KR102675714B1 - Organopolysiloxane compound and active energy ray curable composition containing the same - Google Patents

Abstract

[Project] To provide an organopolysiloxane that satisfies both hardness and toughness and provides an alkali-developable cured film, and an active energy ray-curable composition containing this organopolysiloxane that can be used as a negative resist material. .
[Solution] An organopolysiloxane compound having structural units represented by the following formulas (I) and (II).

(In the formula, 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 independently represent the number of carbon atoms. represents a divalent hydrocarbon group of 1 to 10, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer that satisfies 0≤n≤2, and m represents an integer that satisfies 0≤m≤2.)

Description

Organopolysiloxane compound and active energy ray curable composition containing the same {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, it relates to an organopolysiloxane compound having an alkali-soluble site and an active energy ray-curable composition containing the same.

As LSI becomes more highly integrated and faster, there is a demand for finer resist patterns in the semiconductor device manufacturing process.　 Additionally, in the manufacture of flexible devices such as organic EL, resist materials with bending resistance and toughness are required.

In general, a positive photoresist whose solubility in an alkaline developer increases when exposed to light is often used for the resist pattern. In the positive photoresist, naphthoquinonediazide sulfonic acid used as a photosensitizer generates sulfonic acid, thereby forming a metal wiring. It has the problem of corroding parts.

On the other hand, negative photoresists using a mixture of photocurable resin and alkali-soluble resin do not have this problem, but the hardened product has weak strength and insufficient photostability and thermal stability, so it is considered unsuitable for fine patterning. .

Organopolysiloxane compounds containing organic functional groups are preferable as photoresist materials because they have excellent properties such as weather resistance, heat resistance, impact resistance, crack resistance, and processability.

For example, in Patent Document 1, an organopolysiloxane compound is synthesized by hydrolytic condensation of methyltrimethoxysilane, 3-(trimethoxysilyl)propyl succinic anhydride, and 3-acryloxypropyltrimethoxysilane, Developability and corrosiveness are being examined.

In Patent Document 2, an organopolysiloxane compound is synthesized by hydrolytic condensation of tetraethoxysilane, 3-(trimethoxysilyl)propyl succinic anhydride, and 3-(meth)acryloxypropyltrimethoxysilane, and ethylenic It is mixed with a compound having two or more unsaturated groups and a radical photopolymerization initiator, and the heat resistance transparency, pencil hardness, developability, etc. of the cured product are examined.

Additionally, (meth)acrylate is widely used as an unsaturated compound having radical polymerization.

However, in general, hard (meth)acrylates have the problem of being brittle and prone to cracking, while flexible (meth)acrylates have problems of having poor curability and being prone to swelling in solvents.

Therefore, studies are being conducted to improve the toughness of the cured product by including urethane bonds in the components of the (meth)acrylate compound, thereby coagulating the molecules with each other through hydrogen bonds derived from the urethane bonds.

For example, Patent Document 3 discloses an example in which silsesquioxane was synthesized by hydrolytic condensation of 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 capable of alkali development.

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

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 by alkali, and that contains this organopolysiloxane and has an activity that can be used as a negative resist material. The purpose is to provide an energy ray curable composition.

The present inventors have conducted extensive studies to achieve the above object, and as a result, an organopolysiloxane compound 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 has been found. The present invention was completed by discovering that the composition provides a cured film that is excellent in hardness and toughness and is alkali-developable by irradiation with active energy rays.　 In addition, in the present invention, (meth)acryloyloxy group means acryloyloxy group or methacryloyloxy group.

That is, the present invention

1. An organopolysiloxane compound characterized by having structural units represented by the following formulas (I) and (II),

(In the formula, 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 independently represent the number of carbon atoms. represents a divalent hydrocarbon group of 1 to 10, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer that satisfies 0≤n≤2, and m represents an integer that satisfies 0≤m≤2.)

2. An organopolysiloxane compound of 1, which further has a structural unit represented by the following formula (III) and whose ratio of the total number of alkoxy groups and hydroxyl groups directly bonded to silicon atoms to the number of silicon atoms is 0.3 or less,

(In the formula, R ⁷ independently represents a hydrogen atom, an alkyl group with 1 to 8 carbon atoms that may be substituted with a halogen atom, a phenyl group, (meth)acryloyloxypropyl group, or glycidoxypropyl group. )

3. An active energy ray curable composition containing the organopolysiloxane compound of 1 or 2 and a photopolymerization initiator,

4. The active energy ray curable composition of 3 further containing a polymerizable unsaturated compound other than the organopolysiloxane compound,

5. The active energy ray curable composition of 3 or 4 further containing a solvent;

6. A cured product obtained by curing the active energy ray curable composition of any one of 3 to 5,

7. Resist film containing the cured product of 6

provides.

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 exhibits radical curability by various active energy rays and is capable of forming radicals. By curing, a cured film excellent in hardness and toughness is provided.　 In addition, since the obtained cured film has alkali solubility and can be easily developed, the curable composition containing the organopolysiloxane compound of the present invention is also useful as a negative photoresist material.

Hereinafter, the present invention will be described in detail.

(1) Organopolysiloxane compound

The organopolysiloxane compound according to the present invention is characterized by having structural units 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 independently represent a carbon atom. represents a divalent hydrocarbon group having 1 to 10 atoms, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer that satisfies 0≤n≤2, and m represents an integer that satisfies 0≤m≤2. .

Additionally, when two R ^1s exist, they may be the same or different from each other, and when two R ^5s exist, they may be the same or different from each other.

The divalent hydrocarbon group having 1 to 10 carbon atoms for R ² , R ³ and R ⁶ may be straight chain, branched or cyclic, and specific examples thereof include methylene, ethylene, trimethylene, propylene, tetramethylene and hexane. straight-chain, branched, or cyclic alkylene groups such as xylene, decylene, and cyclohexylene groups; Arylene groups such as phenylene and xylylene groups 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 structural units of general formulas (I) and (II), the curability of the curable composition containing the organopolysiloxane compound, and the hardness and crack resistance of the cured product obtained from the composition, From the viewpoint of bending resistance and water resistance, in general formulas (I) and (II), R ¹ is a methyl group, R ² is a trimethylene group, R ³ is an ethylene group, R ⁴ is a hydrogen atom, and R ⁵ It is preferable that is a methyl group and R ⁶ is a trimethylene group.

In addition, the organopolysiloxane compound of the present invention is effective in suppressing the condensation reaction due to the condensable functional group, and from the viewpoint of crack resistance, water resistance, and weather resistance of the obtained cured product, the structural unit represented by the following general formula (III) It is preferable that 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, and more preferably 0.2 or less.

In formula (III), R ⁷ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms optionally substituted with a halogen atom, a phenyl group, (meth)acryloyloxypropyl group, or glycidoxypropyl group. It represents energy.

The alkyl group having 1 to 8 carbon atoms for R ⁷ may be straight-chain, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-. Examples include butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl groups, and some or all of the hydrogen atoms of these alkyl groups may be substituted with halogen atoms.

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 phenyl group having 1 to 4 carbon atoms is preferable, and a methyl group or phenyl group is more preferable.

In the present invention, as the organopolysiloxane compound having structural units represented by the above formulas (I) to (III), a 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 meaning as above, R ⁸ represents a hydrogen atom, methyl group, ethyl group, n-propyl group or i-propyl group, a , b, c, d, e and f are 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+ It represents a number that satisfies b+c+d+e+f=1, and g represents a number that satisfies 0≤g≤0.3.

The above a is preferably a number that satisfies 0.05≤a≤0.6, and is more preferably 0.1≤a≤0.5 from the viewpoint of the curability of the composition containing the organopolysiloxane compound and the hardness, scratch resistance, and crack resistance of the cured product.　

The above b is preferably a number that satisfies 0.05≤b≤0.6, and is 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 that satisfies 0≤c≤0.03, and from the viewpoint of viscosity (workability) of the organopolysiloxane compound, 0≤c≤0.01 is more preferable.

The d is preferably a number that satisfies 0≤d≤0.4, and is more preferably 0≤d≤0.2 from the viewpoint of crack resistance and bending resistance of the resulting cured product.

The above e is preferably a number that satisfies 0≤e≤0.4, and from the viewpoint of hardness of the resulting cured product, 0≤e≤0.3 is more preferable.

The f is preferably a number that satisfies 0≤f≤0.7, and is more preferably 0.2≤f≤0.6 from the viewpoint of the viscosity (workability) of the organopolysiloxane compound and the hardness of the resulting cured product.

The above g is preferably a number that satisfies 0≤g≤0.3, and is effective in suppressing the condensation reaction due to the condensable functional group. However, considering the crack resistance, water resistance, and weather resistance of the resulting cured product, 0≤g≤0.2 A number that satisfies is more desirable.

The organopolysiloxane compound of the present invention may have a single composition or may be 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 is preferably 200 to 100,000, more preferably 500 to 5,000, in terms of polystyrene conversion as determined by gel permeation chromatography (GPC).

Within this range, condensation proceeds sufficiently, the organopolysiloxane compound has excellent preservability, and can be quickly removed in alkali development.

The viscosity of the organopolysiloxane compound of the present invention is not particularly limited, but from the viewpoint of workability and processability, the viscosity at 25°C as measured by a rotational viscometer is preferably 50 to 100,000 mPa·s, and 100 to 20,000 mPa. ·s is more preferable.

In addition, the organopolysiloxane compound of the present invention preferably has a nonvolatile content of 90% by mass or more excluding organic solvents and the like.　 If the volatile content decreases, the deterioration of the appearance and the deterioration of the mechanical properties due to the generation of voids when the composition is cured are suppressed.

The organopolysiloxane compound of the present invention can be produced according to a general organopolysiloxane production method.

For example, the organopolysiloxane 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 hydrolysable silane containing an organic group having an acid anhydride group. .

Specifically, there is a method of producing an organopolysiloxane compound by performing hydrolytic condensation in the presence of a catalyst using a hydrolyzable silane represented by the following formula (V) and, if necessary, other hydrolysable silanes. .

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 It represents energy.)

As the alkoxy group having 1 to 6 carbon atoms for Toxi, t-butoxy, and pentyloxy groups can be mentioned.

Examples of the organic group having a urethane bond and a (meth)acryloyloxy group for R ⁹ include the groups shown below bonded to the silicon atom in the formula (I).

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

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

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

Additionally, other hydrolyzable silanes used as needed are not particularly limited as long as they can be used to produce an organopolysiloxane compound by hydrolytic condensation with the hydrolyzable silane represented by the general formula (IV).

Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, p -Styryltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidoxypropyltrime Toxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxy Trialkoxysilanes such as silane and 3-acryloyloxypropyltriethoxysilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxy Dialkoxysilanes such as propylmethyldiethoxysilane; Trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-methacryloyl Monoalkoxysilanes such as oxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylmethoxysilane, and 3-acryloxypropyldimethylethoxysilane, or their hydrolysis Condensates of hexamethyldisiloxane, 1,3-di(3-glycidoxypropyl)tetramethyldisiloxane, 1,3-di(3-methacryloyloxypropyl)tetramethyldisiloxane, 1,3-di (3-acryloxypropyl)tetramethyldisiloxane, etc. are mentioned.

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, carbonic acid, methanesulfonic acid, and trifluoric acid. Lomethane sulfonic acid, etc. can be mentioned.

The amount of catalyst used is not particularly limited, but considering the rapid progress of the reaction and the ease of catalyst removal after the reaction, it is preferably in the range of 0.0002 to 0.5 mole per mole of hydrolysable silane.

The amount ratio of hydrolysable silane and water required for the hydrolytic condensation reaction is not particularly limited, but considering the ease of removing water after the reaction as well as preventing deactivation of the catalyst and allowing the reaction to proceed sufficiently, the ratio is 1 mole of hydrolysable silane. A ratio of 0.1 to 10 moles of water is preferable.

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

Additionally, in the case of hydrolysis condensation, an organic solvent may be used.　 Specific examples of organic solvents 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 described above 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 includes known photopolymerization initiators such as acetophenone series, benzoin series, acylphosphine oxide series, benzophenone series, and thioxanthone series. It can be selected and used appropriately.

Specific examples of photopolymerization initiators include benzophenone, benzyl, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, and 1-hydroxy. Cyclohexylphenylketone, acylphosphine oxide derivative, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide , 2,4,6-trimethylbenzoyldiphenylphosphine, etc., and these may be used individually or in combination of two or more types.

The photopolymerization initiator can be obtained as a commercial product, and commercial products include, for example, 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, Lucirin TPO (all made by BASF Japan), etc. can be mentioned.

Considering that the amount of the photopolymerization initiator used is to improve the curability of the composition and prevent a decrease in the surface hardness of the cured product, the total amount of the organopolysiloxane compound of the present invention and the polymerizable unsaturated compound used as necessary is 100. It is preferably 0.1 to 20 parts by mass relative to parts by mass.

The active energy ray-curable composition of the present invention may contain polymerizable unsaturated compounds other than the organopolysiloxane compound of the present invention.

Specific examples of polymerizable unsaturated compounds include 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, 3-(meth) Acryloyloxyglycerin mono(meth)acrylate, urethane acrylate, epoxy acrylate, ester acrylate, etc. are mentioned.

When using a polymerizable unsaturated compound, its content is preferably 1 to 1,000 parts by mass with respect 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 contains metal oxide fine particles, silicone resin, silane coupling agent, diluting solvent, plasticizer, filler, sensitizer, light absorber, light stabilizer, polymerization inhibitor, heat ray reflector, antistatic agent, Various additives such as antioxidants, antifouling agents, water repellency imparting agents, antifoaming agents, colorants, thickeners, and leveling agents may be included as long as they do not impair the purpose of the present invention.

The active energy ray-curable composition of the present invention is obtained by uniformly mixing 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 considering that it improves molding or application workability and suppresses the occurrence of streaks, etc., the viscosity at 25°C measured by a rotational viscometer is First, 100,000 mPa·s or less is preferable, and 20,000 mPa·s or less is more preferable.　 Additionally, the lower limit of 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, especially as a resist, and is applied to at least one side of a substrate directly or through at least one other layer and cured to form a film. A formed covered article can be obtained.

The substrate is not particularly limited, but includes silicon wafers, metals, plastic molded bodies, ceramics, glass, and composites thereof.

In addition, substrates whose surfaces have been treated with chemical conversion, corona discharge treatment, plasma treatment, acid or alkaline solution, or decorative plywood whose surfaces are coated with different types of paints than the substrate body can also be used.

The application method of the coating agent may be appropriately selected from known methods. For example, various application methods such as spin coating, bar coater, brush application, spray, dipping, flow coating, roll coating, curtain coating, and knife coating can be used. You can.

As a light source for curing the active energy ray curable composition, a light source containing light with 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, etc. .

The irradiation amount is not particularly limited, but is preferably 10 to 5,000 mJ/cm2, and more preferably 20 to 1,000 mJ/cm2.

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

[Example]

Hereinafter, the present invention will be described in more detail by describing examples and comparative examples, but the present invention is not limited to the following examples.

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

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

[1] Synthesis of an organopolysiloxane compound containing an acid anhydride group and an acryloyloxy group bonded through a urethane bond

[Example 1-1]

While stirring 348.3 g (3.0 mol) of hydroxyethyl acrylate (manufactured by Osaka Yuki Chemical Industries, Ltd.) in the reactor, 3-isocyanate propyltrimethoxysilane (KBM-9007, manufactured by Shin-Etsu Chemical Industries, Ltd.) was stirred. ) After adding 1115.9 g (3.0 mol) of agent), 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).

To this, 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 were added, and when it became uniform, 147.6 g of ion-exchanged water was added, It was stirred at 25°C for 4 hours.　 35.9 g of Kyowad 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 4,500 mPa·s, 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 results of NMR were a = 0.35, b = 0.14, c = 0, d = 0, e = 0, f = 0.51, 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-(trimethoxysilyl)propyl succinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane, and 6.9 g of methanesulfonic acid. It was added to the reactor, and when it became uniform, 165.6 g of ion-exchanged water was added and stirred at 25°C for 2 hours.　 34.5 g of Kyowad 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, 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 results of NMR were a = 0.22, b = 0.23, c = 0, d = 0, e = 0, f = 0.55, 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-(trimethoxysilyl)propyl succinic anhydride, 136.2 g (1.0 mol) of methyltrimethoxysilane, hexamethyldisiloxane 487.1 g (3.0 mol) and 6.3 g of methanesulfonic acid were added to 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 Kyowad 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, 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 results of NMR were a = 0.26, b = 0.09, c = 0, d = 0.10, e = 0, f = 0.55, 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-(trimethoxysilyl)propyl succinic anhydride, 240.4 g (2.0 mol) of dimethyldimethoxysilane, 487.1 hexamethyldisiloxane g (3.0 mol), 7.9 g of methanesulfonic acid was added to the reactor, and when it became uniform, 190.8 g of ion-exchanged water was added and stirred at 25°C for 2 hours.　 39.6 g of Kyowad 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, 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 NMR 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-(trimethoxysilyl)propyl succinic anhydride, 480.8 g (4.0 mol) of dimethyldimethoxysilane, and 5.0 g of methanesulfonic acid. It was added to the reactor, and when it became uniform, 324.0 g of ion-exchanged water was added and stirred at 25°C for 4 hours.　 24.9 g of Kyowad 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 with 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 results of NMR were a = 0.32, b = 0.17, c = 0, d = 0, e = 0.51, f = 0, g = 0.9, respectively. .

[2] Synthesis of an organopolysiloxane compound containing an acryloyloxy group without a urethane bond and an acid anhydride group

[Comparative Example 1-1]

702.9 g (3.0 mol) of 3-acryloyloxypropyltrimethoxysilane, 262.3 g (1.0 mol) of 3-(trimethoxysilyl)propyl succinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane, 5.1 g (3.0 mol) of methanesulfonic acid. g was added into the reactor, and when it became uniform, 147.6 g of ion-exchanged water was added and stirred at 25°C for 4 hours.　 25.3 g of Kyowad 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 with 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 results of NMR 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 that has an acryloyloxy group bonded through a urethane bond and does not contain an acid anhydride group.

[Comparative Example 1-2]

285.6 g (4.0 mol) of compound 1 represented by the above formula (VI), 487.13 g (3.0 mol) of hexamethyldisiloxane, and 7.5 g of methanesulfonic acid were added to the reactor, and when uniform, 129.6 g of ion-exchanged water was added, It was stirred at 25°C for 4 hours.　 37.4 g of Kyowad 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 with 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 results of NMR were a = 0.42, b = 0, c = 0, d = 0, e = 0, f = 0.58, and g = 0.13, respectively. .

[4] Production of active energy ray curable composition and its cured product

[Examples 2-1 to 2-5, Comparative Examples 2-1, 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 and 0.5 parts by mass of Darocure 1173 (radical photopolymerization initiator, manufactured by BASF) were mixed, and the thickness was obtained. A film was produced by pouring it into a mold attached with a release film to a thickness of 0.2 mm, irradiating it with light with a high-pressure mercury lamp at an integrated irradiation amount of 600 mJ/cm2, and curing it.

Pencil hardness and bending resistance were measured for the obtained film.　 The results are shown in Table 1.

(1) Pencil hardness

Measured under a load of 750 g according to JIS K5600-5-4.

(2) Flexibility

Measurements were made using a cylindrical mandrel (type 1) in accordance with JIS K5600-5-1, and regarding bending resistance, the film that cracked in the 8mmϕ test was set to >8mmϕ.

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 acryloyloxy groups bonded through urethane bonds, have pencil hardness and bending resistance. While both properties are good, it can be seen that the cured product of Comparative Example 2-1, which does not have a urethane bond, does not have bending resistance.

[5] Preparation of coating compositions and coated articles

[Examples 3-1 to 3-5, Comparative Examples 3-1, 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 and 0.5 parts by mass of Darocure 1173 (radical photopolymerization initiator, manufactured by BASF) were mixed, The coating composition is spin-coated on a silicon wafer at a rotation speed of 1,500 rpm, and irradiated with light through a photomask having a predetermined pattern so that the coating film has an exposed area and an unexposed area with a high-pressure mercury lamp at an integrated irradiation amount of 600 mJ/cm2, A coating was formed by curing, thereby producing a coating article.　 Thereafter, the coated article was immersed in a 0.1% by 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 under an optical microscope. If no residue remained, the KOH developability was rated as OK, and if it remained, it was rated as NG.　 The results are shown in Table 2.

As shown in Table 2, only for coated articles coated with the coating compositions of Examples 3-1 to 3-5 and Comparative Example 1-1 containing 3-(trimethoxysilyl)propyl succinic anhydride as a component. KOH developability was shown, showing the superiority of the organopolysiloxane compound having a polymerizable functional group of the present invention.

Claims (7)

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

(In the formula, 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 independently represent the number of carbon atoms. represents a divalent hydrocarbon group of 1 to 10, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer that satisfies 0≤n≤2, and m represents an integer that satisfies 0≤m≤2.) The organopolysiloxane according to claim 1, which further has a structural unit represented by the following formula (III), and wherein the ratio of the sum of the number of alkoxy groups directly bonded to silicon atoms and the number of hydroxyl groups directly bonded to silicon atoms to the number of silicon atoms is 0.3 or less. compound.

(In the formula, R ⁷ independently represents a hydrogen atom, an alkyl group with 1 to 8 carbon atoms that may be substituted with a halogen atom, a phenyl group, (meth)acryloyloxypropyl group, or glycidoxypropyl 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 comprising a polymerizable unsaturated compound other than the organopolysiloxane compound. The active energy ray curable composition according to claim 3, further containing a solvent. A cured product obtained by curing the active energy ray curable composition according to claim 3. A resist film comprising the cured product according to claim 6.