + f = 1, and g represents a number satisfying 0 ≦ g ≦ 0.3.

The number of a above preferably satisfies 0.05 ≦ a ≦ 0.6, and is 0.1 from the viewpoint of curability of the composition containing the organopolysiloxane compound, hardness of the cured product, scratch resistance, and crack resistance. ≤a ≤ 0.5 is more preferable.
The above 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 c is preferably a number satisfying 0 ≦ c ≦ 0.03, and more preferably 0 ≦ c ≦ 0.01 from the viewpoint of viscosity (workability) of the organopolysiloxane compound.
The number of d that satisfies 0 ≦ d ≦ 0.4 is preferable, and 0 ≦ d ≦ 0.2 is more preferable from the viewpoint of crack resistance and bending resistance of the obtained cured product.
The number of e that satisfies 0 ≦ e ≦ 0.4 is preferable, and 0 ≦ e ≦ 0.3 is more preferable from the viewpoint of the hardness of the obtained cured product.
The above f is preferably a number satisfying 0 ≦ f ≦ 0.7, and more preferably 0.2 ≦ f ≦ 0.6 from the viewpoint of the viscosity (workability) of the organopolysiloxane compound and the hardness of the obtained cured product.
The above g is preferably a number satisfying 0 ≦ g ≦ 0.3, which is effective in suppressing the condensation reaction by the condensing functional group, and from the viewpoints of crack resistance, water resistance, and weather resistance of the obtained cured product. In consideration of, a number satisfying 0 ≦ g ≦ 0.2 is more preferable.

The organopolysiloxane compound of the present invention may be a single composition or a mixture of a plurality of compounds having different compositions.

The average molecular weight of the organopolysiloxane compound of the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC) is preferably 200 to 100,000, more preferably 500 to 5,000. preferable.
Within such a range, the condensation has proceeded sufficiently, the organopolysiloxane compound has excellent storage stability, and can be quickly removed in alkaline development.

The viscosity of the organopolysiloxane compound of the present invention is not particularly limited, but from the viewpoint of workability and workability, the viscosity at 25 ° C. measured by a rotational viscometer is preferably 50 to 100,000 mPa · s. More preferably, 100 to 20,000 mPa · s.
Further, the organopolysiloxane compound of the present invention preferably has a non-volatile content of 90% by mass or more excluding organic solvents and the like. When the volatile content is reduced, deterioration of appearance and deterioration of mechanical properties due to void generation when the composition is cured are suppressed.

The organopolysiloxane compound of the present invention can be produced according to a general method for producing an organopolysiloxane.
For example, 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 are condensed to obtain the organopolysiloxane compound of the present invention. be able to.
Specifically, a hydrolyzable silane represented by the following formula (V) and, if necessary, other hydrolyzable silanes are used to hydrolyze and condense in the presence of a catalyst to obtain an organopolysiloxane compound. The method of manufacturing is mentioned.

R ⁹ SiX ₃ (V)
(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 is independent of each other and has 1 to 1 chlorine atom or carbon atom number. Represents 6 alkoxy groups.)

The alkyl group of X having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy and n-. Butoxy, t-butoxy, pentyloxy group and the like can be mentioned.
Examples of the organic group having a urethane bond of R ⁹ and a (meth) acryloyloxy group include the groups shown below bonded to a silicon atom in the above formula (I).

（式中、Ｒ²〜Ｒ⁴は、上記と同じ意味を表す。）

(In the formula, R ^{2 to} R ⁴ have the same meaning as above.)

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

（式中、Ｒ²〜Ｒ⁴、Ｒ⁶およびＸは、上記と同じ意味を表す。）

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

Further, as other hydrolyzable silanes used as needed, especially those capable of producing an organopolysiloxane compound by hydrolyzing and condensing with the hydrolyzable silane represented by the above general formula (V). It is not limited.
Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and the like. 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Trialkoxysilanes such as 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3- Dialkoxysilanes such as methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane; trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, 3- Glycydoxypropyl dimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyl Monoalkoxysilanes such as dimethylethoxysilane, hexamethyldisiloxane, which is a hydrolysis condensate of these, 1,3-di (3-glycidoxypropyl) tetramethyldisiloxane, 1,3-di (3-methacryloyl). Examples thereof include oxypropyl) tetramethyldisiloxane and 1,3-di (3-acryloxypropyl) tetramethyldisiloxane.

The catalyst used for condensation is not particularly limited, but an acidic catalyst is preferable, and specific examples thereof include hydrochloric acid, formic acid, acetic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, benzoic acid, lactic acid, and carbonic acid. , Methane sulfonic acid, trifluoromethane sulfonic acid and the like.
The amount of the catalyst used is not particularly limited, but in consideration of the rapid progress of the reaction and the ease of removal of the catalyst after the reaction, 0.0002 to 0. For 1 mol of hydrolyzable silane. A range of 5 mol is preferred.

The amount ratio of the hydrolyzable silane to the water required for the hydrolyzing condensation reaction is not particularly limited, but it is possible to prevent the catalyst from being deactivated to allow the reaction to proceed sufficiently and to remove water after the reaction. Considering the ease, a ratio of 0.1 to 10 mol of water is preferable with respect to 1 mol of hydrolyzable silane.
The reaction temperature at the time of hydrolysis condensation is not particularly limited, but is -10 to 150 ° C. in consideration of improving the reaction rate and preventing the decomposition of the organic functional group of the hydrolyzable silane. preferable.

An organic solvent may be used for hydrolysis condensation. Specific examples of the organic solvent include methanol, ethanol, propanol, acetone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene and the like.

(2) Active Energy Ray Curable Composition The active energy ray curable composition of the present invention contains the above-mentioned 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 known acetophenone-based, benzoin-based, acylphosphine oxide-based, benzophenone-based, thioxanthone-based, and the like are known. It can be appropriately selected from the photopolymerization initiators and used.
Specific examples of the photopolymerization initiator include benzophenone, benzyl, Michler's ketone, thioxanthone derivative, benzoin ethyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, and acyl. Phosphine oxide derivative, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine, which may be used alone or in combination of two or more.

The photopolymerization initiator can be obtained as a commercially available product, and examples of the commercially available products include DaroCure 1173, DaroCure MBF, Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 379EG, Irgacure 651, Irgacure 754, Irgacure 784. , Irgacure 819, Irgacure 819DW, Irgacure 907, Irgacure 1800, Irgacure 2959, Lucillin TPO (all manufactured by BASF Japan Ltd.) and the like.

The amount of the photopolymerization initiator used is the organopolysiloxane compound of the present invention and, if necessary, in consideration of improving the curability of the composition and preventing a decrease in the surface hardness of the cured product. 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass of the total amount of the polymerizable unsaturated compound.

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, ethylene oxide-modified bisphenol A di (meth) acrylate, and trimethyl propantri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, Examples thereof include urethane acrylate, epoxy acrylate and ester acrylate.
When a polymerizable unsaturated compound is used, the content thereof is preferably 1 to 1,000 parts by mass with respect to 100 parts by mass of the organopolysiloxane compound of the present invention.

The active energy ray-curable composition of the present invention contains metal oxide fine particles, silicone resin, silane coupling agent, diluting solvent, plasticizer, filler, sensitizer, light absorber, light stabilizer, and polymerization inhibitor. Various additives such as agents, heat ray reflecting agents, antistatic agents, antioxidants, antifouling agents, water repellent agents, defoaming agents, colorants, thickeners, leveling agents, etc. impair the object of the present invention. It may be included in a range that does not exist.

The active energy ray-curable composition of the present invention can be obtained by uniformly mixing each of the above components according to a conventional method.
The viscosity of the active energy ray-curable composition of the present invention is not particularly limited, but it is measured by a rotational viscometer in consideration of improving molding or coating workability and suppressing the occurrence of streaks and the like. The viscosity at 25 ° C. is preferably 100,000 mPa · s or less, and more preferably 20,000 mPa · s or less. The lower limit of the viscosity at 25 ° C. is preferably 10 mPa · s or more.

The active energy ray-curable composition of the present invention described above can be suitably used as a coating agent, particularly as a resist application, and is applied directly to at least one surface of a substrate or through at least one other layer. Then, by curing it, a coated article having a film formed can be obtained.

The base material is not particularly limited, and examples thereof include silicon wafers, metals, plastic molded bodies, ceramics, glass, and composites thereof.
In addition, the surface of these base materials is treated with chemical conversion treatment, corona discharge treatment, plasma treatment, acid or alkaline solution, or decorative plywood whose surface layer is coated with a different type of paint from the base material body. Can also be used.

The coating agent may be appropriately selected from known methods. For example, various coating methods such as spin coating, bar coater, brush coating, spraying, dipping, flow coating, roll coating, curtain coating, and knife coating may be used. Can be used.

As a light source for curing the active energy ray-curable composition, a light source containing light having a wavelength in the range of 200 to 450 nm, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. Can be mentioned.
Although the irradiation amount is not particularly limited but is preferably ^{10~5,000mJ / cm 2, 20~1,000mJ / cm} 2 is more preferable.
The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following, the volatile content is a value measured according to JIS C2133, and the weight average molecular weight is tetrahydrofuran (THF) as a developing solvent using GPC (gel permeation chromatography, manufactured by HLC-8220 Tosoh Co., Ltd.). It is a value measured as.
The values of a to g in the average formula ( IV ) were calculated from the results of ^{1 1} H-NMR and ^{29 Si-NMR measurements.}

[1] Synthesis of an organopolysiloxane compound containing an acid anhydride group and an acryloyloxy group bonded via a urethane bond [Example 1-1]
3-Isocyanatepropyltrimethoxysilane (KBM-9007, Shin-Etsu Chemical Co., Ltd.) while stirring 348.3 g (3.0 mol) of hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) in the reactor. (Manufactured) After adding 615.9 g (3.0 mol), the mixture was stirred at 25 ° C. for 1 hour to obtain 964.2 g (3.0 mol) of the compound represented by the following formula (VI).
Add 262.3 g (1.0 mol) of 3- (trimethoxysilyl) propyl succinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane, and 7.2 g of methanesulfonic acid to this, and when it becomes uniform, ionize. 147.6 g of exchanged water was added, and the mixture was stirred at 25 ° C. for 4 hours. 35.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. having a viscosity of 4,500 mPa · s at 25 ° C., a volatile content of 1.3% by mass, and a weight average molecular weight of 1,350. The values of a to g in the average formula (IV) calculated from the NMR results are a = 0.35, b = 0.14, c = 0, d = 0, e = 0, f = 0.51, respectively. g = 0.04.

[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- (trimethoxysilyl) propyl succinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane. ), 6.9 g of methanesulfonic acid was added into the reactor, and when it became uniform, 165.6 g of ion-exchanged water was added, and the mixture was stirred at 25 ° C. for 2 hours. 34.5 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 3,200 mPa · s at 25 ° C., a volatile content of 2.5% by mass, and a weight average molecular weight of 1,530. The values of a to g in the average formula (IV) calculated from the NMR results are a = 0.22, b = 0.23, c = 0, d = 0, e = 0, f = 0.55, respectively. g = 0.02.

[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- (trimethoxysilyl) propyl anhydride succinic acid, 136.2 g (1.0 mol) of methyltrimethoxysilane. ), Hexamethyldisiloxane 487.1 g (3.0 mol) and 6.3 g of methanesulfonic acid were added into the reactor, and when it became uniform, 147.6 g of ion-exchanged water was added and stirred at 25 ° C. for 2 hours. .. 31.3 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 2,990 mPa · s at 25 ° C., a volatile content of 2.1% by mass, and a weight average molecular weight of 1,770. The values of a to g in the average formula (IV) calculated from the NMR results are a = 0.26, b = 0.09, c = 0, d = 0.10, e = 0, f = 0, respectively. 55, g = 0.08.

[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- (trimethoxysilyl) propyl anhydride succinic acid, 240.4 g (2.0 mol) of dimethyldimethoxysilane. , Hexamethyldisiloxane 487.1 g (3.0 mol) and 7.9 g of methanesulfonic acid were added into the reactor, and when they became uniform, 190.8 g of ion-exchanged water was added, and the mixture was stirred at 25 ° C. for 2 hours. 39.6 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 7,200 mPa · s at 25 ° C., a volatile content of 3.1% by mass, and a weight average molecular weight of 1,620. The values of a to g in the average formula (IV) calculated from the results of NNMR are a = 0.32, b = 0.10, c = 0, d = 0, e = 0.14, and f = 0, respectively. 44, g = 0.09.

[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- (trimethoxysilyl) propyl succinic anhydride, 480.8 g (4.0 mol) of dimethyldimethoxysilane. , 5.0 g of methanesulfonic acid was added to the reactor, 324.0 g of ion-exchanged water was added when the mixture became uniform, and the mixture was stirred at 25 ° C. for 4 hours. 24.9 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a liquid having a viscosity of 23,000 mPa · s at 25 ° C., 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 are a = 0.32, b = 0.17, c = 0, d = 0, e = 0.51, f = 0, respectively. It was g = 0.9.

[2] Synthesis of an organopolysiloxane compound containing an acryloyloxy group having no urethane bond and an acid anhydride group [Comparative Example 1-1]
3-Acryloyloxypropyltrimethoxysilane 702.9 g (3.0 mol), 3- (trimethoxysilyl) propyl anhydride succinic acid 262.3 g (1.0 mol), hexamethyldisiloxane 487.1 g (3.0 mol), 5.1 g of methanesulfonic acid was added into the reactor, and when it became uniform, 147.6 g of ion-exchanged water was added, and the mixture was stirred at 25 ° C. for 4 hours. 25.3 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a liquid having a viscosity of 190 mPa · s at 25 ° C., 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 are a = 0, b = 0.14, c = 0, d = 0.42, e = 0, f = 0.44, respectively. g = 0.08.

[3] Synthesis of an organopolysiloxane compound having an acryloyloxy group bonded via a urethane bond and not containing an acid anhydride group [Comparative Example 1-2]
Add 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 to the reactor to make it uniform. At that point, 129.6 g of ion-exchanged water was added, and the mixture was stirred at 25 ° C. for 4 hours. 37.4 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a liquid having a viscosity of 1,290 mPa · s at 25 ° C., 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 (IV) calculated from the NMR results are a = 0.42, b = 0, c = 0, d = 0, e = 0, f = 0.58, g =, respectively. It was 0.13.

[4] Production of active energy ray-curable composition and cured product thereof [Examples 2-1 to 2-5, Comparative Examples 2-1 and 2-2]
10 parts by mass of each organopolysiloxane compound obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2, DaroCure 1173 (radical photopolymerization initiator, manufactured by BASF) 0.5 The parts by mass are mixed, poured into a mold with a release film attached so that the thickness is 0.2 mm, and the film is cured by irradiating with light so ^{that the cumulative irradiation amount is 600 mJ / cm 2 with a high-pressure mercury lamp.} Manufactured.
The pencil hardness and bending resistance of the obtained film were measured. The results are shown in Table 1.
(1) Pencil hardness Measured under a load of 750 g according to JIS K5600-5-4.
(2) Bending resistance Measured using a cylindrical mandrel (type 1) according to JIS K5600-5-1, the bending resistance was set to> 8 mmφ for films with cracks in the 8 mmφ test. ..

As shown in Table 1, the cured products of Examples 2-1 to 2-5 and Comparative Example 2-2, which are organopolysiloxane compounds containing an acryloyloxy group bonded via a urethane bond, have a pencil hardness and a pencil hardness. It can be seen that while both the bending resistance characteristics are good, the cured product of Comparative Example 2-1 having no urethane bond does not have bending resistance.

[5] Production of coating composition and coated article [Examples 3-1 to 3-5, Comparative Examples 3-1 and 3-2]
10 parts by mass of each organopolysiloxane compound obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2, DaroCure 1173 (radical photopolymerization initiator, manufactured by BASF) 0.5 The parts by mass are mixed, and the coating composition is spin-coated on a silicon wafer at a rotation speed of 1,500 rpm so that the coating film has an exposed part and an unexposed part through a photomask having a predetermined pattern. A film was formed by irradiating light with a high-pressure mercury lamp so as to have an integrated irradiation amount of 600 mJ / cm ² and curing the film to produce a coated article. Then, the coated article was immersed in a 0.1% by mass KOH aqueous solution for development, and the unexposed coating composition was removed. After washing with water, the film residue remaining on the substrate was observed with an optical microscope. If no residue remained, KOH developability was OK, and if it remained, it was NG. The results are shown in Table 2.

As shown in Table 2, 3- only in (trimethoxysilyl) propyl film article coated with Examples 3-1 to 3-5 and Comparative Examples 3-1 Coating compositions containing succinic anhydride component KOH developability is observed, showing the superiority of the organopolysiloxane compound having a polymerizable functional group of the present invention.

Claims (7)

An organopolysiloxane compound having a structural unit represented by the following formulas (I) and (II).

(In the formula, R ¹ and R ⁵ represent hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, or i-propyl groups independently of each other, and R ² , R ^{3 and R 6} are independent of each other. Then, it represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer satisfying 0 ≦ n ≦ 2, and m represents 0 ≦ m ≦. Represents an integer that satisfies 2.) Further, it has a structural unit represented by the following formula (III), and the total ratio of the number of alkoxy groups directly bonded to the silicon atom and the number of hydroxyl groups directly bonded to the silicon atom to the number of silicon atoms is 0.3 or less. The organopolysiloxane compound according to claim 1.

(In the formula, R ⁷ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxy, which may be substituted with a hydrogen atom or a halogen atom independently of each other. Represents a propyl group.) An active energy ray-curable composition containing the organopolysiloxane compound according to claim 1 or 2 and a photopolymerization initiator. The active energy ray-curable composition according to claim 3, further containing a polymerizable unsaturated compound other than the organopolysiloxane compound. The active energy ray-curable composition according to claim 3 or 4, further containing a solvent. A cured product obtained by curing the active energy ray-curable composition according to any one of claims 3 to 5. A resist film made of the cured product according to claim 6.