JP2018039875A - Photocurable composition and cured product containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable composition allowing for formation of a polymer material which has good moldability, is lightweight, and has a high relative dielectric constant.SOLUTION: The photocurable composition is provided that contains as essential components, (a) silsesquioxane represented by general formula (1), (b) an ethylenic unsaturated-functional monomer, (c) an ethylenic unsaturated polyfunctional monomer and (d) a photopolymerization initiator. In general formula (1), A is a divalent hydrocarbon group which may be substituted with a cyano group and has 2 to 20 carbon atoms and includes a methylene group and/or a methine group, where at least one or more of each of the groups are substituted with NR (R represents hydrogen atoms or the like), N, or a combination thereof. The nitrogen atoms, the nitrogen atom and the silicon atom, and the nitrogen atom and the cyano group are not adjacent to each other, the NC-CH-CH- group in the formula (1) is bonded to the nitrogen atom contained in A. B represents a divalent hydrocarbon group having 1 to 10 carbon atoms. m is an integer of 1 to 150, n is an integer of 0 to 50, and m+n is 4 to 150.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable composition and a cured product thereof.

Polymer materials are generally characterized by excellent insulation, flexibility and light weight, and are used in electrical and electronic equipment applications, such as film capacitors, gate insulating films for field effect transistors, and resin antennas. It is used as
In addition, a transparent resin that transmits light is a useful material that is widely used in optical devices such as lenses and optical waveguides, display devices such as displays, and the like.

A film capacitor is required to have a large capacity and a small size, and it is known that the capacity is proportional to the relative dielectric constant of the film used and inversely proportional to the film thickness. Therefore, when the film thickness is the same, the higher the relative dielectric constant of the film, the more the capacitance of the capacitor is increased, so that a high-capacity film capacitor can be obtained.
Polymer materials such as polypropylene, polyester, and polyphenylene sulfide used for film capacitors have low dielectric constants alone, and therefore other dielectrics are added for the purpose of improving the dielectric constant.
For example, Patent Document 1 discloses a polymer composition containing polyphenylene sulfide and dielectric ceramics such as strontium titanate, and describes that the composition can be used for capacitors and antennas.

  Regarding materials used for resin antennas, Patent Document 2 discloses a dielectric elastomer laminate in which dielectric ceramics are added to an elastomer as an intermediate layer to increase the relative dielectric constant. It is described that it contributes to. Further, when a synthetic resin is used for the insulating film of the field effect transistor, a resin having a higher relative dielectric constant is preferable because the transistor capacity increases.

Actuators, which are devices that convert mechanical energy when a certain amount of energy is input, are a type of transducer.
There are several types of actuators, but actuators using dielectric elastomers, which are polymeric materials, can convert electrical energy into mechanical energy, and are flexible thin films, so there are various types of actuators such as micropumps and speakers. Application to various uses has been studied (see Patent Document 3). Conversely, it is known that dielectric elastomers can be used for transducers that convert mechanical energy into electrical energy (see Patent Document 4).
Since the amount of displacement when a constant voltage is applied to the dielectric elastomer sandwiched between the electrodes is proportional to the relative dielectric constant of the elastomer, it is desirable to increase the relative dielectric constant in order to increase the energy conversion efficiency. In this regard, for example, Patent Document 5 discloses a dielectric elastomer in which dielectric ceramic particles having a relative dielectric constant of 1000 or more are dispersed in a crosslinked rubber.

JP 2000-501549 Gazette JP 2006-290939 A JP-T-2001-524278 Special table 2003-505865 gazette JP 2007-153961 A Special table 2010-505995 gazette

For each of the applications described above, a resin having a high relative dielectric constant is required.
If dielectric ceramics such as strontium titanate are blended into the polymer material as in the technique of Patent Document 2, the relative dielectric constant is improved, but in order to obtain a sufficient effect, it is necessary to blend in a large amount. However, the moldability deteriorates and a problem such as a hard material occurs.
Further, in order to mix and uniformly disperse an inorganic material such as dielectric ceramics in a polymer material, special treatment such as appropriate surface treatment with a silane coupling agent is required.
Furthermore, dielectric ceramics have a large specific gravity, and the light weight characteristic of polymer materials may be impaired.

In Patent Document 6, the use of a fluorine-based polymer such as vinylidene fluoride having a high relative dielectric constant is examined, but it cannot be said that the fluorine-based polymer is expensive and highly versatile.
Accordingly, there is a demand for a polymer material having an improved relative dielectric constant without significantly affecting the lightness, moldability, and mechanical properties that are inherent characteristics of the polymer material.

  The present invention has been made in view of the above circumstances. A photocurable composition capable of forming a polymer material having good moldability, light weight, and high dielectric constant, and a cured product using the same. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors cured a photocurable composition containing a silsesquioxane having a 2-cyanoethyl group, a specific polymerizable monomer, and a photopolymerization initiator. As a result, it was found that a transparent and lightweight polymer material having a high relative dielectric constant was obtained, and the present invention was completed.

That is, the present invention
1. (A) Silsesquioxane having a 2-cyanoethyl group represented by the following general formula (1), (b) one or more ethylenically unsaturated monofunctional monomers, (c) one or more ethylenically unsaturated A photocurable composition comprising a polyfunctional monomer and (d) a photopolymerization initiator as essential components;
[In the formula, A may be the same or different and is a divalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted with a cyano group, and the divalent hydrocarbon group includes a methylene group and / or Or an NR (R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or 2-cyanoethyl, which includes a methine group, and at least one of these methylene groups and methine groups is a divalent heteroatom linking group. Represents a group), N is a trivalent heteroatom linking group, or a combination thereof. However, these heteroatom linking groups, the heteroatom linking group and the silicon atom, and the heteroatom linking group and the cyano group are not adjacent to each other, and the NC—CH ₂ —CH ₂ — group in the formula is contained in A. To a heteroatom linking group.
B may be the same or different and represents a C1-C10 divalent hydrocarbon group.
m represents an integer of 1 to 150, n represents an integer of 0 to 50, and m + n is 4 to 150. ]
2. (B) 1 photocurable composition in which at least one of the components is an ethylenically unsaturated monofunctional monomer having a cyano group,
3. (B) one photocurable composition in which at least one of the components is an α, β-unsaturated carboxylic acid ester having a cyano group or an α, β-unsaturated nitrile,
4). (C) The photocurable composition according to any one of 1 to 3, wherein the component is an α, β-unsaturated carboxylic acid ester of a polyhydric alcohol,
5. Furthermore, (e) any one of the photocurable composition containing 1-4 containing a solvent,
6). Hardened | cured material which the photocurable composition in any one of 1-5 hardened | cured,
7). Polymer material having a semi-interpenetrating polymer network structure or an interpenetrating polymer network structure obtained by curing a mixture of a polymer substance having a chain or network structure and any one of photocurable compositions 1 to 5 I will provide a.

The photocurable composition of the present invention can be obtained by a simple method and is stable and has a long shelf life if stored in the dark.
In addition, the cured product obtained by curing the photocurable composition of the present invention has a highly flexible side chain of silsesquioxane having a 2-cyanoethyl group, which is an essential component. Excellent and dielectric constant is high.
Furthermore, since the cured product of the present invention is a transparent polymer material in which constituent components are not uniformly aggregated inside the material and is uniformly mixed, it is transparent and does not contain ceramics having a high specific gravity, and thus is lightweight.
The polymer material made of the cured product of the present invention having such features can adjust the electrical properties and mechanical properties by appropriately selecting the type and composition of the constituent monomers, and therefore, the polymer actuator and It can be suitably used as an insulating film for organic transistors.

Hereinafter, the present invention will be specifically described.
[1] [Constituent Component of Photocurable Composition]
(A) Silsesquioxane having 2-cyanoethyl group The photocurable composition of the present invention contains silsesquioxane having a 2-cyanoethyl group represented by the following general formula (1) as an essential component.

In the formula (1), A may be the same or different and is a divalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted with a cyano group, and the divalent hydrocarbon group is a methylene group. And / or NR, wherein at least one of these methylene and methine groups is a divalent heteroatom linking group (R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or 2 -Represents a cyanoethyl group), N which is a trivalent heteroatom linking group, or a combination thereof. However, these heteroatom linking groups, the heteroatom linking group and the silicon atom, and the heteroatom linking group and the cyano group are not adjacent to each other, and the NC—CH ₂ —CH ₂ — group in the formula is contained in A. To a heteroatom linking group.

  Specific examples of the divalent hydrocarbon group serving as the skeleton of A include ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decandiyl group, undecandiyl group, Linear alkanediyl groups such as dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, hexadecanediyl group, heptadecanediyl group, octadecanediyl group, nonadecanediyl group, eicosandiyl group; 2-methylpropane Diyl group, 4-methylheptanediyl group, 4-ethylheptanediyl group, 4-propylheptanediyl group, 2-butylheptanediyl group, 3-propyloctanediyl group, 2-butylnonanediyl group, 4-methyldecanediyl group Group 4-e Branched chain alkanediyl groups such as rudecandidiyl group, 3-propyldecanediyl group, 2-butyldecanediyl group, 3-butylundecandiyl group; cyclohexanediyl group, ethylcyclohexanediyl group, propylcyclohexanediyl group, 4-ethyl Cyclic alkanediyl groups such as -1-methyl-2-propylcyclohexanediyl group, 4-ethyl-2-methyl-1-propylcyclohexanediyl group; 1-ethyl-4-methylbenzenediyl group, 1,4-dimethyl Benzenediyl group, 1,3-dimethylbenzenediyl group, trimethylbenzenediyl group, butylbenzenediyl group, heptylbenzenediyl group, 4-butylindenediyl group, 5-butylindenediyl group, 4-methyl-1-propylindene Diyl group, 5-methyl-1- Arenediyl groups such as propylindendiyl group, 2-methyl fluorenediyl group, 3-butyl fluorenediyl group, 2-methyl-9-propyl fluorenediyl group, 3-methyl-9-propyl fluorenediyl group, etc. Is mentioned. In particular, from the viewpoint of the flexibility and compatibility of the structure of the silsesquioxane side chain of the formula (1), a straight chain alkanediyl group having 3 to 16 carbon atoms and a branched chain alkane having 4 to 16 carbon atoms. A diyl group and a cyclic alkanediyl group having 7 to 16 carbon atoms are preferred.

  As described above, in the divalent hydrocarbon group serving as the skeleton of A, at least one, preferably 1 to 6, more preferably 1 of the methylene group and methine group constituting the divalent hydrocarbon group. ˜3 are substituted by NR, which is a divalent heteroatom linking group, N, which is a trivalent heteroatom linking group, or a combination thereof.

  Specific examples of the monovalent hydrocarbon group of R in the above NR include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, etc., 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms A linear alkyl group of 3 to 20 carbon atoms such as isopropyl group, sec-butyl group, tert-butyl group, isobutyl group, isopentyl group, neopentyl group, isohexyl group, 2-ethylhexyl group and isooctyl group, preferably carbon A branched alkyl group having 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexane A cyclic alkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, such as a syl group, a cyclooctyl group, a 4-tert-butylcyclohexyl group; a phenyl group, a tolyl group, dimethyl group C6-C12 aryl groups such as phenyl group, trimethylphenyl group, naphthyl group, and biphenyl group; C7-10 carbon atoms such as benzyl group, α-phenethyl group, β-phenethyl group, phenylpropyl group, and phenylbutyl group And an aralkyl group. In particular, from the viewpoint of compatibility, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 5 to 8 carbon atoms, and an aryl group having 6 to 9 carbon atoms. An aralkyl group having 7 to 9 carbon atoms is preferred.

  Specific examples of the substituent A in the general formula (1) are shown below. However, * in a formula shows the coupling | bonding position to an adjacent carbon atom or a silicon atom.

(In the formula, R independently represents the same meaning as described above.)

(In the formula, R independently represents the same meaning as described above.)

On the other hand, B may be the same or different and represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
Specific examples of the divalent hydrocarbon group include methylene, ethanediyl, ethenediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, etc. Chain aliphatic divalent hydrocarbon group; branched chain aliphatic divalent hydrocarbon group such as 2-methylpropanediyl group, 2-methylbutanediyl group, 3-methylpentanediyl group; cyclic such as cyclohexanediyl group Aliphatic divalent hydrocarbon group; 1,3-benzenediyl group, 1,4-benzenediyl group, 2-methyl-1,4-benzenediyl group, 3-methyl-1,4-benzenediyl group, 2, 5-dimethyl-1,4-benzenediyl group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenedi group Group, 4-ethylbenzene-1,2-diyl group, and aromatic divalent hydrocarbon group such as 4-propyl-1,3-diyl group.
Among these, a linear aliphatic divalent hydrocarbon group having 1 to 5 carbon atoms is preferable from the viewpoint of flexibility and compatibility of the structure of the silsesquioxane side chain of the formula (1).

M represents an integer of 1 to 150, preferably 4 to 100, more preferably 6 to 50. n represents an integer of 0 to 50, and the value of m + n is 4 to 150, preferably 6 to 100, and more preferably 8 to 80.
When the value of m + n is less than 4, the molecular weight of the compound of the general formula (1) is small and volatilizes from the photocurable composition or the cured product. When the value of m + n exceeds 150, the compatibility between the compound of general formula (1) and the other components contained in the photocurable composition of the present invention is reduced, and a uniform photocurable composition is obtained. It becomes difficult.

The number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) of silsesquioxane having the 2-cyanoethyl group of the general formula (1) is the stability of the cured product or the photocurable composition. From a compatibility viewpoint, Preferably it is 300-50,000, More preferably, it is 400-40,000, More preferably, it is 500-30,000.
The dispersity (Mw / Mn) of the silsesquioxane having the 2-cyanoethyl group of the general formula (1) is preferably 1.0 to 2.0, more preferably from the viewpoint of material uniformity. It is 1.0-1.8, More preferably, it is 1.0-1.6.

  The silsesquioxane having a 2-cyanoethyl group represented by the general formula (1) contained in the photocurable composition of the present invention may be a single compound or a mixture. When the compound of the general formula (1) is produced from hydrolyzable silane by the method described later, it is easy to use it as a mixture.

  In the photocurable composition of the present invention, the content of the silsesquioxane having a 2-cyanoethyl group represented by the general formula (1) as the component (a) is the relative dielectric constant or photocuring of the cured product. From the viewpoint of the transparency of the composition, it is 1 to 90% by mass, preferably 5 to 70% by mass, and more preferably 10 to 50% by mass, based on the total amount with the component (b) described later.

The silsesquioxane having a 2-cyanoethyl group represented by the general formula (1) is obtained by, for example, hydrolysis / condensation of a silane having a 2-cyanoethyl group represented by the following general formula (2), or It can be produced by co-hydrolysis / condensation of a silane having a 2-cyanoethyl group represented by the general formula (2) and a silane having a cyano group represented by the following general formula (3).
In this case, the silane having a 2-cyanoethyl group represented by the following general formula (2) may be used alone or in combination of two or more. Moreover, when coexisting the silane represented by the following general formula (3), the silane represented by the general formula (3) may be used alone, or two or more kinds may be mixed and used. .

(In the formula, A and B represent the same meaning as described above, and X independently represents a group which is hydrolyzable by bonding to a silicon atom.)

Specific examples of the group which is bonded to the silicon atom of X and exhibits hydrolyzability include a C1-C6 organoxy group, a C1-C3 acyloxy group, and a halogen atom.
Specific examples of the organoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, isopropoxy group, isobutoxy group, sec -Alkoxy groups such as butoxy group, tert-butoxy group, isopentyloxy group, 2-pentyloxy group, cyclopentyloxy group, cyclohexyloxy group; alkenoxy groups such as vinyloxy group, 2-propenoxy group; and phenoxy group .
Specific examples of the acyloxy group having 1 to 3 carbon atoms include an acetoxy group, a propanoyloxy group, and a butanoyloxy group.
Specific examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
X in the general formula (2) and X in the general formula (3) may be the same or different.

Hydrolysis / condensation of the silane having a 2-cyanoethyl group of the general formula (2) can be performed by a known method. For example, a silane having a 2-cyanoethyl group and water are reacted in a solvent.
Specific examples of the solvent include hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, toluene, xylene, mesitylene; methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol and the like. Alcohol solvents; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, 1,2-dimethoxyethane, etc. And ether solvents.

During the hydrolysis and condensation, the reaction is accelerated by adding an acid or base as a catalyst or heating.
Specific examples of the acid used as the catalyst include carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid and benzoic acid; sulfonic acids such as methanesulfonic acid, toluenesulfonic acid and dodecylbenzenesulfonic acid; hydrochloric acid, sulfuric acid and nitric acid And inorganic acids such as phosphoric acid.
Specific examples of the base include organic amines and ammonia such as ethyldimethylamine, diethylmethylamine, triethylamine, tributylamine, diisopropylethylamine; sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonium carbonate, sodium carbonate, potassium carbonate, Examples include inorganic bases such as ammonium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

  The same method can be used when hydrolyzing and condensing a silane having a 2-cyanoethyl group of the general formula (2) in the presence of the silane represented by the general formula (3).

  It is represented by the general formula (1) obtained by hydrolysis / condensation of the silane represented by the general formula (2) or the co-hydrolysis / condensation of the silane represented by the general formula (2) and the general formula (3). In the silsesquioxane, the non-hydrolyzed substituent X and the hydrolyzed substituent OH that has not undergone condensation may remain as the substituent OR. In the silsesquioxane represented by the general formula (1), the ratio of the silicon atom to which the substituent X or OH is bonded is all silicon atoms from the viewpoint of the stability of the photocurable composition or the cured product. Among these, Preferably it is 0-25 mol%, More preferably, it is 0-15 mol%.

  The 2-cyanoethyl group-containing silane compound represented by the general formula (2) can be obtained by Michael addition reaction of the compound represented by the general formula (4) and acrylonitrile.

(In the formula, A and X have the same meaning as described above, but the hydrogen atom H in the formula is bonded to the heteroatom linking group contained in A.)

  The compounding ratio of the compound represented by the general formula (4) and acrylonitrile is not particularly limited, but acrylonitrile is preferably 1 to 4 mol, more preferably 1 to 1 mol per 1 mol of the compound represented by the general formula (4). 3 mol, more preferably 1 to 2.2 mol.

In the above production method, a catalyst may be added for the purpose of accelerating the reaction.
Specific examples of the catalyst include trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, 1,1,2,2,2 -Sulfonic acids such as pentafluoroethanesulfonic acid; carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, succinic acid and benzoic acid; metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide; potassium Alkali metal alkoxides such as methoxide, sodium methoxide, potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide; ammonium carbonate, sodium carbonate, potassium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases, etc. Sulfonic acids, metal hydroxides are preferred.

  Although the usage-amount of a catalyst is not specifically limited, 0.0001-0.5 mol with respect to 1 mol of compounds represented by General formula (4) from the point of reactivity and productivity, More preferably, 0.001-0.3 mol More preferably, it is 0.01-0.1 mol.

Although reaction temperature is not specifically limited, It is 0-200 degreeC, Preferably it is 30-150 degreeC, More preferably, it is 50-130 degreeC.
Although reaction time is not specifically limited, It is 1 to 60 hours, Preferably it is 1 to 30 hours, More preferably, it is 1 to 20 hours.
The reaction atmosphere may be air, but is preferably an inert gas atmosphere such as nitrogen or argon.

The above reaction proceeds even without solvent, but a solvent can also be used.
Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, toluene and xylene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. Aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, and the like. These solvents may be used alone or in combination of two or more. Also good.
Among the above solvents, alcohol solvents are particularly preferable because they have an effect of promoting the reaction.

When the catalyst is used after completion of the reaction, it is preferable to neutralize the catalyst. This is because, if an attempt is made to purify by distillation without neutralization, the reverse Michael reaction may proceed during the distillation and the yield may decrease. Examples of the acid or base used for neutralization include the same as those used for the catalyst.
Although the usage-amount of a neutralizing agent is not specifically limited, It is 1.0-2.0 mol with respect to 1 mol of catalysts to be used, Preferably it is 1.0-1.8 mol, More preferably, it is 1.0-1.5 mol.
The neutralizing agent used in excess may be further neutralized by adding an acid or a base. Examples of the reverse neutralizing agent used include the same as those used for the catalyst. The reverse neutralizing agent used is preferably in the range of 1.0 to 2.0 mol, particularly 1.0 to 1.5 mol with respect to 1 mol of the neutralizing agent used in excess.
The 2-cyanoethyl group-containing silane compound obtained by the above production method may be used after further purification by various purification methods such as distillation, filtration, washing, column separation, solid adsorbent, etc., depending on the target quality. it can.
In order to remove a small amount of impurities such as a catalyst and obtain a high purity, purification by distillation is preferable.

(B) Ethylenically unsaturated monofunctional monomer The ethylenically unsaturated monofunctional monomer which is the component (b) of the present invention acts as a compatibilizer when used together with the component (a), and is a uniform and transparent composition give.
Specific examples of the component (b) include a compound having an acryloyl group or a methacryloyl group, a compound having a vinyl group, and the like. Among these, an ethylenically unsaturated monofunctional monomer having a cyano group is effective and preferable as a compatibilizer for the component (a).
Specific examples of the ethylenically unsaturated monofunctional monomer having a cyano group include α, β-unsaturation such as 2-cyanoethyl (meth) acrylate, 3-cyanopropyl (meth) acrylate and 4-cyanophenyl (meth) acrylate. Carboxylic acid ester; α, β-unsaturated nitrile such as (meth) acrylonitrile; α-cyanoacrylic acid ester such as methyl α-cyanoacrylate, ethyl α-cyanoacrylate, tert-butyl α-cyanoacrylate, and the like. Among these, α, β-unsaturated carboxylic acid ester having a cyano group is preferable from the viewpoint of balance between stability and reactivity.

  On the other hand, ethylenically unsaturated monofunctional monomers having no cyano group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) ) Acrylate, sec-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornenyl (meth) acrylate (Meth) acrylic acid esters such as dirate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate; N, Unsaturated amides such as N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, acryloylmorpholine; (meth) acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, etc. Unsaturated carboxylic acids: aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, methoxystyrene; methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, N-substituted maleimides such as butyl maleimide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; N-vinylamides such as N-vinylpyrrolidone, N-vinylcaprolactam and N-vinylacetamide; allyl glycidyl Examples thereof include allyl ethers such as ether and glyceryl allyl ether.

  The ethylenically unsaturated monofunctional monomer of component (b) can be used alone or in combination of a plurality of compounds. When a plurality of compounds are mixed and used, the mechanical properties and thermal properties of the cured product can be arbitrarily adjusted.

  The content of the component (b) in the photocurable composition of the present invention is based on the sum of the components (a) and (b) from the viewpoint of the uniformity of the photocurable composition or the electrical properties of the cured product. Is preferably 10 to 99% by mass, more preferably 30 to 95% by mass, and still more preferably 50 to 90% by mass.

(C) Ethylenically unsaturated polyfunctional monomer The ethylenically unsaturated polyfunctional monomer which is the component (c) of the present invention acts as a crosslinking agent. As the component (c), a compound containing a plurality of ethylenically unsaturated groups can be used. For example, an α, β-unsaturated carboxylic acid ester of a polyhydric alcohol, or a compound having a plurality of vinyl groups or a plurality of allyl groups can be used. Among these, α, β-unsaturated carboxylic acid esters of polyhydric alcohols are preferable because they have a wide variety of structures, and thus the mechanical properties of the cured product can be arbitrarily adjusted. (C) The ethylenically unsaturated polyfunctional monomer of a component can be used individually or in combination of 2 or more types.

  Among these ethylenically unsaturated polyfunctional monomers, examples of the α, β-unsaturated carboxylic acid ester of polyhydric alcohol include bis (4- (meth) acryloxypolyethoxyphenyl) propane, neopentyl glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, ethylene glycol diglycidyl ether (meth) acrylic acid adduct, propylene glycol di Glycidyl ether (meth) acrylic acid adduct, diethylene glycol diglycidyl ether (meth) acrylic acid adduct, neopentyl glycol diglycidyl ether (meth) acrylic acid adduct, 1,6-hexanediol diglycidyl ether (meth) acrylate, Phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate toluene diisocyanate urethane Α, β-unsaturated carboxylic acid esters of dihydric alcohols such as repolymers; trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytri (meth) acrylate, tris (meth) Α of trihydric alcohols such as acryloyloxyethyl isocyanurate, glycerin ethoxytri (meth) acrylate, glycerin propoxytri (meth) acrylate, glycerin diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate , Β-unsaturated carboxylic acid ester; pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol etoxy Α, β-unsaturated carboxylic acid esters of tetrahydric alcohols such as citetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, Pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, etc. Can be mentioned. Examples of the compound having a plurality of vinyl groups or allyl groups include diallyl phthalate, triallyl trimellitate, allyl (meth) acrylate, and vinyl norbornene.

  In the photocurable composition of the present invention, the content of the component (c) is the components (a), (b) and (c) from the viewpoint of the solvent resistance of the cured product or the elongation and strength of the cured product. Preferably it is 0.001-95 mass% with respect to the sum total of a component, More preferably, 0.01-90 mass% is contained.

(D) Photopolymerization initiator The photopolymerization initiator which is the component (d) of the present invention initiates photoradical polymerization.
Component (d) includes, for example, intramolecular cleavage photopolymerization initiators such as alkylphenones, benzoins, acylphosphine oxides, oxime esters, and biimidazoles, hydrogen such as benzophenones, thioxanthones, and α-diketones. A pull-out photopolymerization initiator can be used.

As the intramolecular cleavage type photopolymerization initiator, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy -2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Alkylphenones such as -1- [4- (4-morpholinyl) phenyl] -1-butanone; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; (2,4,6- Acylphosphine oxides such as trimethylbenzoyl) diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide 1- [4- (phenylthio) -2- (O-benzoyloxime)]-1,2-octanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxy ) Oxime esters such as ethanone; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 Biimidazoles such as 5′-tetraphenyl-1,2′-biimidazole may be mentioned.
Examples of the hydrogen abstraction type photopolymerization initiator include benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone and 2-carboxybenzophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, Examples include thioxanthones such as 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone; α-diketones such as camphorquinone and benzyl.

  These photoinitiators can be used individually or in combination of 2 or more types. Among these photopolymerization initiators, alkylphenones are preferable from the viewpoint of compatibility in the photocurable composition.

  The content of the component (d) in the photocurable composition of the present invention is such that the components (a), (b), ( Preferably it is 0.001-10 mass% with respect to the sum total of c) component and (d) component, More preferably, it is 0.01-2 mass%.

In addition to the photopolymerization initiator, a reducing compound may be used in combination for promoting the polymerization. In particular, it is useful to combine a hydrogen abstraction type photopolymerization initiator and a reducing compound.
The reducing compound is typically an aromatic tertiary amine, and specific examples thereof include aminobenzoic acids such as 4-dimethylaminobenzoic acid, 4-diethylaminobenzoic acid and 3-dimethylaminobenzoic acid; 4 -Aminobenzoic acid esters such as methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, lauryl 4-dimethylaminobenzoate, ethyl 3-dimethylaminobenzoate; dimethylamino-p- And aniline derivatives such as toluidine, diethylamino-p-toluidine, and p-tolyldiethanolamine. Of these aromatic tertiary amines, aminobenzoic acid and aminobenzoic acid esters are preferred.
The content of such a reducing compound is usually preferably in the range of 0.001 to 20 mol, more preferably 0.005 to 10 mol with respect to 1 mol of the photopolymerization initiator.

(E) Solvent The photocurable composition of the present invention may optionally contain a solvent.
Specific examples of usable solvents include hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, toluene, xylene, mesitylene, etc .; methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert- Alcohol solvents such as butanol and propylene glycol monomethyl ether; Nitrile solvents such as acetonitrile, propionitrile, benzonitrile and 3-methoxypropionitrile; Amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Diethyl Ether solvents such as ether, tetrahydrofuran, cyclopentyl methyl ether, 1,2-dimethoxyethane, anisole; ethyl acetate, isopropyl acetate, propylene glycol monomethyl ether Ester solvents such as ether acetate. These solvents can be used singly or as a mixture of two or more. However, when mixing a plurality of solvents, it is preferable to use solvents compatible with each other. Moreover, it is preferable that the solvent to be used can melt | dissolve the component of the photocurable composition of this invention at room temperature.

  When the component (e) is added, the content is usually 0.01 to 10 times by mass with respect to the total of the components (a) to (d) described above. A cured product is obtained as a gel by curing while containing the solvent.

The photocurable composition of the present invention is stable at room temperature under conditions where no light is irradiated, but may contain a polymerization inhibitor as long as the properties of the composition such as transparency and curability can be maintained.
Specific examples of the polymerization inhibitor include hydroquinones such as hydroquinone monomethyl ether, hydroquinone mono n-butyl ether, hydroquinone monobenzyl ether, hydroquinone monocyclohexyl ether, 4-methoxy-1-naphthol; 2,6-bis (tert-butyl) ) -4-methylphenol, octadecyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, 2 , 4-Bis- (n-octylthio) -6- (4-hydroxy-3,5-ditert-butylanilino) -1,3,5-triazine, 3,5-ditert-butyl-4-hydroxybenzylphos Phonate-diethyl ester, 6-ter Hindered phenols such as butyl-o-cresol; 6-tert-butyl-2,4-xylenol, 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4 -Hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, 2, 4-bis (octylthiomethyl) -o-cresol, 2,4-bis (dodecylthiomethyl) -o-cresol, 2-tert-butylphenol, 2,4-ditert-butylphenol, 2-tert-amylphenol, And semi-hindered phenols such as 2,4-ditert-amylphenol. These polymerization inhibitors may be used alone or in combination of two or more.

  In the case of adding a polymerization inhibitor, the content of the components (b) and (c) is from the viewpoint of improving the stability and preventing coloring while ensuring the curing reactivity of the photocurable composition of the present invention. The total amount is preferably 0.001 to 2% by mass, more preferably 0.05 to 1% by mass, and still more preferably 0.01 to 0.1% by mass.

[2] Photocurable composition The photocurable composition of the present invention comprises the above-mentioned component (a), component (b), component (c), component (d), and optionally component (e), for example, It is obtained by stirring and mixing at normal temperature and normal pressure, and is a uniform liquid at normal temperature and transparent.
Addition of the component (a) improves electrical characteristics such as relative permittivity of the material. By adding the component (b), the compatibility between the component (a) and other components is improved, and a transparent and uniform polymer material is obtained. By adding the component (c), the mechanical properties of the cured product can be adjusted. The components (b) and (c) are photopolymerizable compounds, and the mechanical properties and thermal properties of the cured product are determined according to the selection of these compounds and the blending ratio.

[3] Cured product of photocurable composition The photocurable composition of the present invention can be cured by irradiating light, and the essential component (c) is a cross-linking agent. A polymer material comprising a cured product having a structure is obtained.
Specifically, it is cured by irradiating the photocurable composition with light such as ultraviolet rays or visible rays. The wavelength of the light to be irradiated is selected according to the kind of the added photopolymerization initiator. For example, 254 nm, 365 nm (i-line), 405 nm (h-line), 436 nm (g-line) ultraviolet light or visible light Light is most preferably used.

The amount of ultraviolet rays to be irradiated is preferably about 10 to 1,000 mJ / cm ² . Moreover, you may further heat at 50-200 degreeC after light irradiation as needed. Although heating time is arbitrary, 10 to 500 minutes are preferable. Moreover, in order to remove a low molecular weight uncured product and a solvent, after light irradiation, for example, it may be washed with a solvent such as the component (e) or a solvent such as cyclohexane or vacuum dried. Two or more of these post-treatments may be combined.

  Since the photocurable composition of the present invention is liquid at room temperature, it can be cured using a mold, or it can be applied on a substrate and cured as a thin film.

[4] Polymer material having semi-interpenetrating polymer network (semi-IPN) structure or interpenetrating polymer network (IPN) structure Polymer material having chain or network structure, and photocurable composition of the present invention The polymer material in which the mixture with the product is cured has a semi-interpenetrating polymer network (semi-IPN) structure or an interpenetrating polymer network (IPN) structure.
Specifically, a polymer material having a semi-IPN structure or an IPN structure is formed by impregnating a photocurable composition of the present invention with a polymer material having a chain or network structure, and then irradiating with light. It can be cured or obtained by impregnating the photocurable composition of the present invention with a polymer material having a chain or network structure and irradiating with light in a swollen state.
When a chain polymer material is used, a semi-interpenetrating polymer network (semi-IPN) is formed. On the other hand, when a polymer material having a network structure is used, a transparent polymer material is used. An interpenetrating polymer network (IPN) is formed. By forming a semi-IPN or IPN and combining a polymer substance, the mechanical properties and thermal properties of the polymer material can be improved.

  Specific examples of the polymer substance having a chain or network structure include, from the viewpoint of compatibility, polyacrylate, polyurethane acrylate, polyvinyl chloride, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene fluoride, and the like. Examples include polymer substances.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not restrict | limited to the following Example.

(1) Synthesis of 2-cyanoethyl group-containing organoxysilane [Synthesis Example 1] Synthesis of 3- [N, N-bis (2-cyanoethyl) amino] propyltrimethoxysilane

A reflux condenser and a stirrer were attached to a 100 mL three-necked flask, and the interior was purged with nitrogen. This flask was charged with 179.1 g (1.00 mol) of 3-aminopropyltrimethoxysilane and 4.5 g (0.03 mol) of trifluoromethanesulfonic acid, and 118.1 g (2.22 mol) of acrylonitrile at 4.degree. It was dripped over 5 hours. After completion of the dropping, the reaction solution was heated and stirred at 120 ° C. for 13 hours.
The resulting solution was neutralized by adding 5.9 g (0.03 mol) of 28 mass% sodium methoxide methanol solution, and then 70.3 mg of succinic acid was added. The reaction solution was distilled to obtain 168.8 g of a fraction having a boiling point of 192 to 193 ° C./0.16 kPa.
As a result of measuring GC-MS spectrum and ¹ H-NMR spectrum of this liquid, it was confirmed to be the title compound.
GC-MS (EI) m / z: 285 (M ^<+> ), 245
¹ H-NMR (600 MHz, δ in CDCl ₃ ): 0.60-0.67 (m, 2H), 1.51-1.59 (m, 2H), 2.46 (t, J = 7.2 Hz) , 4H), 2.51-2.55 (m, 2H), 2.85 (t, J = 6.9 Hz, 4H), 3.57 (s, 9H) ppm.

[Synthesis Example 2] Synthesis of 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane

A reflux condenser and a stirrer were attached to a 100 mL three-necked flask, and the interior was purged with nitrogen. This flask was charged with 47.0 g (0.20 mol) of 3- (butylamino) propyltrimethoxysilane and 334.5 mg (0.002 mol) of trifluoromethanesulfonic acid, and 11.4 g (0.21 mol) of acrylonitrile was 115 The solution was added dropwise at 125 ° C. over 2.5 hours. After completion of the dropping, the reaction solution was heated and stirred at 115 ° C. for 1.5 hours.
The obtained solution was neutralized by adding 460.6 g (0.002 mol) of a 28 mass% sodium methoxide methanol solution, and then 28.1 mg of succinic acid was added. The reaction solution was distilled to obtain 43.1 g of a fraction having a boiling point of 136-137 ° C./0.15 kPa.
As a result of measuring GC-MS spectrum and ¹ H-NMR spectrum of this liquid, it was confirmed to be the title compound.
GC-MS (EI) m / z: 288 (M ^<+> ), 248
¹ H-NMR (600 MHz, δ in CDCl ₃ ): 0.59-0.65 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H), 1.27-1.34 (m , 2H), 1.37-1.43 (m, 2H), 1.49-1.56 (m, 2H), 2.39-2.45 (m, 6H), 2.77 (t, J = 7.2 Hz, 2H), 3.56 (s, 9H) ppm.

Synthesis Example 3 Synthesis of 3- [N- (2-cyanoethyl) -N-methylamino] propyltrimethoxysilane

A reflux condenser and a stirrer were attached to a 100 mL three-necked flask, and the interior was purged with nitrogen. Into this flask, 50.0 g (0.25 mol) of 3- (methylamino) propyltrimethoxysilane and 350.1 mg (0.0023 mol) of trifluoromethanesulfonic acid were charged, and 17.8 g (0.33 mol) of acrylonitrile was added in an amount of 80 to The solution was added dropwise at 105 ° C. over 1.5 hours. After completion of the dropping, the reaction solution was heated and stirred at 95 ° C. for 1.5 hours.
The obtained solution was neutralized by adding 452.4 g (0.0023 mol) of 28 mass% sodium methoxide methanol solution, and then 27.1 mg of succinic acid was added. The reaction solution was distilled to obtain 53.9 g of a fraction having a boiling point of 121 ° C./0.18 kPa.
As a result of measuring GC-MS spectrum and ¹ H-NMR spectrum of this liquid, it was confirmed to be the title compound.
GC-MS (EI) m / z: 246 (M ^<+> ), 206
¹ H-NMR (600 MHz, δ in CDCl ₃ ): 0.60-0.67 (m, 2H), 1.52-1.59 (m, 2H), 2.25 (s, 3H); 36-2.40 (m, 2H), 2.45 (t, J = 7.2 Hz, 2H), 2.70 (t, J = 7.2 Hz, 2H), 3.56 (s, 9H) ppm .

Synthesis Example 4 Synthesis of 3- [N- (2-cyanoethyl) piperazino] propyltriethoxysilane

A reflux condenser and a stirrer were attached to a 100 mL three-necked flask, and the interior was purged with nitrogen. To this flask, 29.1 g (0.10 mol) of 1- (3-triethoxysilylpropyl) piperazine was charged, and 5.8 g (0.11 mol) of acrylonitrile was added dropwise at 71 to 78 ° C. over 1.5 hours. After completion of the dropping, the reaction solution was heated and stirred at 75 ° C. for 2.0 hours.
The obtained reaction liquid was distilled to obtain 22.2 g of a fraction having a boiling point of 158 to 160 ° C./0.08 kPa.
As a result of measuring GC-MS spectrum and ¹ H-NMR spectrum of this liquid, it was confirmed to be the title compound.
GC-MS (EI) m / z: 343 (M ⁺ )
¹ H-NMR (600 MHz, δ in CDCl ₃ ): 0.56-0.62 (m, 2H), 1.20 (t, J = 6.9 Hz, 9H), 1.54-1.61 (m , 2H), 2.30-2.35 (m, 2H), 2.47-1.51 (m, 2H), 3.79 (q, J = 6.9 Hz, 6H) ppm.

(2) Synthesis of silsesquioxane [Synthesis Example 5] Synthesis of silsesquioxane S1

A 100 mL four-necked round bottom flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was purged with nitrogen, and air and moisture were shut off by bubbling nitrogen through the top of the reflux condenser opened to the outside air. . Into the flask was charged 14.27 g (50 mmol) of 3- [N, N-bis (2-cyanoethyl) amino] propyltrimethoxysilane obtained in Synthesis Example 1 and 5 g of acetone, and deionized water while stirring the mixture. 2.70 g (150 mmol) was added and stirred at room temperature for 20 hours.
When the gel permeation chromatography (hereinafter referred to as GPC) measurement of the reaction mixture was performed, the raw material 3- [N, N-bis (2-cyanoethyl) amino] propyltrimethoxysilane and a low molecular weight less than 1,000 were obtained. The molecular weight oligomer had disappeared. Mw of the product was 2,767, Mn was 2,517 (each in terms of polystyrene by GPC), and the dispersity (Mw / Mn) was 1.10. The reaction mixture was concentrated under reduced pressure, and the residue was vacuum-heated and dried at 80 ° C. to obtain a pale yellow oil.
When an infrared absorption spectrum of this oily substance was measured, a cyano group stretching vibration peak was observed at 2,247 cm ⁻¹ and a Si—O bond stretching vibration peak was observed at 1,000 to 1,100 cm ^−1. It was determined that the desired silsesquioxane S1 was obtained.

[Synthesis Example 6] Synthesis of silsesquioxane S2

A 100 mL four-necked round bottom flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was purged with nitrogen, and air and moisture were shut off by bubbling nitrogen through the top of the reflux condenser opened to the outside air. . In the flask, 14.42 g (50 mmol) of 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane obtained in Synthesis Example 2, 0.51 g (5.0 mmol) of triethylamine, and acetone 5 g was charged and the temperature of the mixture was adjusted to 50 ° C. while stirring. To this mixture, 2.70 g (150 mmol) of deionized water was added and stirred at 50 ° C. for 10 hours.
When GPC measurement of the reaction mixture was performed, the raw material 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane and the low molecular weight oligomer having a molecular weight of less than 1,000 were lost. Mw of the product was 2,737, Mn was 2,561 (each in terms of polystyrene by GPC), and the dispersity (Mw / Mn) was 1.08. The reaction mixture was concentrated under reduced pressure, and the residue was vacuum-heated and dried at 80 ° C. to obtain a pale yellow oil.
When an infrared absorption spectrum of this oily substance was measured, a cyano group stretching vibration peak was observed at 2,247 cm ⁻¹ and a Si—O bond stretching vibration peak was observed at 1,000 to 1,100 cm ^−1. It was determined that the desired silsesquioxane S2 was obtained.

[Synthesis Example 7] Synthesis of silsesquioxane S3

A 100 mL four-necked round bottom flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was purged with nitrogen, and air and moisture were shut off by bubbling nitrogen through the top of the reflux condenser opened to the outside air. . Into the flask was charged 12.32 g (50 mmol) of 3- [N- (2-cyanoethyl) -N-methylamino] propyltrimethoxysilane obtained in Synthesis Example 3 and 5 g of acetone, and the mixture was deionized while stirring. 2.70 g (150 mmol) of water was added and stirred at room temperature for 20 hours.
When GPC measurement of the reaction mixture was performed, the raw material 3- [N- (2-cyanoethyl) -N-methylamino] propyltrimethoxysilane and a low molecular weight oligomer having a molecular weight of less than 800 disappeared. Mw of the product was 2,939, Mn was 2,507 (each in terms of polystyrene by GPC), and the dispersity (Mw / Mn) was 1.17. The reaction mixture was concentrated under reduced pressure, and the residue was vacuum-heated and dried at 80 ° C. to obtain a pale yellow oil.
When an infrared absorption spectrum of this oily substance was measured, a cyano group stretching vibration peak was observed at 2,247 cm ⁻¹ and a Si—O bond stretching vibration peak was observed at 1,000 to 1,100 cm ^−1. It was determined that the desired silsesquioxane S3 was obtained.

[Synthesis Example 8] Synthesis of silsesquioxane S4

A 100 mL four-necked round bottom flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was purged with nitrogen, and air and moisture were shut off by bubbling nitrogen through the top of the reflux condenser opened to the outside air. . The flask was charged with 17.18 g (50 mmol) of 3- [N- (2-cyanoethyl) piperazino] propyltriethoxysilane obtained in Synthesis Example 4 and 5 g of acetone, and 2.70 g of deionized water while stirring the mixture. (150 mmol) was added and stirred at room temperature for 20 hours.
When GPC measurement of the reaction mixture was performed, the raw material 3- [N- (2-cyanoethyl) piperazino] propyltriethoxysilane and a low molecular weight oligomer having a molecular weight of less than 1,000 were lost. Mw of the product was 2,081, Mn was 1,171 (each in terms of polystyrene by GPC), and the dispersity (Mw / Mn) was 1.78. The reaction mixture was concentrated under reduced pressure, and the residue was vacuum-dried at 80 ° C. to give a white solid.
Was measured infrared absorption spectrum of the solid, since the stretching vibration peak of Si-O bonds were observed on the stretching vibration peak and 1,000～1,100Cm ^-1 cyano group 2,247Cm ^-1, It was determined that the desired silsesquioxane S4 was obtained.

[Synthesis Example 9] Synthesis of mixed silsesquioxane M1

A 100 mL four-necked round bottom flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was purged with nitrogen, and air and moisture were shut off by bubbling nitrogen through the top of the reflux condenser opened to the outside air. . In the flask, 3.46 g (12 mmol) of 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane obtained in Synthesis Example 2, 8.69 g (40 mmol) of cyanoethyltriethoxysilane, triethylamine 0.26 g (2.6 mmol) and 5.2 g of acetone were charged and the temperature was adjusted to 50 ° C. To this mixture, 2.81 g (156 mmol) of deionized water was added and stirred at 50 ° C. for 10 hours.
When GPC measurement of the reaction mixture was performed, the raw materials 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane and cyanoethyltriethoxysilane disappeared. Further, low molecular weight oligomers having a molecular weight of less than 800 were also lost. The product had a Mw of 2,293, a Mn of 1,937 (each in terms of polystyrene by GPC), and a dispersity (Mw / Mn) of 1.18. The reaction mixture was concentrated under reduced pressure, and the residue was vacuum-dried at 80 ° C. to give a white solid.
Was measured infrared absorption spectrum of the solid, since the stretching vibration peak of Si-O bonds were observed on the stretching vibration peak and 1,000～1,100Cm ^-1 cyano group 2,249Cm ^-1, It was determined that the desired silsesquioxane M1 was obtained.

[Synthesis Example 10] Synthesis of mixed silsesquioxane M2

A 100 mL four-necked round bottom flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was purged with nitrogen, and air and moisture were shut off by bubbling nitrogen through the top of the reflux condenser opened to the outside air. . In the flask, 6.92 g (24 mmol) of 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane obtained in Synthesis Example 2, 8.69 g (40 mmol) of cyanoethyltriethoxysilane, triethylamine 0.32 g (3.2 mmol) and 5.2 g of acetone were charged and the temperature was adjusted to 50 ° C. To this mixture, 3.46 g (192 mmol) of deionized water was added and stirred at 50 ° C. for 10 hours.
When GPC measurement of the reaction mixture was performed, the raw materials 3- [N-butyl-N- (2-cyanoethyl) amino] propyltrimethoxysilane and cyanoethyltriethoxysilane disappeared. Further, low molecular weight oligomers having a molecular weight of less than 800 were also lost. Mw of the product was 2,350, Mn was 2,050 (each in terms of polystyrene by GPC), and the dispersity (Mw / Mn) was 1.15. The reaction mixture was concentrated under reduced pressure, and the residue was vacuum-dried at 80 ° C. to give a colorless oil.
When the infrared absorption spectrum of this oily substance was measured, a cyano group stretching vibration peak was observed at 2,249 cm ⁻¹ and a Si—O bond stretching vibration peak was observed at 1,000 to 1,100 cm ^−1. It was determined that the desired silsesquioxane M2 was obtained.

(3) Preparation of photocurable composition and cured product [Examples 1-2, Comparative Examples 1-2]
(A) Silsesquioxane S1 obtained in Synthesis Example 5 as component, 2-cyanoethyl acrylate (CEA) as component (b), 1,4-butanediol diacrylate (BDA) as component (c), (d) Example 2) 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMP) as a component and 3-methoxypropionitrile (MPN) as a component (e) were mixed in the formulation shown in Table 1, and Example 1 A photocurable composition of ~ 2 was obtained.
Moreover, the photocurable composition of Comparative Examples 1-2 which mixed other components except the silsesquioxane S1 obtained by the synthesis example 5 with the mixing | blending shown in Table 1 was obtained.

Unit: g

The obtained photocurable composition was filled in a quartz glass mold having a depth of 1 mm and cured by irradiation with ultraviolet light having a central wavelength of 365 nm in a nitrogen atmosphere. Furthermore, it vacuum-dried at 80 degreeC, and obtained rubber-like hardened | cured material E1 and E2, and C1 and C2, respectively.
Table 2 shows the appearance and relative dielectric constant (1 kHz, 25 ° C.) of the cured products E1 and E2 and C1 and C2.

[Examples 3 to 8, Comparative Example 3]
Table 3 shows silsesquioxanes S1 to S4, M1, M2 obtained in Synthesis Examples 5 to 10 as component (a), CEA as component (b), BDA as component (c), and HMP as component (d). It mixed by the mixing | blending which shows, and obtained the photocurable composition of Examples 3-8.
Moreover, the other component except the silsesquioxane obtained by the synthesis examples 5-10 was mixed by the mixing | blending shown in Table 3, and the photocurable composition of the comparative example 3 was obtained.

Unit: g

Separately, a photocurable composition prepared by mixing 50 g of CEA, 1.15 g of BDA, 0.66 g of HMP and 50 g of MPN was prepared and photocured by the same method as in Example 1 above, and then 1/1 (v / v) The operation of immersing and washing in the mixed solution for 3 hours was performed twice, followed by vacuum drying at 80 ° C. to obtain a rubber-like transparent polymer substance CEA-S.
When this polymer material CEA-S was immersed in the curable compositions of Examples 3 to 8 and Comparative Example 3 at room temperature for 3 hours, CEA-S was swollen by these compositions. The excess compositions of Examples 3 to 8 and Comparative Example 3 adhered to the surface of the swollen CEA-S were wiped off, and then cured by irradiation with ultraviolet light having a central wavelength of 365 nm in a nitrogen atmosphere. Furthermore, it vacuum-dried at 80 degreeC and obtained rubber-like hardened | cured material E3-E8 and C3. These cured products are considered to form an interpenetrating polymer network (IPN).
Table 4 shows the appearance and relative dielectric constant (1 kHz, 25 ° C.) of the cured products E3 to E8 and C3.

Claims (7)

(A) Silsesquioxane having a 2-cyanoethyl group represented by the following general formula (1), (b) one or more ethylenically unsaturated monofunctional monomers, (c) one or more ethylenically unsaturated A photocurable composition comprising a polyfunctional monomer and (d) a photopolymerization initiator as essential components.
[In the formula, A may be the same or different and is a divalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted with a cyano group, and the divalent hydrocarbon group includes a methylene group and / or Or an NR (R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or 2-cyanoethyl, which includes a methine group, and at least one of these methylene groups and methine groups is a divalent heteroatom linking group Represents a group), N is a trivalent heteroatom linking group, or a combination thereof. However, these heteroatom linking groups, the heteroatom linking group and the silicon atom, and the heteroatom linking group and the cyano group are not adjacent to each other, and the NC—CH ₂ —CH ₂ — group in the formula is contained in A. To a heteroatom linking group.
B may be the same or different and represents a C1-C10 divalent hydrocarbon group.
m represents an integer of 1 to 150, n represents an integer of 0 to 50, and m + n is 4 to 150. ]   The photocurable composition according to claim 1, wherein at least one of the components (b) is an ethylenically unsaturated monofunctional monomer having a cyano group.   The photocurable composition according to claim 1, wherein at least one of the components (b) is an α, β-unsaturated carboxylic acid ester having a cyano group or an α, β-unsaturated nitrile.   The photocurable composition according to any one of claims 1 to 3, wherein the component (c) is an α, β-unsaturated carboxylic acid ester of a polyhydric alcohol.   Furthermore, (e) The photocurable composition of any one of Claims 1-4 containing a solvent.   Hardened | cured material which the photocurable composition of any one of Claims 1-5 hardened | cured.   A semi-interpenetrating polymer network structure or an interpenetrating polymer network structure obtained by curing a mixture of a polymer material having a chain or network structure and the photocurable composition according to any one of claims 1 to 5. A polymer material having