JPWO2019194107A1 - Resin composition - Google Patents

Abstract

A novel resin composition having excellent heat resistance, which is suitably used as a material for an insulating film in electronic parts, and has a compound (a) represented by the formula (1) and a resin (b) having a hydrogen-bonding group. And a resin composition containing a polymerization initiator (c). (In formula (1), A is a divalent organic group, Y is a linear alkylene having 1 to 18 carbon atoms or an alkylene having a branch, and the alkylene has 2 or more carbon atoms. In some cases, an oxygen atom (-O-) may be inserted between any CC bonds, -CO- may be inserted between the terminal CN bonds, and m is 0 or 1. Yes, X is a group represented by the following formula (2).) [Chemical formula 2] (In formula (2), R1 and R2 are independently hydrogen or methyl, respectively.)

Description

The present invention relates to a novel resin composition used as a material for an insulating film in an electronic component such as a printed wiring board or a semiconductor package substrate.

In recent years, in order to meet the demand for weight reduction of mobile terminals equipped with a display unit such as a liquid crystal, it has been studied to change the raw material of electronic component members from glass to plastic. Since plastic is inferior in scratch resistance to glass, a method of preventing scratch by surface treatment with a hard coating agent is widely used. As a compound for improving the scratch resistance of a hard coat agent, (meth) acryloyl groups at both ends of the molecule obtained by reacting an isocyanate-containing (meth) acrylate with an organopolysiloxane having alcohol at both ends of the molecule. A curable organopolysiloxane having the above has been proposed (Patent Document 1, Patent Document 2). Further, a radiation-curable organopolysiloxane composition (Patent Document 3) having excellent adhesiveness to a plastic base material and deep curability has also been proposed. However, Patent Documents 1 and 2 have a problem of improving the scratch resistance of the cured film formed by the compound or the composition, and do not describe the heat resistance. Further, Patent Document 3 has a problem of adhesiveness of the composition and does not describe heat resistance.

A curable composition containing a polyfunctional acrylate compound has been proposed for the purpose of improving curing with high sensitivity and storage stability (Patent Document 4). Further, a reactive monomer having a urea bond has been proposed for the purpose of obtaining a cured product having high adhesion, high heat resistant temperature, good chemical resistance and the like (Patent Document 5).

Japanese Unexamined Patent Publication No. 2015-196748 Publication of international patent application WO2015 / 152288 Japanese Unexamined Patent Publication No. 6-184256 Japanese Unexamined Patent Publication No. 2008-88251 JP-A-2007-55993

The curable composition described in Patent Document 4 is used for a color filter, and is not suitable as a material for an insulating film in an electronic component or the like. Further, in Patent Document 5, for example, general-purpose curability that can be used for various purposes such as resist, sealing, paint, adhesive / adhesive, printing plate, print calibration, lens, dental material, surface treatment, battery material and the like. Although the composition is disclosed, it does not describe the reactivity when cured by using a light source such as an LED light source having a small amount of ultraviolet energy, and is a material for an insulating film that is particularly required to have heat resistance and electrical insulation. It is not specialized for.
Therefore, an object of the present invention is to provide a novel resin composition having excellent heat resistance and reactivity suitable as a material for an insulating film in an electronic component such as a printed wiring board or a semiconductor package substrate.

The present invention uses a novel urea-bonded tetrafunctional (meth) acrylate compound having a urea bond and a (meth) acryloyl group, so that a high reaction rate can be obtained even when a light source having a small amount of ultraviolet energy such as an LED light source is used. Based on the new finding that a cured film having excellent heat resistance and electrical insulating properties, which can be cured with the above and is suitable as a material for an insulating film in an electronic component, can be obtained, and has the following configuration.

[1] A resin composition containing the compound (a) represented by the formula (1), the resin (b) having a hydrogen-bonding group, and the polymerization initiator (c).

(In the formula (1), A is a divalent organic group, Y is a linear alkylene having 1 to 18 carbon atoms or an alkylene having a branch, and any alkylene has 2 or more carbon atoms. An oxygen atom (-O-) may be inserted between the CC bonds, -CO- may be inserted between the terminal CN bonds, m is 0 or 1, and X is. It is a group represented by the following formula (2).)

(In formula (2), R ₁ and R ₂ are independently hydrogen or methyl, respectively.)

[2] The resin composition according to [1], wherein the hydrogen-bonding group in the resin (b) is a group having active hydrogen.

[3] The above-mentioned resin (b) according to [1] or [2], wherein the resin (b) contains at least one of a siloxane compound having a three-dimensional crosslinked structure represented by the following formula (3) or the following formula (4) in the structure. Resin composition.

(In the formula (4), R ₉ is a group selected from a linear alkyl having 1 to 22 carbon atoms or an alkyl having a branch, an aryl having 1 to 9 carbon atoms, or an aryl alkyl having 7 to 21 carbon atoms. , These groups may have any hydrogen substituted with halogen, and if the alkyl has 2 or more carbon atoms, oxygen atoms (-O-), cycloalkylene, between arbitrary CC bonds, cycloalkenylene, phenylene, naphthalene may be inserted. However, the total number of carbon atoms in R ₉ is never greater than 30.)
[4] The resin composition according to [3], wherein _{R 9} in the formula (4) is methyl or phenyl.

[5] The resin composition according to any one of [1] to [4], wherein A in the formula (1) has a structure represented by the formula (5).

(In formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms, and Z is 1 to 4 carbon atoms. It is an alkylene of, and n is an integer of 0 to 150.)
[6] The resin composition according to [5], wherein m in the formula (1) is 0.
[7] The resin composition according to [5] or [6], wherein in formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 are methyl and Z is trimethylene.} ..

[8] A cured film obtained from the resin composition according to any one of [1] to [7].
[9] An electronic component having the cured film according to [8].

By using a urea-bonded tetrafunctional (meth) acrylate compound having a urea bond and a (meth) acryloyl group, it can be cured with a high reaction rate using an LED light source having a small amount of energy or the like. By using the resin composition containing the urea-bonded tetrafunctional (meth) acrylate compound, it has heat resistance and electrical insulation suitable as a material for an insulating film of electronic parts such as a printed wiring board and a semiconductor package substrate. A good cured film can be obtained. Further, by optimizing the structure of the urea-bonded tetrafunctional (meth) acrylate compound, it is possible to adjust the compatibility of the resin composition and the flexibility of the cured film.

Hereinafter, embodiments of the present invention will be specifically described with respect to each component contained in the resin composition.
<Compound (a)>
Compound (a) is a urea-bonded tetrafunctional (meth) acrylate compound represented by the following formula (1).

(In the formula (1), A is a divalent organic group, Y is a linear alkylene having 1 to 18 carbon atoms or an alkylene having a branch, and any alkylene has 2 or more carbon atoms. An oxygen atom (-O-) may be inserted between the CC bonds, -CO- may be inserted between the terminal CN bonds, m is 0 or 1, and X is. It is a group represented by the following formula (2). Here, the alkylene in which an oxygen atom (−O−) is inserted between the CC bonds of Y is, for example, an alkylene having an ethyleneoxy structure or a propyleneoxy structure. It means one having an oxy structure.)

(In formula (2), R ₁ and R ₂ are independently hydrogen or methyl, respectively.)

As used herein, "(meth) acrylate" is used to indicate acrylate and / or methacrylate.
In the reaction of the (meth) acrylate, the "functional" moiety is the (meth) acryloyl group because the double bond of the (meth) acryloyl group is radically polymerized. The urea-bonded tetrafunctional (meth) acrylate has two structures represented by the above formula (2) on both sides of the divalent organic group A via a urea bond or a linking group containing a urea bond. Refers to a (meth) acrylate having a total of four (meth) acryloyl groups.

The urea-bonded tetrafunctional (meth) acrylate can be hydrogen-bonded to a resin having a hydrogen-bonding group by a urea bond. Therefore, since the resin having no photocurable substituent can be immobilized by hydrogen bonds, it is possible to form a cured film by irradiating with light such as ultraviolet rays or visible light. Therefore, a photocurable resin composition having desired properties can be prepared by using a resin having various properties as a resin having a hydrogen-bonding group.

By using urea-bonded tetrafunctional (meth) acrylate, a cured film (cured product) has a high reaction rate even when a UV-LED irradiation carrier device with a lower amount of ultraviolet energy than a high-pressure mercury irradiation device is used. Can be produced. Therefore, the energy efficiency when producing the cured film is improved.

From the viewpoint of obtaining a cured product having good heat resistance, the divalent organic group A contained as a part of the urea-bonded tetrafunctional (meth) acrylate compound is a divalent organic group having three or more aromatic rings. Alternatively, a divalent organic group having a structure represented by the formula (5) is preferable. Here, assuming that the number of aromatic rings is one, the number of naphthalene rings is two, the number of fluorene rings is two, and the number of anthracene rings is three.

(In formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms, and Z is 1 to 4 carbon atoms. It is an alkylene of, and n is an integer of 0 to 150.)

Examples of the divalent organic group having three or more aromatic rings include a divalent organic group derived from an aromatic diamine compound having three or four aromatic rings, which will be described later. Further, as an example of the divalent organic group represented by the formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are methyl, and Z is trimethylene. The group is mentioned.

<Synthesis method>
The urea-bound tetrafunctional (meth) acrylate contained in the resin composition of the present invention can be synthesized, for example, by the synthetic methods 1 to 3 described below.
<Synthesis method 1>
The urea-bonded tetrafunctional (meth) acrylate is a diamine compound having amino groups at both ends represented by the following formula (6) and a monoisocyanate compound having two (meth) acryloyl groups represented by the following formula (7). Is obtained by reacting.

(In formula (6), A is the same group as in formula (1).)

(In formula (7), R ₁ and R ₂ are the same groups as in formula (2).)

The diamine compound represented by the formula (6) has an aromatic having three or more aromatic rings from the viewpoint of improving the heat resistance of the cured film obtained by using the resin composition containing a urea-bonded tetrafunctional (meth) acrylate. A group diamine compound or a siloxane diamine compound having a structure represented by the following formula (8) is preferable.

(In formula (8), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms, and Z is 1 to 4 carbon atoms. It is an alkylene of, and n is an integer of 0 to 150.)

When the urea-bonded tetrafunctional (meth) acrylate is used as the resin composition, n of the silicone chain of the siloxane diamine compound represented by the formula (8) is set to 0 to 20 in the resin composition. It is preferable because the compatibility with other components can be improved.

Specific examples of the diamine compound represented by the formula (6) used as a raw material for the urea-bonded tetrafunctional (meth) acrylate are shown below.
Examples of the aromatic diamine compound having three aromatic rings include 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis (4-aminophenoxy). -2,5-di-t-butylbenzene, 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene, N, N-bis (4-aminophenyl) terephthalamide, 1,3 -Bis (3-aminophenoxy) benzene, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] Benzene can be mentioned.

Examples of the aromatic diamine compound having four aromatic rings include 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, and bis (4- (4-). 3-Aminophenoxy) phenyl) sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 4,4'-(biphenyl-2,5-diylbis) Oxy) bisaniline, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl, 4,4'-bis (4-aminophenoxy) benzophenone can be mentioned.

Examples of the siloxane diamine compound represented by the formula (8) include 1,3-bis (aminomethyl) tetramethyldisiloxane, 1,3-bis (2-aminoethyl) tetramethyldisiloxane, and 1,3-bis (2). 3-Aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, 1,5-bis (3-aminopropyl) hexamethyltrisiloxane, α, ω-bis (3-aminopropyl) Aminopropyl) polydimethylsiloxane. As these siloxane diamine compounds, commercially available products or those obtained by synthesis can be used. Commercially available siloxane diamine compounds include, for example, Silaplane FM33 series (trade name, manufactured by JNC Co., Ltd.), X22 series (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BY16 series (trade name, manufactured by Toray Dow Corning Co., Ltd.). Co., Ltd.) and the like. As a method for synthesizing a siloxane diamine compound, for example, both-terminal dimethylsilylpolydimethylsiloxane (for example, trade name: Silaplane FM11 series, manufactured by JNC Co., Ltd.) is reacted with allylamine or the like in the presence of a platinum catalyst. There is a method of synthesizing.

_{From the viewpoint of availability, a siloxane diamine compound in which R 3} , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are all methyl and Z is trimethylene is preferable in the formula (8).
By this synthetic method, a urea-bound tetrafunctional (meth) acrylate having m in the formula (1) can be synthesized.

As the monoisocyanate compound having two (meth) acryloyl groups represented by the formula (7), a commercially available product or a compound obtained by synthesis can be used. For example, Japanese Patent Application Laid-Open No. 2007-55993 (Patent Document 5) discloses a method for obtaining the compound. Examples of commercially available products include Calends BEI (trade name, manufactured by Showa Denko KK).

A catalyst may be used for the purpose of enhancing the reactivity of the diamine compound represented by the formula (6) with the monoisocyanate having a (meth) acryloyl group represented by the formula (7). Examples of the catalyst include a tin catalyst (for example, dibutyltin dilaurate), an amine-based catalyst (for example, triethylenediamine), a carboxylate catalyst (for example, lead naphthenate and potassium acetate), a trialkylphosphine catalyst (for example, triethylphosphine), and a titanium-based catalyst (for example). , Product name: Organics TA-21, Organics TA-30, Organics TC-750, etc., manufactured by Matsumoto Fine Chemical Co., Ltd., Zyrosine-based catalyst (for example, Product name: Organics ZC-150, Matsumoto Fine Chemical Co., Ltd.) ), Etc. can be used.

<Synthesis method 2>
The urea-bonded tetrafunctional (meth) acrylate contained in the resin composition of the present invention includes a diamine compound having amino groups at both ends represented by the formula (6) and two (meth) compounds represented by the following formula (9). ) It can be obtained by reacting with a monocarboxylic acid compound having an acryloyl group.

(In formula (6), A is the same group as in formula (1).)

(In the formula (9), R ₁ and R ₂ represent the same group as in the formula (2), Y ₁ is a linear alkylene having 1 to 18 carbon atoms or an alkylene having a branch, and the carbon number of the alkylene is When is 2 or more, an oxygen atom (-O-) may be inserted between arbitrary CC bonds.)

The monocarboxylic acid compound having two (meth) acryloyl groups represented by the formula (9) includes a monocarboxylic acid compound having one amino group in the molecule represented by the following formula (10) and the following formula ( It can be synthesized by a reaction with a monoisocyanate compound having two (meth) acryloyl groups represented by 7).

_{(Y 1} in equation (10) is the same group as in equation (9).)

(In formula (7), R ₁ and R ₂ are the same groups as in formula (2).)

Examples of the monocarboxylic acid compound having one amino group in the molecule represented by the formula (10) include the following.

For the purpose of enhancing the reactivity between the monocarboxylic acid compound having one amino group in the molecule represented by the formula (10) and the monoisocyanate compound having two (meth) acryloyl groups represented by the formula (7). Condensing agents and catalysts may be used. Examples of the condensing agent include N, N'-dicyclohexylcarbodiimide and 1-hydroxybenzotriazole, and examples of the catalyst include N, N-dimethyl-4-aminopyridine.

By this synthetic method, a urea-bound tetrafunctional (meth) acrylate having m in the formula (1) can be synthesized. By setting m in the formula (1) to 1, it is possible to impart flexibility to the urea-bonded tetrafunctional (meth) acrylate and adjust the reactivity of the (meth) acryloyl group. That is, the urea-bonded tetrafunctional (meth) acrylate of the formula (1) having m of 1 has a smaller ratio of (meth) acrylate per molecule than that having m of 0, so that flexibility is increased and curing is performed. The flexibility of the object is improved. Further, the urea-bound tetrafunctional (meth) acrylate having m of 1 in the formula (1) has a longer molecular chain constituting the skeleton portion of the polymer (polymer) than the acrylate having m of 0. The degree of freedom of the molecule increases. Then, as the number of hydrogen-bonding functional groups (NH groups) in the compound increases, the interaction between the molecules increases, so that it is expected to exert an aggregation effect. As a result, the urea-bonded tetrafunctional (meth) acrylate of the formula (1) having m of 1 becomes highly reactive in photopolymerization.

<Synthesis method 3>
The urea-linked tetrafunctional (meth) acrylate of the present invention has a diamine compound having amino groups at both ends represented by the formula (6) and a mono having two (meth) acryloyl groups represented by the following formula (11). It can be obtained by reacting with a halogen compound.

(In formula (6), A is the same group as in formula (1).)

(In the formula (11), R ₁ and R ₂ represent the same group as in the formula (2), W represents a halogen, and Y ₂ is a linear alkylene having 1 to 18 carbon atoms or an alkylene having a branch. , When the alkylene has 2 or more carbon atoms, an oxygen atom (−O−) may be inserted between arbitrary CC bonds.)

The monohalogen compound having two (meth) acryloyl groups represented by the formula (11) is a monohalogen compound having one amino group in the molecule represented by the following formula (12) and the following formula (7). It can be synthesized by reaction with a monoisocyanate compound having two (meth) acryloyl groups represented by.

(In formula (12), Y ₂ is the same group as in formula (11), and W is a halogen.)

(In formula (7), R ₁ and R ₂ are the same groups as in formula (2).)

Examples of the monohalogen compound having one amino group in the molecule represented by the formula (12) include the following.

An inorganic base may be used in combination for the purpose of enhancing the reactivity of the monoisocyanate compound having two (meth) acryloyl groups and the monohalogen compound having one amino group in the molecule. Examples of the inorganic base include calcium carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
By this synthetic method, a urea-bound tetrafunctional (meth) acrylate having m in the formula (1) can be synthesized.

<Resin (b) having a hydrogen-bonding group>
In the present specification, the resin (b) having a hydrogen-bonding group refers to a resin other than the compound (a) and having a substituent capable of hydrogen-bonding to the compound (a). The substituent that can hydrogen bond with compound (a) refers to a group that hydrogen bonds with a urea bond contained in compound (a), and is a hydrogen atom covalently bonded to an atom having a high electronegativity such as nitrogen, oxygen, and sulfur. Examples thereof include a group having (active hydrogen) and a group capable of hydrogen bonding with active hydrogen.

Examples of the group having such active hydrogen include groups having active hydrogen such as hydroxy, carboxyl, active hydrogen-containing amide bond, urea bond, urethane bond, silanol and the like.

Examples of the resin having hydroxy include polyether polyols, polyester polyols, polycarbonate polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, phenol resins and the like.

Polyether polyols include glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin- tetrahydrofuran adduct, glycerin-ethyleneoxide propylene adduct adduct, trimethylolpropane-ethyleneoxide adduct, trimethylolpropane-propylene oxide adduct. Adducts, Trimethylol Propane- tetrahydrofuran Adducts, Trimethylol Propane-ethylene Oxide Propylene Adducts, Dipenta Esritol-Ethethylene Oxide Adducts, Dipenta Esritol-propylene Oxide Adducts, Dipenta Esritol- Examples thereof include a tetrahydrofuran adduct, dipentaesritol-ethylene oxide propylene adduct adduct, and the like.

Examples of the polyester polyol include a polycondensate obtained by reacting a polyfunctional alcohol with a polybasic acid under known conditions.

Examples of polyfunctional alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2-methyl. -1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2,3,4-tetrahydroxy Butane, glycerin, trimethylolpropane, 1,2-cyclohexaneglycol, 1,3-cyclohexaneglycol, 1,4-cyclohexaneglycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2 , 7-Decalin glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A and the like.

Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, and azeline. Acids, sebacic acids and other saturated aliphatic dicarboxylic acids (11 to 13 carbon atoms) such as maleic acid, fumaric acid, itaconic acid and other unsaturated aliphatic dicarboxylic acids such as orthophthalic acid, isophthalic acid and terephthalic acid. , Toluenedicarboxylic acid, naphthalenedicarboxylic acid, other aromatic dicarboxylic acids, such as hexahydrophthalic acid, other alicyclic dicarboxylic acids, for example, other carboxylic acids such as dimer acid, hydrogenated dimer acid, het acid, etc. And acid anhydrides derived from these carboxylic acids, such as oxalic acid anhydride, succinic acid anhydride, maleic anhydride, phthalic acid anhydride, 2-alkyl anhydride (12-18 carbon atoms) succinic acid, tetrahydrophthalic acid anhydride, Examples thereof include trimellitic anhydride and acid halides derived from these carboxylic acids and the like, for example, oxalic acid dichloride, adipate dichloride, sebacic acid dichloride and the like.

Examples of the polycarbonate polyol include one or more ring-opening polymers such as ε-caprolactone, γ-butyrolactone, and γ-valerolactone, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-. Examples thereof include a copolymer of a dihydric alcohol such as 1,5-pentanediol or 1,6-hexanediol and a ring-opening polymer.

Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-mentioned polyfunctional alcohol with a polyfunctional halohydrin such as epichlorohydrin and β-methylepichlorohydrin.
Examples of the vegetable oil polyol include hydroxy group-containing vegetable oils such as castor oil and coconut oil. For example, castor oil polyol or ester-modified castor oil polyol obtained by reacting castor oil fatty acid with polyoxypropylene polyol and the like can be mentioned.

Examples of the polyolefin polyol include polybutadiene polyol and a partially Ken-valent ethylene-vinyl acetate copolymer.
Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxy group-containing (meth) acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxy group-containing (meth) acrylate.

Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, and polyhydroxyalkylmalate. , Polyhydroxyalkyl fumarate and the like.

Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( Alkyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate and the like. Meta) acrylates (1-12 carbon atoms), eg aromatic vinyls such as styrene, vinyltoluene, α-methylstyrene, eg vinyl cyanide such as (meth) acrylonitrile, eg (meth) acrylic acid, fumaric acid , Maleic acid, Itaconic acid and other carboxyl-containing vinyl monomers, or alkyl esters thereof, such as ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di. Alcan polyol poly (meth) acrylates such as (meth) acrylates, trimethylolpropane di (meth) acrylates, trimethylolpropane tri (meth) acrylates, for example 3- (2-isocyandia-2-propyl) -α-methylstyrene. Vinyl monomers containing isocyanates such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyl. Trimethoxysilane, 3-acryloxypropyltriethoxysilane, Cyraplane FM0711 (trade name, manufactured by JNC Co., Ltd.), Cyraplane FM0721 (trade name, manufactured by JNC Co., Ltd.), Cyraplane FM0725 (trade name, manufactured by JNC Co., Ltd.) Silicone compound having an ethylenically unsaturated group such as (manufactured by Co., Ltd.), vinylidene fluoride (VdF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF). ), Perfluoro (alkyl vinyl ether) and the like.

The phenol resin is a resin having a phenolic hydroxy group, and can be synthesized, for example, by condensation polymerization of phenols and formaldehyde using an acidic or basic catalyst.

Examples of the resin having carboxyl include an acid-modified polyolefin resin obtained by modifying each polymer of a polyolefin resin such as polyethylene and polypropylene with an acid having an unsaturated bond, and an acid having an unsaturated bond in each polymer of ethylene rubber. Examples thereof include an acid-modified ethylene rubber modified with, and an acid-modified styrene-based elastomer obtained by modifying each polymer of a styrene-based elastomer with an acid having an unsaturated bond. The acid used for acid denaturation is not particularly limited as long as the effect of the present invention is not impaired, and for example, unsaturated carboxylic acid or a derivative thereof can be used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, abietinic acid, neoavietic acid, and parastrolic acid, and examples of the unsaturated carboxylic acid derivative include maleic acid. Examples thereof include monoesters, maleic anhydride, itaconic acid monoesters, itaconic anhydride, fumaric acid monoesters, fumaric acid anhydride, pimaric acid, isopimaric acid, and dehydroavietic acid.

As the resin having an active hydrogen-containing amide bond (active hydrogen-containing amide group), a reaction product obtained by reacting a polyfunctional amine having a primary amino group with the above-mentioned resin having a carboxyl, a polyfunctional resin. Examples thereof include a product obtained by reacting the isocyanate of the above with a resin having a carboxyl, a reaction product obtained by polymerizing an unsaturated double-bonding compound having an amide group, and the like.

Examples of the polyfunctional amine having a primary amino group include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptanediamine. Linear aliphatic alkylene diamines such as 1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4- Butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4- Fats such as butanediamine, branched aliphatic alkylenediamines such as 2,3-dimethyl-1,4-butanediamine, cyclohexanediamines, methylcyclohexanediamines, isophoronediamines, norbornandimethylamines, tricyclodecanedimethylamines, mensendiamines, etc. Aromatic diamines such as cyclic diamine, p-phenylenediamine, m-phenylenediamine, p-xylylene diamine, m-xylylene diamine, 4,4'-diaminodiphenylmethane, benzenetriamine, melamine, 2,4,6- Examples thereof include triamines such as triaminopyrimidine, tetraamines such as 2,4,5,6-tetraaminopyrimidine and the like.

Polyfunctional isocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthaline diisocyanate, and triphenylmethane tri. Isocyanate, Banoc D-750, Chris Bonn NK (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Death Module L (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) (Manufactured by Co., Ltd.), Takenate D102 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), Isocyanate 143L (trade name, manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

Examples of unsaturated double-binding compounds having an amide group include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methylol. Polymers of (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, Examples thereof include a copolymer of an unsaturated double-binding compound having these amide groups and a copolymerizable compound.

As the resin having an active hydrogen-containing amide bond, a commercially available product can be used. Examples of commercially available resins having an active hydrogen-containing amide bond include nylon 6, nylon 6, 6, nylon 6, 10, nylon 6, T, and nylon MXD6 (trade names, all manufactured by DuPont). ..

As the resin having a urea bond, the above-mentioned polyfunctional isocyanate is reacted with the above-mentioned polyfunctional primary amine, or the above-mentioned polyfunctional isocyanate is reacted with water, and the amino group generated by hydrolysis of the isocyanate remains. Polyurea obtained by reacting the isocyanate of the above can be mentioned.

Examples of the resin having a urethane bond include polyurethane obtained by reacting the above-mentioned polyfunctional isocyanate with the above-mentioned resin having a hydroxy group.
A urethanization catalyst can be used as a curing reaction initiator for the purpose of accelerating the curing reaction of forming a resin having a urethane bond. Examples of the urethanization catalyst include an organometallic urethanization catalyst and a tertiary amine urethanization catalyst.

Organic metal-based urethanization catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanate, lead naphthenate, nickel naphthenate, cobalt naphthenate. Examples thereof include organic metal-based urethanization catalysts.

Examples of the tertiary amine-based urethanization catalyst include triethylenediamine, N, N, N', N', N'-pentamethyldipropylene triamine, N, N, N', N', N'-pentamethyldiethylenetriamine, and N. , N, N', N'-tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2- (N, N dimethylamino) -ethyl-3- (N, N dimethylamino) propyl ether, N, N '-Dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, triethylamine, N, N-dimethylacetylamine, N, N-dimethyldodecylamine, N, N-dimethylhexadecylamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N-dimethylbenzylamine, morpholin, N-methylmorpholin, N-ethylmorpholin, N- (2-dimethylaminoethyl) morpholin, 4 , 4'-oxydiethylene dimorpholine, N, N'-dimethylpiperazine, N, N'-diethylpiperazine, N, -methyl-N'-dimethylaminoethylpiperazin, 2,4,6-tri (dimethylaminomethyl) Phenol, tetramethylguanidine, 3-dimethylamino-N, N-dimethylpropionamide, N, N, N', N'-tetra (3-dimethylaminopropyl) methanediamine, N, N-dimethylaminoethanol, N, N, N', N'-tetramethyl-1,3-diamino-2-propanol, N, N, N'-trimethylaminoethylethanolamine, 1,4-bis (2-hydroxypropyl) -2-methylpiperazine , 1- (2-Hydroxypropyl) imidazole, 3,3-diamino-N-methylpropylamine, 1,8-diazobicyclo (5,4,5) -undecene-7, N-methyl-N-hydroxyethylpiperazin And so on.
These can be used alone or in combination of two or more.

Examples of the resin having silanol include a silicone resin having silanol at the terminal or side chain, and a resin obtained by hydrolyzing a resin containing hydrolyzable silyl such as an alkoxy group at the terminal or side chain.

The silicone resin has a three-dimensional crosslinked structure containing silanol-containing additive-curable silicone, silanol-containing heat-curable silicone resin, silanol-modified organic functional group-modified modified silicone resin, and silanol. Siloxane compounds can be mentioned.

The addition-curable silicone resin having silanol can be obtained by a hydrosilylation reaction between a silicone having silanol and hydrosilyl and a silicone having alkenyl, or a silicone having hydrosilyl and a silicone having silanol and alkenyl. Examples of the catalyst used in the hydrosilylation reaction include a transition metal catalyst, and examples of the transition metal catalyst used are platinum, rhodium, iridium, ruthenium, palladium, molybdenum, iron, cobalt, nickel, manganese and the like. Of these, platinum catalysts are more preferred. These catalysts can be used as a homogeneous catalyst dissolved in a solvent, or as a solid catalyst supported on carbon, silica, or the like. It may be used in the form in which phosphine, amine, potassium acetate and the like coexist. ^{The preferred amount of the transition metal catalyst used is 1 × 10 -6} to 1 × ^10-2 mol as the transition metal catalyst atom with respect to 1 mol of hydrosilyl in the silicone resin.

The condensation-curable silicone resin having silanol can be obtained by partially leaving silanol during the dealcoholization and dehydration reactions of the alkoxysilyl and the silicone having silanol. In the condensation reaction, a condensation catalyst can be used for the purpose of accelerating the reaction. Examples of the condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, and titanium complexes (for example, trade names: Organix TA-21, Organix TA-30, Organix TC-750, etc., Matsumoto Fine Chemicals Co., Ltd. ), Metal complexes such as tin complexes, metal alkoxides, and the like. The amount of silanol condensation catalyst in 100% by weight of the raw material used in the condensation reaction is, for example, 0.00001 to 0.1% by weight, preferably 0.00002 to 0.01% by weight, and more preferably 0.0005 to 0.0005. It is 0.001% by weight.

The modified silicone resin modified with an organic functional group having silanol is a silicone in which some of the organic groups of the silicone resin having silanol are replaced with organic functional groups, and the organic functional groups include amino, hydroxy, epoxy, and so on. Examples include mercapto, carboxyl, vinyl, allyl, styryl, and (meth) acryloyl. The substitution position of the organic functional group may be either the terminal of the silicone or the position of the side chain.

The resin (b) having a hydrogen-binding group contained in the resin composition of the present invention has a three-dimensional crosslinked structure containing silanol among silicone resins for the purpose of increasing the surface hardness of the cured film and the glass transition temperature. It preferably contains a siloxane compound. Examples of the siloxane compound having a three-dimensional crosslinked structure include _{a Q unit structure composed of the structural unit "SiO 2} " in which silicon does not have an organic substituent R, or a structural unit "RSiO _{3" in which silicon has one organic substituent R.} A siloxane compound having a T-unit structure consisting of " _{/ 2" can be mentioned.} The Q unit structure is represented by the following formula (3), and the T unit structure is represented by, for example, the following formula (4).

(In the formula (4), R ₉ is a group selected from a linear alkyl having 1 to 22 carbon atoms or an alkyl having a branch, an aryl having 1 to 9 carbon atoms, or an aryl alkyl having 7 to 21 carbon atoms. , These groups may have any hydrogen substituted with halogen, and if the alkyl has 2 or more carbon atoms, oxygen atoms (-O-), cycloalkylene, between arbitrary CC bonds, cycloalkenylene, phenylene, naphthalene may be inserted. However, the total number of carbon atoms in R ₉ is never greater than 30.)

A siloxane compound having a three-dimensional crosslinked structure can be obtained by hydrolyzing and condensing a silane compound having a hydrolyzable group to partially leave silanol. The siloxane compound having a three-dimensional crosslinked structure is a siloxane compound mainly having a three-dimensional crosslinked structure, and is called a silicone resin or a silicone alkoxy oligomer.

Specific examples of the silane compound having a hydrolyzable group are shown below.
Examples of the silane compound having a Q unit structure having a hydrolyzable group from which the structure represented by the formula (3) can be obtained include tetramethoxysilane, a partially hydrolyzed condensate (methyl silicate) of tetramethoxysilane, tetraethoxysilane, and tetra. Examples thereof include a partially hydrolyzed condensate of ethoxysilane (ethyl silicate), for example, ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, methyl silicate 51, and methyl silicate 53A (trade names, all manufactured by Corcote Co., Ltd.). Commercially available products such as can be used.
Examples of the silane compound having a T unit structure having a hydrolyzable group from which the structure represented by the formula (4) can be obtained include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and ethyltrimethoxy. Silane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, propyltripropoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, 1,1-dimethylethyltrimethoxysilane, 1,1-dimethylethyltriethoxysilane, isobutyltrimethoxysilane, isobutyl Triethoxysilane, pentyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyl Trimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, docosyltriethoxysilane, methoxymethyltrimethoxysilane, methoxymethyltriethoxysilane , Methoxypropyltrimethoxysilane, ethoxymethyltriethoxysilane, ethoxyethyltriethoxysilane, butoxyethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenyltriisopropoxysilane, phenylmethyltrimethoxy Silane, phenylmethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropyltriethoxysilane, 4-phenylbutyltrimethoxysilane, 2-methylphenyl Trimethoxysilane, 2-methylphenyltriethoxysilane, 3-methylphenyltrimethoxysilane, 3-methylphenyltriethoxysilane, 4-methylphenyltrimethoxy Silane, 4-methylphenyltriethoxysilane, 3,5-dimethylphenyltrimethoxysilane, 1-cyclohexyl-4-trimethoxysilylbenzene, 3- (4-methylphenyl) propyltrimethoxysilane, 3-methoxyphenyltrimethoxy Silane, 3-methoxyphenyl trimethoxysilane, 3-methoxyphenyl triethoxysilane, 4-methoxyphenyl trimethoxysilane, 4-methoxyphenyl triethoxysilane, phenoxymethyltrimethoxysilane, phenoxymethyltriethoxysilane, 3-phenoxypropyl Trimethoxysilane, cyclobutyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cycloheptiltrimethoxysilane, cycloheptiltriethoxysilane, cyclooctyltrimethoxysilane, cyclooctyl Triethoxysilane, 4-methylcyclohexyltriethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltriethoxysilane, (bicyclo [2.2.1] hept-5-en-2-yl) trimethoxysilane , (Vicyclo [2.2.1] hept-5-en-2-ylethyl) trimethoxysilane, (bicyclo [2.2.1] hept-5-en-2-ylethyl) triethoxysilane, bicyclo [2] .2.1] Hepta-2,5-diene-7-triethoxysilane, 1-naphthylrimethoxysilane, 1-naphthylriethoxysilane, 2-naphthylrimethoxysilane, 2-naphthylriethoxysilane, 1-naphthyl Methyltrimethoxysilane, 2-naphthylmethyltrimethoxysilane, 4-biphenyltrimethoxysilane, 4-biphenyltriethoxysilane, 1-phenoxy-4-triethoxysilylbenzene, tricyclo [3.3.1.13,7] Decane-1-triethoxysilyl, tricyclo [3.3.1.13,7] decane-2-triethoxysilane, 5-triethoxysilyl-2-norbornene, 2-triethoxysilylnorbornan, 3-methacryoxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane, trifluoroethyltrimethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-fluorophenyl Examples thereof include rutrimethoxysilane, 4-fluorophenyltrimethoxysilane, 3-fluorophenyltriethoxysilane, 4-fluorophenyltriethoxysilane, and pentafluorophenyltrimethoxysilane.
In terms expressing inter alia resulting resin composition excellent heat resistance, it is R ₉ is methyl or phenyl of formula (4), methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Is preferable.

In addition to at least one unit structure having a Q unit structure and a T unit structure, the above-mentioned siloxane compound has an M unit structure consisting of _{a structural unit "R 3} SiO _{1/2" in which three organic substituents R are attached to silicon, and silicon.} It may further contain at least one unit structure selected from the D unit structure composed of the structural unit "R _{2 SiO" in which two organic substituents R are attached.}
Specific examples of the silane compound having a hydrolyzable group that can obtain such a structure are shown below.

Examples of the silane compound having an M unit structure having a hydrolyzable group include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, and triphenylmethoxy. Silane, triphenylethoxysilane, triphenylpropoxysilane, triphenylbutoxysilane, dimethylphenylmethoxysilane, triisopropylmethoxysilane, tricyclohexylmethoxysilane, dimethylethylethoxysilane, dimethylbutylethoxysilane, dimethylphenylethoxysilane, diethylphenylethoxy Examples thereof include silane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane.

Examples of the D-unit structure silane compound having a hydrolyzable group include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane, and methylethyl. Examples thereof include polysiloxane compounds having dimethoxysilane, methylphenyldiethoxysilane, methylcyclohexyldimethoxysilane, silanol and / or alkoxysilyl (polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane). Examples of the polysiloxane compound having silanol and / or alkoxysilyl include 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane and Silaplane FM99 series (trade name, manufactured by JNC Co., Ltd.). ..

Such a silane compound having a hydrolyzable group may be used by mixing with another siloxane compound having a three-dimensional crosslinked structure without being hydrolyzed and condensed, or a siloxane compound having another three-dimensional crosslinked structure in advance. You may use it by reacting with. When used by mixing or reacting with another siloxane compound having a three-dimensional crosslinked structure, the reaction using the condensation catalyst proceeds rapidly, which is preferable. When it is desired to form a transparent cured film, the less colored Organix TA-21 and Organix TA-30 (both trade names, manufactured by Matsumoto Fine Chemical Co., Ltd.) are suitable.

The siloxane compound having a three-dimensional crosslinked structure may be silsesquioxane containing silanol and having only a T unit structure. The structure of silsesquioxane is known to be a ladder structure, a completely condensed structure (cage type structure), an incompletely condensed type structure (partial cage type structure), an amorphous structure (random structure), etc., and is hydrolyzable. It can be synthesized by hydrolyzing and condensing a silane compound having three groups.

The siloxane compound having a three-dimensional crosslinked structure can also be used by purchasing a commercially available product. Commercially available siloxane compounds having a three-dimensional crosslinked structure include RSN-0217, RSN-0220, RSN-0223, RSN-0249, RSN-0255, and RSN-6018 (trade names, all manufactured by Toray Dow Corning Co., Ltd.). ), KR-220L, KR-220LP, KR-480, KR-216 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SR-21, SR-23, SR-13, SR-33 (all) Product name, manufactured by Konishi Chemical Industry Co., Ltd., SO-1400, SO-1430, SO-1444, SO-1450, SO-1455, SO-1458, SO-1460 (all product names, manufactured by Hybrid Plastics Co., Ltd.) ) Can be mentioned. _{Among them, R 9} in formula (4) is phenyl RSN-0217, SR-21, SR-23, and R ₉ in formula (4) is methyl KR-220L, KR-220LP, SR-13, formula (4). RSN-0220, RSN-0223 containing phenyl and methyl as _{R 9} in, RSN-0249, RSN-0255 , RSN-6018, KR-480, SR-33, SO-1458, SO-1460 is obtained a resin composition It is preferable because the product exhibits excellent heat resistance.

Further, since the compound (a) has active hydrogen, a resin having a substituent capable of hydrogen-bonding to the active hydrogen is also included in the resin (b) having a hydrogen-bonding group. Examples of such a substituent include a nitrogen-containing heterocycle such as a lactam ring, pyridyl, imidazole, and triazine ring, and a carbonyl-containing group such as an amide, imide, lactone ring, and carboxy. These substituents can form hydrogen bonds with compound (a) even if they do not contain active hydrogen.

Examples of the resin having a nitrogen-containing heterocycle include polyimide (trade name: Capton, manufactured by Toray Co., Ltd., trade name: AURUM, manufactured by Mitsui Kagaku Co., Ltd., etc.), polyamideimide, polyetherimide, polybenzimidazole, and poly. Examples thereof include benzoxazole, methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified melamine resin, melamine resin such as methyl butyl mixed etherified melamine resin, and the like. Examples of the carbonyl-containing resin include polyvinyl acetate resin, urea resin, polycarbonate resin, polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyarylate (trade name: U polymer, etc.). Unitica Co., Ltd.), alkyd resin, etc. can be mentioned. A monomer that can constitute these resins or a polymer of this monomer is added to the resin composition of the present invention. These monomers and their polymers may be used alone or in combination of two or more.

The amount of the resin (b) having a hydrogen-bonding group used (content in the resin composition) is preferably 1 to 20 parts by weight with respect to 1 part by weight of the compound (a) represented by the formula (1). It is preferably 2 to 10 parts by weight. When the amount used is 1 part by weight or more, a cured film having sufficient heat resistance and electrical insulation can be obtained. On the other hand, when the amount used is 20 parts by weight or less, the polymerization rate becomes slow and the reaction rate does not decrease.

The resin composition of the present invention contains a resin (b) having a hydrogen-bonding group, and the resin (b) having the hydrogen-bonding group hydrogen-bonds to the compound (a) represented by the formula (1). be able to. Therefore, even a resin having no photocurable substituent can be immobilized in the resin composition by hydrogen bonding, and is immobilized by hydrogen bonding by irradiating light such as ultraviolet rays or visible light or heating. It is possible to form a cured film containing the resin. As described above, by using a resin (b) having various properties as the resin (b) having a hydrogen-bonding group, a photocurable or thermosetting resin composition having desired properties can be prepared.

<Polymerization initiator (c)>
A photopolymerization initiator can be used as the polymerization initiator (c) of the resin composition of the present invention. The photopolymerization initiator is a compound that causes a polymerization reaction of a reactive monomer by irradiating it with an active energy ray such as ultraviolet rays or visible light. Specific examples of such a photopolymerization initiator include benzophenone and Michler's ketone. , 4,4'-Bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2- Methyl-4'-isopropylpropiophenone, 2-hirodoxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 1 -Hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) ) Phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminoethyl benzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) Benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (T-Hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3' -Di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (4'-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (3', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (triclo Lomethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) ) -S-Triazine, 4- [pn, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5-( 2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p) -Dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2' -Bis (2,4-dichlorophenyl) -4,4', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4' , 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2 '-Bimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, Bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, bis (2,4,6-trimethylbenzoyl) ) Phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned.
Among these, 2-hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2- (dimethylamino)- 2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone is preferred.
The above photopolymerization initiator may be used alone or in combination of two or more.

In addition, a thermal polymerization initiator can be used as the polymerization initiator (c) of the resin composition of the present invention. When a thermal polymerization initiator is used, a polymerization reaction is caused by heat to obtain a cured film of the resin composition. That is, the resin composition of the present invention can be made into a thermosetting composition by adding the thermal polymerization initiator as the polymerization initiator (c). Examples of such a thermal polymerization initiator include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds, persulfates and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The amount of the polymerization initiator (c) used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the compound (a) represented by the formula (1). .. When the amount used is 0.1 part by weight or more, the polymerization rate is sufficient and the polymerization is not easily inhibited by oxygen or the like. On the other hand, when the amount used is 20 parts by weight or less, the residue of the polymerization initiator does not remain in the cured film, and a cured film having sufficient adhesion strength and heat resistance can be obtained. Furthermore, it does not cause coloring.

The resin composition of the present invention is other than the compound (a) represented by the formula (1), the resin (b) having a hydrogen-bonding group, and the polymerization initiator (c) as long as the curability and heat resistance are not impaired. Ingredients may be included. Examples of these components include compounds having a radically polymerizable double bond other than the compound (a) represented by the formula (1), resins other than the resin (b) having a hydrogen bonding group, solvents and the like. ..

Compounds having a radically polymerizable double bond other than the compound (a) represented by the formula (1) include (meth) acrylates other than the compound (a) represented by the formula (1) and radicals other than the (meth) acrylate. Resins having unsaturated bonds such as low molecular weight compounds having polymerizable double bonds, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, etc. included.

Specific examples of the (meth) acrylate other than the compound (a) represented by the formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth). ) Acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyalkylene glycol acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, Phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, tetrahydrofurfuryl alcohol acrylic acid multimeric ester, γ-butyrolactone (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meta) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3,5-dimethyl-7-hydroxyadamantyl (meth) acrylate, 3-hydroxy-1- Adamanthyl (meth) acrylate, methacryloyloxynorbornane (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, (meth) acrylate having an imide ring, cyclic trimethylpropanformal (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Ludi (meth) acrylate, butylene glycol di (meth) acrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, tricyclodecanedimethanol diacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylol propanetetra (meth) ) Acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethyl propantri (meth) acrylate, ε -Caprolactone-added ditrimethylol propanetetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate ) Acrylate, bisphenol Fethylene oxide modified di (meth) acrylate, bisphenol Fpropylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide modified di (meth) acrylate, ethylene isocyanurate Oxide-modified di (meth) acrylate, isocyanuric acid propylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, isocyanuric acid propylene oxide-modified tri (meth) acrylate, hydrogenated bisphenol F ethylene oxide-modified di (meth) acrylate Examples thereof include meth) acrylate, hydrogenated bisphenol Fpropylene oxide-modified di (meth) acrylate, hydrogenated bisphenol A ethylene oxide-modified di (meth) acrylate, and hydrogenated bisphenol A propylene oxide-modified di (meth) acrylate.

Specific examples of low molecular weight compounds having a radically polymerizable double bond other than (meth) acrylate include crotonic acid, α-chloroacrylic acid, silicic acid, maleic acid, fumaric acid, N-vinylformamide, and 2-allyl. Methyl oxymethylacrylate, polymethylmethacrylate macromonomer, N-cyclohexylmaleimide, N-phenylmaleimide, styrene, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N , N-Dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.

As the unsaturated polyester resin, a condensation product (unsaturated polyester) obtained by an esterification reaction of a polyhydric alcohol and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) is dissolved in a polymerizable monomer. Can be mentioned.

Unsaturated polyester can be produced by polycondensing an unsaturated acid such as maleic anhydride with a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as phthalic acid, maleic acid, or itaconic acid or an anhydride thereof is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane A polyhydric alcohol such as -1,4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A is reacted as an alcohol component, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, etc. Examples thereof include polybasic acids having no polymerizable unsaturated bond such as tetrahydrophthalic acid, adipic acid, and sebacic acid, or those produced by adding an anhydride thereof as an acid component.

The polyester (meth) acrylate resin includes (1) an epoxy compound containing α, β-unsaturated carboxylic acid ester in a terminal carboxyl polyester obtained from saturated polybasic acid and / or unsaturated polybasic acid and polyhydric alcohol. (Meta) acrylate resin obtained by reacting with (2) Saturated polybasic acid and / or polyester of terminal carboxyl obtained from unsaturated polybasic acid and polyhydric alcohol is reacted with a hydroxyl group-containing acrylate (meth). ) Acrylate resin, (3) Saturated polybasic acid and / or (meth) acrylate resin obtained by reacting (meth) acrylic acid with polyester having a terminal hydroxyl group obtained from unsaturated polybasic acid and polyhydric alcohol. ..

Saturated polybasic acids used as raw materials for polyester (meth) acrylate resins include, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebatic acid, etc., which do not have a polymerizable unsaturated bond. Examples thereof include a basic acid or an anhydride thereof and a polymerizable unsaturated polybasic acid such as fumaric acid, maleic acid, and itaconic acid or an anhydride thereof. Further, the polyhydric alcohol to be reacted as an alcohol component is the same as that of the unsaturated polyester.

The epoxy (meth) acrylate resin has a polymerizable unsaturated bond formed by a ring-opening reaction between a compound having glycidyl (epoxy) and a carboxyl compound having a polymerizable unsaturated bond such as (meth) acrylic acid. Compound (vinyl ester). Usually, an epoxy (meth) acrylate resin dissolved in a polymerizable monomer is used.

Examples of the compound having glycidyl (epoxy) include bisphenol A diglycidyl ether and its high molecular weight homologue, novolak type glycidyl ethers and the like. In addition to (meth) acrylic acid, it contains a reaction product of bisphenol (for example, type A) or a dibasic acid such as adipic acid, sebacic acid, and dimer acid (trade name: Haridaimer 270S, manufactured by Harima Chemicals, Inc.). You may.

As the urethane (meth) acrylate resin, for example, a polyfunctional isocyanate is reacted with a resin having a hydroxy group, and then a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound are further reacted. Examples thereof include radically polymerizable unsaturated group-containing oligomers obtained by. The polyfunctional isocyanate and the resin having a hydroxy group are the same as the resin having a urethane bond.

The hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specifically, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. (Meta) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid mono (meth) acrylate, tris (hydroxyethyl) isocyanul Examples thereof include acid di (meth) acrylate and pentaeslitortri (meth) acrylate.

Examples of the resin other than the resin (b) having a hydrogen-bonding group include a thermosetting resin and a thermoplastic resin. Examples of the thermosetting resin include epoxy resins. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, and glycidyl ester type epoxy resin. , Epoxy-based resins such as polymer-type epoxy resin and biphenyl-type epoxy resin can be mentioned. Epoxy resins have excellent heat resistance, adhesiveness, and chemical resistance, and can be used as needed.
Thermoplastic resins include polyethylene, polypropylene, polyvinylidene chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultrahigh molecular weight polyethylene, and poly-4-methylpentene. , Syndiotactic polystyrene, polyacetal, polyphenylene oxide, fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyether sulfone and the like.

The resin composition of the present invention may contain a solvent.
Examples of the solvent that can be used in the present invention include diethyl ether, tetrahydrofuran, diphenyl ether, dimethoxybenzene, acetone, methanol, ethanol, isopropanol, butyl alcohol, t-butyl alcohol, benzyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, and propio. Nitrile, benzonitrile, ethylene carbonates, propylene carbonate, ethyl acetate, isobutyl acetate, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acid, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionate Methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropion Ethyl acid acid, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, methyl 2-hydroxyisobutyrate, dioxane, ethylene glycol, diethylene glycol, tri Ethyl glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monob Chill ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether , Tetraethylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.
Of these, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, butyl acetate, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, and propylene glycol monomethyl ether are preferable.
The solvent used in the present invention may be one kind or a mixture of two or more kinds.

The amount of the solvent used is the compound (a) represented by the formula (1), the compound having a radically polymerizable double bond other than the compound (a), the resin (b) having a hydrogen bonding group, and the resin (b). The total amount of the resin other than the above, the polymerization initiator (c) and the like may be 1 to 80% by weight in 100% by weight of the composition containing the solvent.

The composition of the present invention may further contain other components as long as the heat resistance is not impaired, from the viewpoint of adjusting various physical properties and the subsequent curing at the time of film formation. Such other components include active energy ray sensitizers, polymerization inhibitors, polymerization initiators, leveling agents, surfactants, plasticizers, UV absorbers, photostabilizers, antioxidants, antistatic agents. , Silane coupling agent can be mentioned.

<Cured film>
The cured film of the present invention is obtained from a resin composition containing a urea-bonded tetrafunctional (meth) acrylate compound. The cured film is formed, for example, by applying a resin composition containing a urea-bonded tetrafunctional (meth) acrylate compound to the surface of a substrate and then irradiating the surface with light such as ultraviolet rays or visible light to cure the coating film. .. By blending a urea-bonded tetrafunctional (meth) acrylate compound, photocurability can be imparted to a resin composition having other components (organic resin, inorganic resin, etc.).

The cured film of the present invention is excellent in heat resistance and electrical insulation, and is also excellent in good balance of adhesion to a substrate such as metal or resin. Therefore, the application of the cured film of the present invention is not particularly limited, but it is suitably used as an insulating film or the like that protects a metal wiring surface or the like forming a predetermined circuit pattern.

When irradiating the resin composition with ultraviolet rays, visible light, or the like, the irradiation amount (exposure amount) may be appropriately selected according to the composition of the composition, ^{but is preferably about 100 to 5,000 mJ / cm 2, and} is preferably about 150 to 5,000 mJ / cm 2. About 2,000 mJ / cm ² is more preferable, and about 180 to 1,000 mJ / cm ² is even more preferable. The wavelength of ultraviolet rays, visible rays, etc. to be irradiated is preferably 200 to 500 nm, more preferably 250 to 450 nm.
In the present invention, the exposure amount is a value measured by an integrated light meter UIT-201 (trade name) equipped with a receiver UVD-365PD (trade name) manufactured by Ushio, Inc.

The exposure machine is equipped with a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a halogen lamp, an electrodeless lamp, a UV-LED lamp, etc. It is preferable that the device irradiates the light and the like. Since the urea-bonded tetrafunctional (meth) acrylate compound has high reactivity, it can be cured at a high reaction rate equivalent to that when a high-pressure mercury lamp is used by using a UV-LED lamp or the like having a low energy amount as a light source. it can. Therefore, according to the resin composition containing the urea-bonded tetrafunctional (meth) acrylate compound, a cured film having good heat resistance can be produced by using a light source having a low energy amount.

Further, if necessary, the cured film cured by irradiation with light may be further heated and fired. For example, the cured film can be cured more firmly by heating and firing at 80 to 250 ° C. for about 10 to 120 minutes.

The resin composition containing the urea-bonded tetrafunctional (meth) acrylate compound of the present invention is, for example, applied to a substrate and cured. The shape of the substrate is not limited to a flat plate shape, but may be a curved surface shape.

The substrate that can be used in the present invention is not particularly limited, but for example, a polyester resin substrate made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or the like; a polyolefin resin substrate made of polyethylene, polypropylene, or the like; polyvinyl chloride, fluorine. Organic polymer film made of resin, acrylic resin, styrene resin, polyamide, polycarbonate, polyimide, etc .; substrate made of cellophane; metal foil; laminated film of resin substrate made of polyimide, etc. and metal foil; glass epoxy resin and metal Laminated board with foil; Paper that has a sealing effect, such as glassin paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol, starch or carboxymethyl cellulose (CMC); silicon wafer, silicon nitride substrate, silicon oxide substrate Silicon-based substrates such as, etc .; Examples thereof include glass substrates such as glass wafers and quartz substrates.

In addition, these substrates are further used as pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents and / or electromagnetic wave inhibitors, etc., as long as they do not adversely affect the effects of the present invention. May contain the additives of.
In addition, at least a part of the surface of the substrate may be subjected to surface treatment such as water repellent treatment, corona treatment, plasma treatment, and / or blast treatment as necessary, and the surface may be subjected to an easy-adhesion layer, a protective film for a color filter, or hard A coat film may be provided.

The thickness of the cured film of the present invention may be appropriately selected depending on the desired application, but is preferably 1 μm to 50 μm, and more preferably 5 μm to 20 μm.

The cured film formed on the above-mentioned substrate can be peeled off from the substrate and used as a material for electronic components, etc., and depending on the application and the substrate used, the cured film can be used as it is without peeling from the substrate, such as an electronic circuit board. As a substrate with a cured film, it can be used as a material for electronic parts and the like.

Examples of the electronic circuit board include a rigid board, a flexible board, and a rigid flexible board.
As the flexible substrate, for example, an ink containing a urea-bonded tetrafunctional (meth) acrylate compound is applied to the entire surface or a predetermined pattern (line) on a film-like substrate such as a polyimide film in which wiring is formed in advance by an inkjet method or the like. Examples thereof include a substrate obtained by applying the coating film to a film, etc. to form a coating film, and then curing the coating film.

The metal forming the wiring (circuit) is not particularly limited, but gold, silver, copper, aluminum or indium tin oxide (ITO) is preferable. The cured film obtained by applying ink containing a urea-bonded tetrafunctional (meth) acrylate compound in a predetermined pattern to the substrate on which these wirings are formed and curing the ink functions as an insulating film or the like that protects the wirings. To do.

<Electronic components>
The electronic component of the present invention includes a cured film or a substrate with a cured film. A flexible electronic component and a display element can be obtained by using a cured film or a substrate with a cured film using a film substrate as the substrate.
For example, an IC chip, a capacitor, a resistor, a fuse, or the like is attached to an electronic circuit board manufactured by using the cured film of the present invention having excellent heat resistance, electrical insulation, adhesion to a substrate, folding resistance, and flame retardancy. By mounting, for example, an electronic component for a liquid crystal display element can be created.

[Synthesis Example 1]
<Synthesis example of urea-bonded tetrafunctional acrylic-modified silicon compound A>
7.0 g of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI, manufactured by Showa Denko KK, hereinafter referred to as "BEI" as appropriate) and 0.1 g of 4-methoxyphenol in tetrahydrofuran (Tokyo Kasei (Tokyo Kasei) The solution dissolved in 27.9 g (manufactured by Co., Ltd.) was stirred at room temperature in a nitrogen atmosphere. 3.0 g of a siloxane diamine compound (trade name: BY16-871, manufactured by Toray Dow Corning Co., Ltd.) diluted with 12.1 g of tetrahydrofuran was added dropwise to the solution over 10 minutes, and the mixture was stirred at 20 to 30 ° C. for 1 hour. A reaction solution was obtained. The solvent of the obtained reaction solution was removed by an evaporator, and then hexane (10.0 g) was added dropwise to remove an excess amount of BEI by decantation. After removing the supernatant, the solvent was removed from the obtained solution using a vacuum pump to obtain a urea-bonded tetrafunctional acrylic-modified silicon compound A (7.6 g, hereinafter appropriately referred to as "silicon compound A"). .. Silicon compound A (compound (a)) is shown below.

<Silicon compound A>

[Synthesis Example 2]
<Synthesis example of urea-bonded tetrafunctional acrylic-modified silicon compound B>
6.1 g of a siloxane diamine compound (trade name: FM3311, manufactured by JNC Co., Ltd.) and 0.1 g of 4-methoxyphenol were dissolved in 24.6 g of tetrahydrofuran, and the mixture was stirred at room temperature in a nitrogen atmosphere. 3.9 g of BEI diluted with 15.4 g of tetrahydrofuran was added dropwise to the solution over 10 minutes, and the mixture was stirred at 20 to 30 ° C. for 1 hour. The solvent of the obtained reaction solution was removed by an evaporator, and then hexane (10.0 g) was added dropwise to remove an excess amount of BEI by decantation. After removing the supernatant, the solvent was removed from the obtained solution using a vacuum pump to obtain a urea-bonded tetrafunctional acrylic-modified silicon compound B (9.5 g, hereinafter appropriately referred to as "silicon compound B"). .. Silicon compound B (compound (a)) is shown below.

<Silicon compound B>

[Synthesis Example 3]
<Synthesis example of urea-bound tetrafunctional acrylic-modified aromatic compound C>
Aromatic diamine compound (trade name: 2,2-bis (4- (4-aminophenoxy) phenylpropane, manufactured by Wakayama Seika Kogyo Co., Ltd.) 7.41 g and 4-methoxyphenol 0.16 g are methyl ethyl ketone (hereinafter, It was appropriately dissolved in 20.0 g (referred to as “MEK”) and stirred at room temperature under a nitrogen atmosphere. 8.61 g of BEI was added dropwise to the solution and stirred at 60 ° C. Subsequently, it was dissolved in 5.00 g of MEK in the solution. 0.10 g of zirconium tetraacetylacetonate (trade name: Organix ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added dropwise, and the mixture was stirred at 60 ° C. for 2 hours. The obtained reaction solution was subjected to solvent removal by an evaporator. A MEK solution of urea-bound tetrafunctional acrylic-modified aromatic compound C (25.58 g, solid content concentration 81 wt%, hereinafter appropriately referred to as “aromatic compound C”) was obtained. Aromatic compound C (compound (a)). ) Is shown below.

<Aromatic compound C>

[Synthesis Example 4]
<Synthesis example of urea-bound tetrafunctional acrylic-modified aromatic compound D>
13.5 g of BEI and 0.2 g of 4-methoxyphenol were dissolved in 37.0 g of tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature. 6.6 g of an aromatic diamine compound (9,9-bis (4-aminophenyl) fluorene) diluted with 50.0 g of tetrahydrofuran was added dropwise to the solution over 8 minutes, and the mixture was stirred at 50 ° C. for 1 hour. Further, 5.2 g of BEI was added dropwise to the reaction solution, and the mixture was stirred at 50 ° C. for 1 hour. The obtained reaction solution was extracted with ethyl acetate-water, washed with saturated brine, and the extract was dried over magnesium sulfate. The extract and magnesium sulfate were separated by filtration, and the solvent was removed by an evaporator to obtain a concentrated solution. It was allowed to stand at room temperature and recrystallized to obtain a white solid. The obtained white solid was washed with ethyl acetate and then vacuum dried to completely remove the solvent. As a result, a urea-bound tetrafunctional acrylic-modified aromatic compound D (8.5 g, hereinafter appropriately referred to as "aromatic compound D") was obtained. Aromatic compound D (compound (a)) is shown below.

<Aromatic compound D>

[Comparative Synthesis Example 1]
<Synthesis example of urea-bonded bifunctional acrylic-modified silicon compound E>
0.85 g of a siloxane diamine compound (trade name: BY16-871, manufactured by Toray Dow Corning Co., Ltd.) and 0.02 g of 4-methoxyphenol were dissolved in 8.00 g of tetrahydrofuran, and the mixture was stirred at room temperature under a nitrogen atmosphere. 1.15 g of 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko KK, hereinafter appropriately referred to as "AOI") was added dropwise to the solution, and the mixture was stirred at 20 to 30 ° C. for 1 hour. The solvent of the obtained reaction solution was removed by an evaporator, and then hexane (10.0 g) was added dropwise to remove an excess amount of AOI by decantation. After removing the supernatant, the solvent was removed from the obtained solution using a vacuum pump to obtain a urea-bonded bifunctional acrylic-modified silicon compound E (1.6 g, hereinafter appropriately referred to as “silicon compound E”). .. The silicon compound E is shown below. The silicon compound E does not correspond to the compound (a) because X in the formula (1) is not a group represented by the formula (2).

<Silicon compound E>

[Comparative synthesis example 2]
<Synthesis example of urethane-bonded tetrafunctional acrylic-modified silicon compound F>
11.72 g of BEI was added dropwise to a solution containing 8.29 g of a siloxane diol compound (trade name: FM4401, manufactured by JNC Co., Ltd.) and 0.2 g of 4-methoxyphenol, and the mixture was stirred at 60 ° C. Subsequently, 0.1 g of zirconium tetraacetylacetone (trade name: Olgatics ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) dissolved in 10.00 g of MEK was added dropwise to the solution, and the mixture was stirred at 60 ° C. for 2 hours. The solvent of the obtained reaction solution was removed by an evaporator. A MEK solution of a urethane-bonded tetrafunctional acrylic-modified silicon compound F (24.79 g, solid content concentration 84 wt%, hereinafter appropriately referred to as “silicon compound F”) was obtained. The silicon compound F is shown below. The silicon compound F does not correspond to the compound (a) because the main chain has a urethane bond instead of the urea bond.

<Silicon compound F>

[Synthesis Example 5]
<Synthesis example of urea-bonded tetrafunctional acrylic-modified aromatic compound G>
Aromatic diamine compound (trade name: 4,4-diaminodiphenyl ether, manufactured by Tokyo Kasei Co., Ltd.) 4.73 g and 0.16 g of 4-methoxyphenol are dissolved in a mixed solvent of 50.00 g of acetonitrile and 50.00 g of acetone, and nitrogen is used. The mixture was stirred at room temperature in an atmosphere. 11.10 g of BEI was added dropwise to the solution, and the mixture was stirred at 60 ° C. Subsequently, 0.08 g of zirconium tetraacetylacetone (trade name: Olgatics ZC-150, manufactured by Matsumoto Fine Chemicals Co., Ltd.) dissolved in 5.00 g of acetonitrile was added dropwise to the solution, and the mixture was stirred at 60 ° C. for 3 hours. .. The solvent of the obtained reaction solution was removed by an evaporator and a vacuum pump. By recrystallization at room temperature, a urea-bonded tetrafunctional acrylic-modified aromatic compound G (15.11 g, hereinafter appropriately referred to as "silicon compound G") was obtained. Aromatic compound G (compound (a)) is shown below.

<Aromatic compound G>

<Preparation of composition 1>
1.200 g of the silicon compound A synthesized in Synthesis Example 1, 0.045 g of an alkylphenone-based photopolymerization initiator (trade name: Irgacure 127, manufactured by BASF, hereinafter appropriately referred to as "IC127") as a curing agent, and MEK2 as a solvent. Composition 1 was obtained by mixing 100 g and 0.700 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation, hereinafter appropriately referred to as "NMP") at room temperature.

<Preparation of composition 2>
Composition 2 was obtained by using the silicon compound B synthesized in Synthesis Example 2 instead of the silicon compound A in the same manner as in the composition 1.

<Preparation of composition 3>
0.120 g of the silicon compound A synthesized in Synthesis Example 1 and 1.080 g of a siloxane compound having a three-dimensional crosslinked structure (trade name: SR-21, manufactured by Konishi Chemical Industry Co., Ltd., hereinafter appropriately referred to as "SR-21"). , 0.020 g of IC127 as a curing agent, 2.100 g of MEK and 0.700 g of NMP (manufactured by Mitsubishi Chemical Corporation) as a solvent were mixed to obtain the composition (resin composition) 3 of the present invention.

<Preparation of composition 4>
The composition (resin composition) 4 of the present invention was obtained by using silicon compound B instead of silicon compound A in the same manner as in composition 3.

<Preparation of composition 5>
The composition of the present invention is obtained by mixing 0.300 g of the silicon compound A synthesized in Synthesis Example 1, 0.900 g of SR-21, 0.050 g of IC127 as a curing agent, and 2.100 g of MEK and 0.700 g of NMP as a solvent. A product (resin composition) 5 was obtained.

<Preparation of composition 6>
The composition (resin composition) 6 of the present invention was obtained by using Irgacure 379EG (trade name, manufactured by BASF, hereinafter appropriately referred to as "IC379EG") instead of IC127 in the same manner as in composition 5.

<Preparation of composition 7>
The composition of the present invention is obtained by mixing 0.180 g of the silicon compound A synthesized in Synthesis Example 1, 1.020 g of SR-21, 0.027 g of IC379EG as a curing agent, and 2.100 g of MEK and 0.700 g of NMP as a solvent. A product (resin composition) 7 was obtained.

<Preparation of composition 8>
The composition 8 was obtained by using the silicon compound E synthesized in Comparative Synthesis Example 1 instead of the silicon compound A in the same manner as in the composition 3.

[Reference example 1]
Composition 1 was applied onto a glass substrate cut into 4 cm × 4 cm, and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, and further dried on a hot plate heated to 135 ° C. for 5 minutes, and then a high-pressure mercury irradiation device (trade name: 8 kW × 1 conveyor type ultraviolet curing device). , Manufactured by Eye Graphics Co., Ltd. ^{, photocured under the condition of 1,000 mJ / cm 2} to obtain a cured film (1). The cured film (1) was a colorless and transparent film without stickiness. The exposure amount was measured using an illuminometer (UVPF-A1 / PD-365, manufactured by Iwasaki Electric Co., Ltd.).

[Reference example 2]
A cured film (2) was obtained in the same manner as in Reference Example 1 except that the composition 2 was used instead of the composition 1. The cured film (2) was a colorless and transparent film without stickiness.

[Example 1]
A cured film (3) was obtained in the same manner as in Reference Example 1 except that the composition 3 was used instead of the composition 1 and the coating was applied on a glass substrate cut into 10 cm × 10 cm.

[Example 2]
A cured film (4) was obtained in the same manner as in Example 1 except that the composition 4 was used instead of the composition 1.

[Comparative Example 1]
A cured film (5) was obtained in the same manner as in Example 1 except that the obtained composition 8 was used instead of the composition 1.

<Evaluation of cured film>
<5% weight reduction>
Measurement was performed in the range of 40 ° C. to 550 ° C. using a differential thermogravimetric simultaneous measuring device (TG / DTA6200, manufactured by Hitachi High-Tech Science Corporation). In order to eliminate an error due to moisture absorption of the film, the weight at 100 ° C. was set to 100%, and the temperature at which the weight was reduced by 5% was set to 5% weight reduction. The results are shown in Table 1.

As is clear from the evaluation results, the cured film obtained by curing the resin composition of the present invention containing a urea-bonded tetrafunctional acrylic-modified silicon compound is a resin composition containing a urea-bonded bifunctional acrylic-modified silicon compound. It had excellent heat resistance as compared with the cured film obtained by curing.
From this result, it can be said that the number of (meth) acrylates bonded to the terminal of the (meth) acrylate compound having a urea bond affects the heat resistance of the cured film obtained by curing the resin composition containing the compound. .. The urea-bonded (meth) acrylate compound having two urea bonds has a resin composition containing a urea-bonded (meth) acrylate compound and a siloxane compound having a three-dimensional crosslinked structure by increasing the number of functional groups to four. It was found that the heat resistance of the cured film formed by the compound was improved. From the viewpoint of forming a cured film having good heat resistance, the content of the siloxane compound having a three-dimensional crosslinked structure in the resin composition is 1 to 20 parts by weight with respect to 1 part by weight of the urea-bonded (meth) acrylate compound. Parts are preferable, and 5 to 15 parts by weight are more preferable.

The components contained in the above-mentioned compositions 1 to 8 are shown in Table 2 below (unit: g).

Compounds A and B: Silicon compounds A and B (tetrafunctional) (Compound (a))
Compound E: Silicon compound E (bifunctional)
Compound SR-21: A siloxane compound (resin (b)) having a three-dimensional crosslinked structure (R _{9: phenyl) represented by the formula (4).}
Hardener IC127: Irgacure 127 (polymerization initiator (c))
Hardener IC379EG: Irgacure 379EG (polymerization initiator (c))

<Measurement of reaction rate 1>
[Example 3]
The composition 5 was applied onto a glass substrate cut into 4 cm × 4 cm and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, further dried on a hot plate heated to 135 ° C. for 5 minutes, and then exposed to 500 to 500 with the same high-pressure mercury irradiation device as in Reference Example 1. The reaction rate of the acryloyl group was measured by changing the range in the range of 2,500 mJ / cm ^2. The reaction rate was determined by the following method.

<Reaction rate>
Using a Fourier transform infrared spectrophotometer (FT / IR-6700, manufactured by JASCO Corporation), the reaction rate was calculated using the following formula.
Reaction rate (%) = {(X1-X2) / X1} x 100
(X1: Peak area ratio P-2 / P-1 before exposure, X2: Peak area ratio P-2 / P-1 after exposure,
P-1: Peak area of silicon-phenyl bond (1440 cm ^-1 ),
P-2: Peak area of acrylic terminal CH bond (1410 cm ^-1 ))

[Example 4]
Example 3 except that the composition 6 was photocured with a UV-LED irradiation transport device (trade name: LSS-08A, manufactured by Sun Energy Co., Ltd.) instead of the high-pressure mercury irradiation device of Example 3. The reaction rate of the acryloyl group was measured by the same method. The results are shown in Table 3.

In general, the amount of energy of ultraviolet rays irradiated by the UV-LED irradiation transport device used in Example 4 is smaller than that of the high-pressure mercury irradiation device, so that the reaction rate is high even if a curing agent suitable for the LED light source is used. It goes down. However, from the results of Examples 3 and 4, even when the UV-LED irradiation carrier is used, high-pressure mercury has the highest reaction rate in UV curing of acrylate by selecting a curing agent suitable for the light source. It can be seen that a cured film can be produced with a reaction rate comparable to that of the above. As is clear from these evaluation results, by using the resin composition of the present invention containing the urea-bonded tetrafunctional (meth) acrylate compound as the compound (a), high-pressure mercury irradiation is performed even when a UV-LED irradiation carrier is used. It was possible to form a cured film comparable to that using the device.

[Example 5]
The composition 7 was applied onto a chromium substrate cut into 9 cm × 7 cm and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, further dried on a hot plate heated to 135 ° C. for 5 minutes, and then 1,000 mJ using the same UV-LED irradiation transfer device as in Example 4. and photocuring conditions / cm ^2, to obtain a colorless transparent cured film (6). Then, aluminum was vapor-deposited using a vacuum vapor deposition apparatus (VE-2030, manufactured by Vacuum Device Co., Ltd.). The volume resistivity measured using an ultra-high resistivity meter (DSM-810, manufactured by Agilent) was 1.9 × 10 ¹⁵ (Ω · cm) and had excellent electrical insulation.

<Preparation of composition 9>
Composition 9 was obtained by mixing 1.800 g of the silicon compound A synthesized in Synthesis Example 1, 0.270 g of IC379EG as a curing agent, and 3.150 g of MEK and 1.050 g of NMP as a solvent.

<Preparation of composition 10>
The composition 10 was obtained by using the acrylic-modified silicon compound F synthesized in Comparative Synthesis Example 2 instead of the silicon compound A in the same manner as in the composition 9.
The components contained in the above-mentioned compositions 9 to 10 are shown in Table 4 below (unit: g).

[Reference example 3]
The composition 9 was applied onto a glass substrate cut into 4 cm × 4 cm, and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, further dried on a hot plate heated to 135 ° C. for 5 minutes, and then 1,000 mJ in the same UV-LED irradiation transfer device as in Example 4. A cured film (7) was obtained by photocuring under the condition of / cm ^2. The obtained cured film (7) was a colorless and transparent film without stickiness.

[Reference Comparative Example 1]
A cured film (8) was obtained in the same manner as in Reference Example 3 except that the composition 10 was used instead of the composition 9.

<Evaluation of cured film>
<Glass transition temperature>
Using a rigid pendulum type viscoelasticity measuring device (“RPT-3000W” manufactured by A & D Co., Ltd.), the temperature was raised from 40 ° C. to 220 ° C., and the glass transition temperature (Tg) was measured. The results are shown in Table 5.

As is clear from the evaluation results, the cured film (7) obtained by curing the (meth) acrylate compound having a urea bond is cured obtained by curing the (meth) acrylate compound having a urethane bond. It had excellent heat resistance as compared with the film (8).
From this result, it can be said that the bonding mode of the main chain of the compound having a urea bond affects the heat resistance of the cured product obtained by curing the compound.

<Preparation of composition 11>
The composition of the present invention is obtained by mixing 0.300 g of the silicon compound A synthesized in Synthesis Example 1, 0.900 g of SR-21, 0.045 g of IC379EG as a curing agent, and 2.100 g of MEK and 0.700 g of NMP as solvents. Resin composition) 11 was obtained.

<Preparation of composition 12>
The composition 12 of the present invention was obtained in the same manner as in the composition 11 except that the silicon compound F synthesized in Comparative Synthesis Example 2 was used instead of the silicon compound A.
The components contained in the above-mentioned compositions 11 to 12 are shown in Table 6 below (unit: g).

<Measurement of reaction rate 2>
[Example 6]
The composition 11 was applied onto a glass substrate cut into 4 cm × 4 cm, and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, further dried on a hot plate heated to 135 ° C. for 5 minutes, and then exposed by the same UV-LED irradiation transfer device as in Example 4. The reaction rate of the acryloyl group was measured by changing the range from 400 to 1,500 mJ / cm ^2. The reaction rate was determined by the same method as in Example 5.

[Comparative Example 2]
The reaction rate of the acryloyl group was measured by the same method as in Example 6 except that the composition 12 was used instead of the composition 11. The results are shown in Table 7.

As is clear from the evaluation results, the cured film obtained by curing the composition containing the (meth) acrylate compound having a urea bond of the present invention is higher than that of the (meth) acrylate compound having a urethane bond. It was reactive. In particular, at a relatively small exposure amount of 1,000 (mJ / cm ² ) or less, the (meth) acrylate compound having a urea bond showed significantly higher reactivity than the (meth) acrylate compound having a urethane bond. ..
From this result, it can be said that the binding mode of the main chain of the tetrafunctional acrylic-modified silicon compound affects the reactivity.

<Preparation of composition 13>
Composition 13 was obtained by mixing 0.540 g of the aromatic compound C synthesized in Synthesis Example 3, 0.081 g of IC379EG as a curing agent, and 3.150 g of MEK and 1.050 g of NMP as a solvent.

<Preparation of composition 14>
The composition 14 was obtained in the same manner as in the composition 13 except that the aromatic compound D synthesized in Synthesis Example 4 was used instead of the aromatic compound C.

<Preparation of composition 15>
The composition 15 was obtained in the same manner as in the composition 13 except that the aromatic compound G synthesized in Synthesis Example 5 was used instead of the aromatic compound C.
The components contained in the above-mentioned compositions 13 to 15 are shown in Table 8 below (unit: g).

Compounds C and D: Aromatic compounds C and D (main chain aromatic ring 4, compound (a))
Compound G: Aromatic compound G (main chain aromatic ring 2, compound (a))

[Reference example 4]
The composition 13 was applied onto a glass substrate cut into 10 cm × 10 cm, and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, further dried on a hot plate heated to 135 ° C. for 5 minutes, and then 1,000 mJ in the same UV-LED irradiation transfer device as in Example 4. A cured film was obtained by photocuring under the condition of / cm ^2. The obtained cured film was a colorless and transparent film without stickiness.

[Reference example 5]
A colorless and transparent cured film was obtained in the same manner as in Reference Example 4 except that the composition 14 was used instead of the composition 13.

[Reference example 6]
A cured film was obtained in the same manner as in Reference Example 4 except that the composition 15 was used instead of the composition 13.

<Evaluation of cured film>
<5 to 20% weight reduction>
Using the same differential thermogravimetric simultaneous measuring device as in Example 1, the measurement was performed in the range of 40 ° C. to 550 ° C. In order to eliminate an error due to moisture absorption of the film, the weight at 100 ° C. was set to 100%, and the temperatures at which the weight was reduced by 5 to 20% were set to 5%, 10%, and 20% weight reduction, respectively. The results are shown in Table 9.

As is clear from the evaluation results, the composition containing a compound having four aromatic rings in the main chain is superior to the composition containing a compound having two aromatic rings in the main chain by curing the composition. A cured film having heat resistance was obtained.
From this result, it can be said that the number of aromatic rings bonded to the main chain of the (meth) acrylate compound having a urea bond affects the heat resistance. A urea-bonded (meth) acrylate compound having four or more aromatic rings in the main chain has a composition containing a urea-linked (meth) acrylate compound and a photopolymerization initiator by increasing the number of aromatic rings to four. It was found that the heat resistance of the cured film formed by the compound was improved.

[Synthesis Example 6]
<Synthesis example of a siloxane compound having a silanol-containing three-dimensional crosslinked structure>
31.8 g of phenyltrimethoxysilane, 33.5 g of tetraethoxysilane, 4.9 g of dimethyldimethoxysilane, and diethylene glycol ethyl in a three-necked flask with an internal volume of 200 ml equipped with a dropping funnel, a reflux condenser, and a thermometer. 34.3 g of methyl ether was charged and sealed with dry nitrogen. After stirring at room temperature for 30 minutes while stirring with a magnetic stirrer, a mixed solution of 14.4 g of ion-exchanged water and 22.4 g of formic acid was added dropwise over 20 minutes. After reacting at room temperature for 1 hour, the mixture was heated at 90 ° C. for 1.5 hours, 100 ° C. for 1 hour, and 140 ° C. for 2.5 hours using an oil bath to stop distilling off the produced methanol and ethanol. Was confirmed and the reaction was terminated. The mixture was allowed to cool to room temperature, mixed with 100 g of ethyl acetate, and then washed with water using a separating funnel until the pH became neutral. Then, the solution was concentrated at room temperature using an evaporator until the weight of the solution reached 50 g to prepare a siloxane compound solution (matrix A) having a silanol-containing three-dimensional crosslinked structure having a solid content concentration of 44% by weight.

Using the same Fourier transform infrared spectrophotometer as in Example 3, the IR spectrum of matrix A was measured, and ^{the presence of a peak of 920 cm -1} attributed to silanol gave silanol (silanol) to the siloxane compound having a three-dimensional crosslinked structure. It was confirmed that 920 cm ^{-1) was contained.} The weight average molecular weight (Mw) determined by GPC analysis of Matrix A was 41,300, and the molecular weight distribution (Mw / Mn) was 5.2. GPC analysis was performed under the conditions shown below.
<GPC>
Equipment: LC-2000Plus series manufactured by JASCO Corporation (detector: differential refractometer)
Solvent: THF / DMF = 1/1 (v / v)
Flow velocity: 0.5 ml / min
Column temperature: 40 ° C
Column used: Showa Denko Corporation, Asahipak GF-1G 7B (guard column) + Asahipak GF-7M HQ, exclusion limit molecular weight (PEG) = 10,000,000)
Standard sample for calibration curve: PSt

<Preparation of composition 16>
0.18 g of silicon compound A synthesized in Synthesis Example 1, 3.673 g of matrix A (1.620 g as a siloxane compound having a three-dimensional crosslinked structure), 0.027 g of IC127, and 2.147 g of NMP as a solvent. Was mixed to obtain the composition 16 of the present invention.

[Example 7]
The composition 16 was applied onto a glass substrate cut into 4 cm × 4 cm and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80 ° C. for 5 minutes, and further dried on a hot plate heated to 135 ° C. for 5 minutes to prepare two uncured films. Only one of the uncured films was photocured in the same high-pressure mercury irradiation device as in Reference Example 1 under ^{the condition of 1,000 mJ / cm 2} , to form a cured film (9), and the remaining one was designated as an uncured film (1). did. The exposure amount was measured using the same illuminometer as in Reference Example 1. The solvent resistance of the prepared uncured film (1) and cured film (9) was evaluated under the following conditions.

<Solvent resistance evaluation>
The uncured film (1) and the cured film (9) obtained in Example 7 were immersed in NMP for 15 minutes at room temperature together with the glass substrate, the weight of the film before and after immersion was measured, and the remaining film was left using the following formula. As a result of calculating the film ratio, the residual film ratio of the uncured film (1) was 4%, and the residual film ratio of the cured film (9) was 83%.
Residual film ratio = (W1-W2) / W1
(W1: Film weight before immersion, W2: Film weight after immersion)

This result was obtained by reacting the acryloyl group in the resin composition even though the resin composition contained only 10% by weight of the urea-bonded tetrafunctional acrylic-modified silicon compound A. It shows that the film has developed solvent resistance. This suggests that the urea-bonded tetrafunctional acrylic-modified silicon compound A and the siloxane compound having a three-dimensional crosslinked structure contained in the matrix A form hydrogen bonds.

[Examples 8 to 10]
Each component was mixed in the blending amount (unit: g) shown in Table 10 to prepare compositions 17 to 19, and cured films (10) to (12) were prepared in the same manner as in Example 4.
<Heat resistance evaluation>
The adhesion of the cured films (10) to (12) before and after the heating test at 200 ° C. for 30 minutes was evaluated by a grid peeling test (cross-cut test). The evaluation tape is No. 3M made by 3M. 610 was used. Those with no peeling were marked with "○", and those with 1 to 100 peeling were marked with "x". As a result, as shown in Table 10, good adhesion was shown before and after the heating test in all the cured films. Since no cracks are generated in the cured film after the heating test, the resin composition of the present invention can be suitably used as an insulating film for a semiconductor that requires a heating step.

Compound SR-23 (manufactured by Konishi Chemical Industry Co., Ltd.): _{A siloxane compound having a three-dimensional crosslinked structure (R 9} : phenyl) represented by the formula (4) (resin (b)).
Compound DMDMS (manufactured by Tokyo Kasei Co., Ltd.): Didimethyldimethoxysilane condensation catalyst TA-30 (manufactured by Matsumoto Fine Chemical Co., Ltd.): Organix TA-30

The resin composition of the present invention has excellent reactivity even in an LED light source, can be used as a protective film for an optical device material whose deterioration due to ultraviolet rays is a problem, and has excellent heat resistance and electrical insulation. Since it has, it can be used as an insulating film for electronic parts such as semiconductors.

Specific examples of the silane compound having a hydrolyzable group are shown below.
Examples of the silane compound having a Q unit structure having a hydrolyzable group from which the structure represented by the formula (3) can be obtained include tetramethoxysilane, a partially hydrolyzed condensate (methyl silicate) of tetramethoxysilane, tetraethoxysilane, and tetra. Examples thereof include a partially hydrolyzed condensate of ethoxysilane (ethyl silicate), for example, ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, methyl silicate 51, and methyl silicate 53A (trade names, all manufactured by Corcote Co., Ltd.). Commercially available products such as can be used.
Examples of the silane compound having a T unit structure having a hydrolyzable group from which the structure represented by the formula (4) can be obtained include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and ethyltrimethoxy. Silane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, propyltripropoxysilane, isopropyl Trimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, 1,1-dimethylethyltrimethoxysilane, 1,1-dimethylethyltriethoxysilane, isobutyltrimethoxysilane, isobutyl Triethoxysilane, pentyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyl Trimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, docosyltriethoxysilane, methoxymethyltrimethoxysilane, methoxymethyltriethoxysilane , Methoxypropyltrimethoxysilane, ethoxymethyltriethoxysilane, ethoxyethyltriethoxysilane, butoxyethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenyltriisopropoxysilane, phenylmethyltrimethoxy Silane, phenylmethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropyltriethoxysilane, 4-phenylbutyltrimethoxysilane, 2-methylphenyl Trimethoxysilane, 2-methylphenyltriethoxysilane, 3-methylphenyltrimethoxysilane, 3-methylphenyltriethoxysilane, 4-methylphenyltrimethoxy Silane, 4-methylphenyltriethoxysilane, 3,5-dimethylphenyltrimethoxysilane, 1-cyclohexyl-4-trimethoxysilylbenzene, 3- (4-methylphenyl) propyltrimethoxysilane, 3-methoxyphenyltrimethoxy Silane, 3-methoxyphenyl trimethoxysilane, 3-methoxyphenyl triethoxysilane, 4-methoxyphenyl trimethoxysilane, 4-methoxyphenyl triethoxysilane, phenoxymethyltrimethoxysilane, phenoxymethyltriethoxysilane, 3-phenoxypropyl Trimethoxysilane, cyclobutyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cycloheptiltrimethoxysilane, cycloheptiltriethoxysilane, cyclooctyltrimethoxysilane, cyclooctyl Triethoxysilane, 4-methylcyclohexyltriethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltriethoxysilane, (bicyclo [2.2.1] hept-5-en-2-yl) trimethoxysilane , (Vicyclo [2.2.1] hept-5-en-2-ylethyl) trimethoxysilane, (bicyclo [2.2.1] hept-5-en-2-ylethyl) triethoxysilane, bicyclo [2] .2.1] Hepta-2,5-diene-7-triethoxysilane, 1-naphthylrimethoxysilane, 1-naphthylriethoxysilane, 2-naphthylrimethoxysilane, 2-naphthylriethoxysilane, 1-naphthyl Methyltrimethoxysilane, 2-naphthylmethyltrimethoxysilane, 4-biphenyltrimethoxysilane, 4-biphenyltriethoxysilane, 1-phenoxy-4-triethoxysilylbenzene, tricyclo [3.3.1.13,7] decane-triethoxy silane, tricyclo [3.3.1.13,7] decan-2-triethoxysilane, 5-triethoxysilyl-2-norbornene, 2-triethoxysilyl-norbornane, 3-methacryloyloxy propyl trimethoxy Methoxysilane, 3-acryloxypropyltrimethoxysilane, trifluoroethyltrimethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-fluorophenyl Examples thereof include rutrimethoxysilane, 4-fluorophenyltrimethoxysilane, 3-fluorophenyltriethoxysilane, 4-fluorophenyltriethoxysilane, and pentafluorophenyltrimethoxysilane.
Among them, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane in which _{R 9} of the formula (4) is methyl or phenyl in that the obtained resin composition exhibits excellent heat resistance. Is preferable.

Specific examples of the (meth) acrylate other than the compound (a) represented by the formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth). ) Acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol acrylate, polyalkylene glycol acrylate, 2-hydroxyethyl (meth) acrylate , 2-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (Meta) acrylate, tetrahydrofurfuryl alcohol acrylic acid multimeric ester, γ-butyrolactone (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-Methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3,5-dimethyl-7-hydroxyadamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate , Methacryloyloxynorbornane (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, (meth) acrylate having an imide ring, cyclic trimethylolpropaneformal (meth) acrylate, 1, 6-Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, tricyclodecanedimethanol diacrylate, trimethylpropantri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, glycerintri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylol propanetetra (meth) Meta) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol F ethylene oxide modification Di (meth) acrylate, bisphenol Fpropylene oxide modified di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide modified di (meth) acrylate, isocyanurate ethylene oxide modified di (meth) acrylate, Isocyanurate propylene oxide modified di (meth) acrylate, isocyanurate ethylene oxide modified tri (meth) acrylate, isocyanurate propylene oxide modified tri (meth) acrylate, hydrogenated bisphenol F ethylene oxide modified di (meth) acrylate, hydrogenated bisphenol F Examples thereof include propylene oxide-modified di (meth) acrylate, hydrogenated bisphenol A ethylene oxide-modified di (meth) acrylate, and hydrogenated bisphenol A propylene oxide-modified di (meth) acrylate.

<Evaluation of cured film>
<5% weight loss temperature>
Measurement was performed in the range of 40 ° C. to 550 ° C. using a differential thermogravimetric simultaneous measuring device (TG / DTA6200, manufactured by Hitachi High-Tech Science Corporation). In order to eliminate an error due to moisture absorption of the film, the weight at 100 ° C. was set to 100%, and the temperature at which the weight was reduced by 5% was set to the 5% weight loss temperature. The results are shown in Table 1.

<Evaluation of cured film>
<5 to 20% weight loss temperature>
Using the same differential thermogravimetric simultaneous measuring device as in Example 1, the measurement was performed in the range of 40 ° C. to 550 ° C. In order to eliminate an error due to moisture absorption of the film, the weight at 100 ° C. was set to 100%, and the temperatures at which the weight was reduced by 5 to 20% were set to 5%, 10%, and 20% weight loss temperatures, respectively. The results are shown in Table 9.

Claims (9)

A resin composition containing the compound (a) represented by the formula (1), the resin (b) having a hydrogen-bonding group, and the polymerization initiator (c).

(In the formula (1), A is a divalent organic group, Y is a linear alkylene having 1 to 18 carbon atoms or an alkylene having a branch, and any alkylene has 2 or more carbon atoms. An oxygen atom (-O-) may be inserted between the CC bonds, -CO- may be inserted between the terminal CN bonds, m is 0 or 1, and X is. It is a group represented by the following formula (2).)

(In formula (2), R ₁ and R ₂ are independently hydrogen or methyl, respectively.) The resin composition according to claim 1, wherein the hydrogen-bonding group in the resin (b) is a group having active hydrogen. The resin composition according to claim 1 or 2, wherein the resin (b) contains at least one of a siloxane compound having a three-dimensional crosslinked structure represented by the following formula (3) or the following formula (4) in the structure. ..

(In the formula (4), R ₉ is a group selected from a linear alkyl having 1 to 22 carbon atoms or an alkyl having a branch, an aryl having 1 to 9 carbon atoms, or an aryl alkyl having 7 to 21 carbon atoms. , These groups may have any hydrogen substituted with halogen,
When the alkyl has two or more carbon atoms, an oxygen atom (−O−), cycloalkylene, cycloalkenylene, phenylene, and naphthalene may be inserted between arbitrary CC bonds. However, the total number of carbon atoms in _{R 9 does not exceed 30.} ) The resin composition according to claim 3, wherein _{R 9} in the formula (4) is methyl or phenyl. The resin composition according to any one of claims 1 to 4, wherein A in the formula (1) has a structure represented by the formula (5).

(In formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms, and Z is 1 to 4 carbon atoms. It is an alkylene of, and n is an integer of 0 to 150.) The resin composition according to claim 5, wherein m in the formula (1) is 0. The resin composition according to claim 5 or ₆ , wherein in the formula (5), R ₃ , R ₄ , R ₅ , R 6, R ₇ and R _{8 are methyl and Z is trimethylene.} A cured film obtained from the resin composition according to any one of claims 1 to 7. The electronic component having the cured film according to claim 8.