KR20190070870A - Organopolysiloxane compound and active energy ray curable composition containing the same - Google Patents

Abstract

The present invention is to provide organopolysiloxane which satisfies both hardness and ductility, and provides a cured film capable of developing alkali, and to an active energy ray-curable composition which can be used as a negative resist material by containing the same. According to the present invention, an organopolysiloxane compound has a composition unit represented by formulas (I) and (II). In the formulas, R^1 and R^5 each independently represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, R^2, R^3 and R^6 independently represent 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 an integer satisfying 0 <= m <= 2.

Description

TECHNICAL FIELD [0001] The present invention relates to an organopolysiloxane compound and an active energy ray-curable composition containing the organopolysiloxane compound and an active energy ray-

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

As LSIs become more highly integrated and increased in speed, there has been a demand for miniaturization of resist patterns in the process of manufacturing semiconductor devices. Further, in the production of a flexible device typified by organic EL, a resist material having flex resistance and toughness is required.

In general, a positive-type photoresist is used in which a resist pattern is exposed to a high solubility in an alkaline developer. In a positive-type photoresist, naphthoquinonediazide sulfonic acid used as a photosensitizer generates sulfonic acid, It has a problem of corrosion.

On the other hand, such a problem does not occur in a negative type photoresist using a mixture of a photo-curing resin and an alkali-soluble resin, but it is considered to be unsuitable for fine patterning because the strength of the cured product is weak and the optical stability and thermal stability are insufficient .

The organopolysiloxane compound containing an organic functional group is also preferable as a photoresist material because of its excellent properties such as weather resistance, heat resistance, impact resistance, crack resistance, workability and the like.

For example, in Patent Document 1, an organopolysiloxane compound is synthesized by hydrolysis and condensation of methyltrimethoxysilane, 3- (trimethoxysilyl) propylsuccinic anhydride and 3-acryloxypropyltrimethoxysilane, Developability and corrosion resistance have been studied.

Patent Document 2 proposes an organopolysiloxane compound synthesized by hydrolysis and condensation of tetraethoxysilane, 3- (trimethoxysilyl) propylsuccinic anhydride and 3- (meth) acryloxypropyltrimethoxysilane to produce an organopolysiloxane A compound having two or more unsaturated groups and a photoradical polymerization initiator, the heat resistance of the cured product, the pencil hardness, developability and the like have been examined.

Further, (meth) acrylate is widely used as an unsaturated compound having a radical polymerizing property.

However, in general, hard (meth) acrylate is problematic in that it is brittle and liable to be cracked, and on the other hand, flexible (meth) acrylate has poor curability and is easily swelled in a solvent.

Thus, studies have been made to improve the toughness of the cured product by causing urethane bonds to be contained in the constituent elements of the (meth) acrylate compound, thereby aggregating the molecules by hydrogen bonds derived from urethane bonds.

For example, Patent Document 3 discloses an example of synthesizing silsesquioxane by hydrolysis and condensation of a trifunctional alkoxysilane having a urethane acrylate structure.

However, there is no known active energy ray curable organopolysiloxane compound which satisfies both the hardness and toughness of a cured product and which gives a cured film capable of developing alkali.

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

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide an organopolysiloxane which satisfies both of hardness and toughness and which gives a cured film capable of developing alkali, and an organopolysiloxane containing this organopolysiloxane, Energy radiation curable composition.

DISCLOSURE OF THE INVENTION As a result of intensive investigations to achieve the above object, the present inventors have found that an organopolysiloxane compound having an organic group having a urethane bond and a (meth) acryloyloxy group and an organic group having an acid anhydride group on a silicon atom The present inventors have found out that the composition is excellent in hardness and toughness by irradiation with active energy rays and gives a cured film capable of developing alkali, thereby completing the present invention. In the present invention, (meth) acryloyloxy group means acryloyloxy group or methacryloyloxy group.

That is,

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

Wherein 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 , 1 to 10 divalent hydrocarbon groups, 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. An organopolysiloxane compound having a structural unit represented by the following formula (III) and having a ratio of a total of an alkoxy group and a hydroxyl group directly bonded to a silicon atom to the number of silicon atoms of not more than 0.3,

(Wherein R ⁷ represents, independently of each other, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxypropyl group. )

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

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

5. 3 or 4 active energy radiation curable compositions 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. A resist film comprising a cured product of 6

.

Since the organopolysiloxane compound of the present invention has an organic group having an urethane bond and a (meth) acryloyloxy group and an organic group having an acid anhydride group on a silicon atom, the organopolysiloxane compound exhibits radical curability due to various active energy rays, By curing, a cured film excellent in hardness and toughness is provided. 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 is also useful as a negative type 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 a constitutional unit represented by the following formulas (I) and (II).

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, R ² , R ³ and R ⁶ independently of one another represent a carbon 2 atoms of 1 to 10 monovalent hydrocarbon group, R ⁴ is a hydrogen atom or a methyl group, n represents an integer satisfying 0≤n≤2, m is an integer satisfying 0≤m≤2 .

When two R &lt; ¹ &gt; are present, they may be the same or different and when two R &lt; ⁵ &gt; exist, they may be the same or different.

The divalent hydrocarbon group of 1 to 10 carbon atoms represented by R ² , R ³ and R ⁶ may be any of linear, branched and cyclic, and specific examples thereof include methylene, ethylene, trimethylene, propylene, A straight chain, branched or cyclic alkylene group such as a silylene, a decylene, and a cyclohexylene group; And arylene groups such as phenylene and xylylene group.

Among them, 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 curing properties of the curable composition containing the organopolysiloxane compound, and the hardness, (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 is a hydrogen atom, Is a methyl group, and R &lt; ⁶ &gt; is a trimethylene group.

The organopolysiloxane compound of the present invention is effective for inhibiting the condensation reaction by a condensing functional group, but is preferably a structural unit (III) represented by the following general formula (III) in view of the crack resistance, water resistance and weather resistance of the resulting cured product And the ratio of the total of the number of alkoxy groups directly bonded to silicon atoms to the number of silicon atoms and the total number of hydroxyl groups is preferably 0.3 or less and more preferably 0.2 or less.

In formula (III), R ⁷ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxypropyl Lt; / RTI &gt;

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁷ may be straight chain, branched or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, Butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl and the like. These alkyl groups may have a part or all of their hydrogen atoms substituted by 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 having 1 to 4 carbon atoms or a phenyl group is preferable, and a methyl group or a phenyl group is more preferable.

In the present invention, as the organopolysiloxane compound having the structural unit 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 meanings as defined above, R ⁸ represents a hydrogen atom, methyl group, ethyl group, n-propyl group or i- , b, c, d, e and f satisfy the relationships 0.1? a? 0.5, 0.1? b? 0.5, 0? c? 0.03, 0? d? 0.4, 0? e? 0.4, 0? f? b + c + d + e + f = 1, and g represents a number satisfying 0? g? 0.3.

A is preferably a number satisfying 0.05? A? 0.6, more preferably 0.1? A? 0.5 in view of the curability of the composition containing the organopolysiloxane compound and the hardness, scratch resistance and crack resistance of the cured product.

B is preferably a number satisfying 0.05? B? 0.6, more preferably 0.1? B? 0.5 in view of alkali developability and viscosity (workability) of the organopolysiloxane compound.

C is preferably a number satisfying 0? C? 0.03, more preferably 0? C? 0.01 in view of the viscosity (workability) of the organopolysiloxane compound.

D is preferably a number satisfying 0? D? 0.4, more preferably 0? D? 0.2 from the viewpoint of crack resistance and flexural resistance of the resulting cured product.

E is preferably a number satisfying 0? E? 0.4, more preferably 0? E? 0.3 in view of the hardness of the resulting cured product.

F is preferably a number satisfying 0? F? 0.7, more preferably 0.2? F? 0.6 in view of the viscosity (workability) of the organopolysiloxane compound and the hardness of the resulting cured product.

G is preferably a number satisfying 0? G? 0.3, and is effective in suppressing the condensation reaction by a condensing functional group, but in view of the crack resistance, water resistance and weather resistance of the resulting cured product, 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 is preferably 200 to 100,000, more preferably 500 to 5,000 in terms of polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC).

With such a range, the condensation proceeds sufficiently, the organopolysiloxane compound is excellent in storability, and can be quickly removed in the alkali 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 캜 measured by a rotational viscometer is preferably from 50 to 100,000 mPa 하고, more preferably from 100 to 20,000 mPa · S is more preferable.

The organopolysiloxane compound of the present invention preferably has a non-volatile content of 90% by mass or more, excluding an organic solvent and the like. When the volatile content is decreased, deterioration of appearance and deterioration of mechanical properties due to generation of voids when the composition is cured are suppressed.

The organopolysiloxane compound of the present invention can be produced by a general method for producing an organopolysiloxane.

For example, the organopolysiloxane compound of the present invention can be obtained by condensing a hydrolyzable silane comprising a urethane bond and a hydrolyzable silane containing an organic group having a (meth) acryloyloxy group and an organic group having an acid anhydride group .

Specifically, there can be mentioned a method of producing an organopolysiloxane compound by hydrolysis and condensation in the presence of a catalyst using a hydrolyzable silane represented by the following formula (V) and, if necessary, other hydrolyzable silanes .

R ⁹ SiX ₃ (V)

(Wherein 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 represents, independently of each other, a chlorine atom or an alkoxy group having 1 to 6 carbon atoms Lt; / RTI &gt;

As the alkoxy group having 1 to 6 carbon atoms for X, the alkyl group in the alkoxy group may be any of linear, branched and cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n- Ethoxy, t-butoxy, pentyloxy group and the like.

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

(Wherein R ² to R ⁴ have the same meanings as defined above.)

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

(Wherein R ² to R ⁴ , R ⁶ and X have the same meanings as defined above.)

The other hydrolyzable silane to be optionally used is not particularly limited as long as it is capable of producing an organopolysiloxane compound by hydrolysis and condensation together with the hydrolyzable silane represented by the general formula (IV).

Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, p (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxy silane, 3-methacryloyloxypropyltrimethoxysilane, Trialkoxysilane such as silane and 3-acryloyloxypropyltriethoxysilane; Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxime Acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxy Dialkoxysilane such as propylmethyldiethoxysilane; Trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-methacryloyl Monoalkoxysilanes such as 3-methacryloyloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylmethoxysilane, and 3-acryloxypropyldimethylethoxysilane, or hydrolysis thereof (3-methacryloxypropyl) tetramethyldisiloxane, 1,3-di (3-glycidoxypropyl) tetramethyldisiloxane, 1,3-di (3-acryloxypropyl) tetramethyldisiloxane, and the like.

The catalyst used for the 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 methanesulfonic acid.

The amount of the catalyst to be used is not particularly limited, but it is preferably in the range of 0.0002 to 0.5 mol based on 1 mol of the hydrolyzable silane, considering the ease of catalyst removal after the reaction as well as the rapid progress of the reaction.

The ratio of the amount of the hydrolyzable silane and the amount of water required for the hydrolysis and condensation reaction is not particularly limited. However, considering the ease of removing the water after the reaction, 0.1 to 10 mol of water is preferable.

The reaction temperature at the time of hydrolysis and condensation is not particularly limited, but from the viewpoint of improving the reaction rate and preventing the decomposition of the organic functional group of the hydrolyzable silane, it is preferably -10 to 150 ° C.

In the hydrolysis and condensation, an organic solvent may 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 above-described 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 a radical species by an active energy ray. The photopolymerization initiator may be any known photopolymerization initiator such as acetophenone, benzoin, acylphosphine oxide, benzophenone, It can be selected and used properly.

Specific examples of the photopolymerization initiator include benzophenone, benzyl, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, Cyclohexyl phenyl ketone, an acylphosphine oxide derivative, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1-one, 4-benzoyl- , 2,4,6-trimethylbenzoyldiphenylphosphine, etc. These may be used alone or in combination of two or more.

The photopolymerization initiator can be obtained as a commercially available product and commercially available products include, for example, DARACURE 1173, DARACURE MBF, IRGACURE 127, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, Irgacure 751, Irgacure 784, Irgacure 819, Irgacure 819DW, Irgacure 907, Irgacure 1800, Irgacure 2959, Lusirin TPO (all manufactured by BASF Japan), etc. .

Considering that the curing property of the composition is improved and the decrease in the surface hardness of the cured product is prevented from being lowered, the amount of the photopolymerization initiator to be used is preferably in the range of 100 to 100 parts by mass of the organopolysiloxane compound of the present invention and the polymerizable unsaturated compound Is preferably 0.1 to 20 parts by mass relative to the mass part.

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, trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) Acryloyloxy glycerin mono (meth) acrylate, urethane acrylate, epoxy acrylate, and ester acrylate.

When a polymerizable unsaturated compound is used, its content is preferably 1 to 1,000 parts by mass per 100 parts by mass of the organopolysiloxane compound of the present invention.

The active energy ray curable composition of the present invention may further contain at least one selected from the group consisting of metal oxide fine particles, silicone resin, silane coupling agent, diluting solvent, plasticizer, filler, sensitizer, light absorber, light stabilizer, polymerization inhibitor, Various additives such as an antioxidant, an antifouling agent, a water repellency-imparting agent, a defoaming agent, a colorant, a thickening agent, and a leveling agent may be added to the composition insofar as the object of the present invention is not impaired.

The active energy ray curable composition of the present invention can be obtained by homogeneously mixing each of the above components in accordance with a conventional method.

The viscosity of the active energy ray curable composition of the present invention is not particularly limited. However, considering that molding or coating workability is improved and occurrence of streaks or the like is suppressed, viscosity at 25 캜 measured by a rotational viscometer Is preferably 100,000 mPa 占 퐏 or less, and more preferably 20,000 mPa 占 퐏 or less. The lower limit of the viscosity at 25 占 폚 is preferably 10 mPa 占 퐏 or more.

The above-mentioned active energy ray-curable composition of the present invention can be suitably used as a coating agent, particularly a resist, and can be applied to at least one side of a substrate directly or through at least one other layer, Thereby forming a coated article.

The substrate is not particularly limited, and examples thereof include a silicon wafer, a metal, a plastic molding, a ceramics, a glass, and a composite thereof.

The surface of these substrates may be treated with a chemical treatment, a corona discharge treatment, a plasma treatment, a substrate treated with an acid or an alkaline solution, or a fancy plywood coated with a coating material of a different type from the surface of the substrate body.

The coating method may be appropriately selected from known methods and 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 .

Examples of the light source for curing the active energy ray-curable composition include light sources including light having a wavelength in the range of 200 to 450 nm such as high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, xenon lamps, .

The irradiation dose is not particularly limited, but is preferably 10 to 5,000 mJ / cm2, 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 way of examples and comparative examples, but the present invention is not limited to the following examples.

In the following, the volatile matter is a value measured according to JIS C2133. The weight average molecular weight is determined by using tetrahydrofuran (THF) as a developing solvent using GPC (gel permeation chromatography, manufactured by HLC-8220, .

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

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

[Example 1-1]

While stirring 348.3 g (3.0 mol) of hydroxyethyl acrylate (manufactured by Osaka Yukigakagaku Kogyo Co., Ltd.) in the reactor, 3-isocyanate propyltrimethoxysilane (KBM-9007, manufactured by Shinetsu Chemical Industry Co., ) Was added to the solution, and the mixture was stirred at 25 占 폚 for 1 hour to obtain 964.2 g (3.0 mol) of the compound represented by the following formula (VI).

Thereto were added 262.3 g (1.0 mol) of 3- (trimethoxysilyl) propylsuccinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane and 7.2 g of methanesulfonic acid, and 147.6 g of ion- Followed by stirring at 25 ° C for 4 hours. And 35.9 g of Kyoward 500SH (manufactured by Kyoe Kagaku Kogyo K.K.) were charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

The obtained reaction product was a liquid viscous at 25 占 폚 with a viscosity of 4,500 mPa 占 퐏, a volatile content of 1.3% by mass, and a weight average molecular weight of 1,350 at 25 占 폚. 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 .

[Example 1-2]

(2.0 mol) of the compound represented by the above formula (VI), 524.7 g (2.0 mol) of 3- (trimethoxysilyl) propylsuccinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane and 6.9 g of methanesulfonic acid The reactor was charged with 165.6 g of ion-exchanged water at the time of becoming homogeneous, and the mixture was stirred at 25 ° C for 2 hours. And 34.5 g of Kyoward 500SH (manufactured by Kyoe Kagaku Kogyo K.K.) were charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

The obtained reaction product was a liquid viscous at 25 占 폚 with a viscosity of 3,200 mPa 占 퐏, a volatile content of 2.5% by mass, and a weight average molecular weight of 1,530 at 25 占 폚. 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 .

[Example 1-3]

(2.0 mol) of the compound represented by the above formula (VI), 262.3 g (1.0 mol) of 3- (trimethoxysilyl) propylsuccinic anhydride, 136.2 g (1.0 mol) of methyltrimethoxysilane, (3.0 mol) of methanesulfonic acid were added to the reactor, and 147.6 g of ion-exchanged water was added at the time of homogeneity, and the mixture was stirred at 25 캜 for 2 hours. And 31.3 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) were added and neutralized by stirring for 2 hours. 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 占 폚 having a viscosity of 2,990 mPa 占 퐏 at 25 占 폚, 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 were a = 0.26, b = 0.09, c = 0, d = 0.10, e = 0, f = 0.55 and g = 0.08 .

[Example 1-4]

(1.0 mol) of 3- (trimethoxysilyl) propylsuccinic anhydride, 240.4 g (2.0 mol) of dimethyldimethoxysilane, 487.1 g of hexamethyldisiloxane g (3.0 mol) of methanesulfonic acid and 7.9 g of methanesulfonic acid were added to the reactor, 190.8 g of ion-exchanged water was added at the time of uniformity, and the mixture was stirred at 25 캜 for 2 hours. , And 39.6 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) were added and neutralized by stirring for 2 hours. 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 占 폚 at a viscosity of 7,200 mPa 占 퐏, a volatile content of 3.1% by mass, and a weight average molecular weight of 1,620 at 25 占 폚. 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, g = 0.09 .

[Example 1-5]

(2.0 mol) of the compound represented by the above formula (VI), 262.3 g (1.0 mol) of 3- (trimethoxysilyl) propylsuccinic anhydride, 480.8 g (4.0 mol) of dimethyldimethoxysilane and 5.0 g of methanesulfonic acid And 324.0 g of ion-exchanged water was added at the time of becoming homogeneous, followed by stirring at 25 캜 for 4 hours. And 24.9 g of Kyoward 500SH (manufactured by Kyoe Kagaku Kogyo K.K.) were charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

The obtained reaction product had a viscosity of 23,000 mPa 에서 at 25 캜, 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 .

[2] Synthesis of an organopolysiloxane compound containing an acryloyloxy group having no urethane bond and an acid anhydride group

[Comparative Example 1-1]

(3.0 mol) of 3-acryloyloxypropyltrimethoxysilane, 262.3 g (1.0 mol) of 3- (trimethoxysilyl) propylsuccinic anhydride, 487.1 g (3.0 mol) of hexamethyldisiloxane, g was added to the reactor, and 147.6 g of ion-exchanged water was added at the time of becoming homogeneous, and the mixture was stirred at 25 캜 for 4 hours. And 25.3 g of Kyoward 500SH (manufactured by Kyoe Kagaku Kogyo K.K.) were charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

The obtained reaction product had a viscosity of 190 mPa 에서 at 25 캜, 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 (V) calculated from the NMR results were a = 0, b = 0.14, c = 0, d = 0.42, e = 0, f = 0.44, g = 0.08 .

[3] Synthesis of an organopolysiloxane compound having an acryloyloxy group bonded through a urethane bond and containing no acid anhydride group

[Comparative Example 1-2]

285.6 g (4.0 mol) of the 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 129.6 g of ion- Followed by stirring at 25 ° C for 4 hours. And 37.4 g of Kyoward 500SH (manufactured by Kyoe Kagaku Kogyo K.K.) were charged and neutralized by stirring for 2 hours. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.

The obtained reaction product had a viscosity at 25 캜 of 1,290 mPa s, 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 were a = 0.42, b = 0, c = 0, d = 0, e = 0, f = 0.58 and g = 0.13 .

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

[Examples 2-1 to 2-5, Comparative Examples 2-1 and 2-2]

10 parts by mass of each of the organopolysiloxane compounds obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2 and 0.5 part by mass of DARACURE 1173 (radical photopolymerization initiator, BASF) were mixed, And the film was cured by irradiating light with a high-pressure mercury lamp so that the cumulative irradiation amount became 600 mJ / cm 2.

The resulting film was measured for pencil hardness and flex resistance. The results are shown in Table 1.

(1) Pencil Hardness

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

(2) Flexibility

The film was measured using a cylindrical mandrel (Type 1) in accordance with JIS K5600-5-1, and with respect to the bending resistance, a film with cracks in the 8 mm? Test was determined to be> 8 mm ?.

As shown in Table 1, in 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, the pencil hardness and flexural strength It can be seen that both of the properties are good, while the cured product of Comparative Example 2-1 having no urethane bond does not have flexural resistance.

[5] Preparation of coating compositions and coated articles

[Examples 3-1 to 3-5, Comparative Examples 3-1 and 3-2]

10 parts by mass of the respective organopolysiloxane compounds obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2, and 0.5 parts by mass of DARACURE 1173 (radical photopolymerization initiator, BASF) were mixed, The coating composition was 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 as to have an exposure dose of 600 mJ / cm 2 with a high-pressure mercury lamp so as to have an exposed portion and an unexposed portion, And the coating was cured to form a coating film article. Thereafter, the film article was immersed in 0.1% by mass aqueous KOH solution and developed to remove the uncoated coating composition. After washing with water, the film residue remaining on the substrate was observed with an optical microscope. When the residue remained, the development of KOH was OK, and when it remained, it was NG. The results are shown in Table 2.

As shown in Table 2, only in the coating films coated with the coating compositions of Examples 3-1 to 3-5 and Comparative Example 1-1 containing 3- (trimethoxysilyl) propylsuccinic anhydride as a component KOH developability, indicating the superiority 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 formulas (I) and (II).

Wherein 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 , 1 to 10 divalent hydrocarbon groups, 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 according to claim 1, which further has a structural unit represented by the following formula (III) and has a ratio of the total number of alkoxy groups and the number of hydroxyl groups directly bonded to silicon atoms to the number of silicon atoms of 0.3 or less.

(Wherein R ⁷ represents, independently of each other, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxypropyl group. ) An active energy ray curable composition comprising the organopolysiloxane compound according to any one of claims 1 to 3 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 comprising 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.