TW202003449A - Resin composition - Google Patents

Abstract

Provided is a novel resin composition having excellent heat resistance, and which is suitable for use as a material for insulating films in electronic components and the like. The resin composition contains: a compound (a) represented by formula (1); a resin (b) having a hydrogen-bonding group; and a polymerization initiator (c). (In formula (1), A is a divalent organic group, Y is a C1-18 straight-chain alkylene or branched alkylene, if said alkylene has 2 or more carbon atoms an oxygen atom (-O-) may be inserted into an arbitrarily-defined C-C bond, -CO- may be inserted into a terminal C-N bond, m is 0 or 1, and X is a group represented by formula (2).) (In formula (2), R1 and R2 are independently hydrogen or methyl.).

Description

Resin composition

The present invention relates to a novel resin composition that can be used as a material for an insulating film in electronic components such as printed wiring boards or semiconductor package substrates.

In recent years, in order to respond to the demand for weight reduction of portable terminals provided with a display unit such as a liquid crystal, it is being studied to change the raw material of components of electronic components from glass to plastic. Compared with glass, plastic is less resistant to damage. Therefore, the method of preventing damage by surface treatment with a hard coating agent is widely used. As a compound for improving the damage resistance of the hard coating agent, a hardening organic polysiloxane having (meth)acryloyl groups at both ends of the molecule is proposed, which is an isocyanate-containing (meth)acrylic acid The ester is obtained by reacting an organic polysiloxane having alcohols at both ends of the molecule (Patent Document 1, Patent Document 2). In addition, a radiation-curable organic polysiloxane composition excellent in adhesiveness with a plastic base material and excellent in-depth curability has also been proposed (Patent Document 3). However, the problem of Patent Document 1 and Patent Document 2 is that the damage resistance of the cured film formed of the compound or the composition is improved, and heat resistance is not described. In addition, the problem of Patent Document 3 is the adhesion of the composition, and heat resistance is not described.

A curable composition containing a multifunctional acrylate compound has been proposed, and its purpose is to improve curing and storage stability at high sensitivity (Patent Document 4). In addition, a reactive monomer having a urea bond has been proposed, and its purpose is to obtain a hardened product having high adhesion, high heat resistance temperature, and good chemical resistance (Patent Document 5). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-196748 [Patent Literature 2] International Patent Application Publication WO2015/152288 [Patent Document 3] Japanese Patent Laid-Open No. 6-184256 [Patent Document 4] Japanese Patent Laid-Open No. 2008-88251 [Patent Document 5] Japanese Patent Laid-Open No. 2007-55993

[Problems to be solved by the invention] The curable composition described in Patent Document 4 is used in a color filter, and is not good as a material for an insulating film in electronic parts and the like. In addition, Patent Document 5 discloses a general hardening composition that can be used for various purposes such as resists, seals, paints, adhesives, printing plates, printing corrections, lenses, dental materials, surface treatments, battery materials, etc. There is no description about the reactivity when curing using a light source with low ultraviolet energy such as a light emitting diode (LED) light source, and it is not particularly specialized as an insulating film that requires heat resistance and electrical insulation s material. Therefore, an object of the present invention is to provide a novel resin composition excellent in heat resistance and reactivity as a material of an insulating film in an electronic component such as a printed wiring board or a semiconductor package substrate. [Means to solve the problem]

The present invention is based on the following new insights, and has the following structure, which is achieved by using a novel urea bond type tetrafunctional (meth)acrylate compound having a urea bond and a (meth)acryloyl group Light sources with low ultraviolet energy, such as LED light sources, can also be hardened with a high reaction rate, and a cured film excellent in heat resistance and electrical insulation, which is preferable as a material for an insulating film in electronic parts and the like, can be obtained.

（式（1）中，A為二價有機基，Y為碳數1～18的直鏈伸烷基或具有分支的伸烷基，於所述伸烷基的碳數為2以上的情況下，可於任意的C-C鍵間插入氧原子（-O-），亦可於末端的C-N鍵間插入-CO-，m為0或1，X為下述式（2）所表示的基） [化2]

（式（2）中，R₁ 及R₂ 分別獨立地為氫或甲基）。[1] A resin composition containing a compound (a) represented by formula (1), a resin (b) having a hydrogen bonding group, and a polymerization initiator (c);

(In formula (1), A is a divalent organic group, Y is a straight-chain alkylene group having 1 to 18 carbon atoms or a branched alkylene group, when the carbon number of the alkylene group is 2 or more , An oxygen atom (-O-) can be inserted between any CC bonds, and -CO- can also be inserted between the CN bonds at the end, m is 0 or 1, X is a group represented by the following formula (2)) [ Change 2]

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

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

（式（4）中，R₉ 為選自碳數1～22的直鏈烷基或具有分支的烷基、碳數1～9的芳基或碳數7～21的芳基烷基中的基，該些基中任意的氫可經鹵素取代，於烷基的碳數為2以上的情況下，可於任意的C-C鍵間插入氧原子（-O-）、伸環烷基、伸環烯基、伸苯基、萘；其中，R₉ 的總碳數不超過30）。 [4]如[3]所述的樹脂組成物，其中式（4）中的R₉ 為甲基或苯基。[3] The resin composition according to [1] or [2], wherein the resin (b) includes a three-dimensional cross-linked structure represented by the following formula (3) or the following formula (4) in the structure At least one of the siloxane compounds; [Chem 3]

(In formula (4), R ₉ is selected from linear alkyl having 1 to 22 carbons or branched alkyl, aryl having 1 to 9 carbons or aryl alkyl having 7 to 21 carbons. In these groups, any hydrogen in these groups may be substituted with halogen. When the carbon number of the alkyl group is 2 or more, an oxygen atom (-O-), a cycloalkyl group, or a ring extension may be inserted between any CC bonds. Alkenyl, phenylene, naphthalene; wherein, the total carbon number of R ₉ does not exceed 30). [4] The resin composition according to [3], wherein R ₉ in the formula (4) is a methyl group or a phenyl group.

（式（5）中，R₃ 、R₄ 、R₅ 、R₆ 、R₇ 及R₈ 分別獨立地為氫或碳數1～30的烷基，Z為碳數1～4的伸烷基，n為0～150的整數）。 [6]如[5]所述的樹脂組成物，其中式（1）中的m為0。 [7]如[5]或[6]所述的樹脂組成物，其中式（5）中，R₃ 、R₄ 、R₅ 、R₆ 、R₇ 及R₈ 為甲基，Z為伸丙基(trimethylene)。[5] The resin composition according to any one of [1] to [4], wherein A in formula (1) is a structure represented by formula (5);

(In formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or an alkyl group having 1 to 30 carbon atoms, and Z is an alkylene group having 1 to 4 carbon atoms. , N is an integer from 0 to 150). [6] The resin composition according to [5], wherein m in 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 groups, and Z is propylene Base (trimethylene).

[8] A hardened film obtained from the resin composition according to any one of [1] to [7]. [9] An electronic component having the hardened film as described in [8]. [Effect of invention]

By using a urea bond type tetrafunctional (meth)acrylate compound having a urea bond and a (meth)acryloyl group, it is possible to use an LED light source with low energy and the like and harden it at a high reaction rate. By using the resin composition containing the urea bond-type tetrafunctional (meth)acrylate compound, it is possible to obtain a material that is preferable as an insulating film for electronic parts such as printed wiring boards or semiconductor package substrates, and is heat-resistant And a hardened film with good electrical insulation. In addition, by optimizing the structure of the urea-bonded tetrafunctional (meth)acrylate compound, the compatibility of the resin composition or the flexibility of the cured film can be adjusted.

（式（1）中，A為二價有機基，Y為碳數1～18的直鏈伸烷基或具有分支的伸烷基，於所述伸烷基的碳數為2以上的情況下，可於任意的C-C鍵間插入氧原子（-O-），亦可於末端的C-N鍵間插入-CO-，m為0或1，X為下述式（2）所表示的基。此處，所謂於Y的C-C鍵間插入氧原子（-O-）的伸烷基，例如是指具有乙烯氧基結構、丙烯氧基結構等伸烷氧基結構者） [化6]

（式（2）中，R₁ 及R₂ 分別獨立地為氫或甲基）Regarding the embodiments of the present invention, each component contained in the resin composition will be specifically described below. <Compound (a)> The compound (a) is a urea bond type tetrafunctional (meth)acrylate compound represented by the following formula (1). [Chem 5]

(In formula (1), A is a divalent organic group, Y is a straight-chain alkylene group having 1 to 18 carbon atoms or a branched alkylene group, when the carbon number of the alkylene group is 2 or more , An oxygen atom (-O-) can be inserted between any CC bonds, and -CO- can be inserted between the CN bonds at the end, m is 0 or 1, and X is a group represented by the following formula (2). Where, the so-called alkylene group in which an oxygen atom (-O-) is inserted between the CC bonds of Y means, for example, those having an alkoxy structure such as an ethyleneoxy structure, a propyleneoxy structure, etc.)

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

In this specification, "(meth)acrylate" is used to mean both or one of acrylate and methacrylate. In the reaction of (meth)acrylate, the double bond of (meth)acryloyl group undergoes radical polymerization, so the "functional" part is (meth)acryloyl group. The urea bond type tetrafunctional (meth) acrylate refers to the following (meth) acrylate: each side of the divalent organic group A is interposed with a urea bond or a linking group containing a urea bond and each has two of the above formulas ( 2) The structure represented has a total of four (meth)acryloyl groups.

The urea bond type tetrafunctional (meth)acrylate can hydrogen bond with a resin having a hydrogen bond group through a urea bond. Therefore, the resin having no photocurable substituents can be fixed by hydrogen bonding, and thus a cured film can be formed by irradiating light such as ultraviolet rays or visible rays. Therefore, by using resins having various properties as the resins having hydrogen bonding groups, a photocurable resin composition having desired properties can be prepared.

By using a urea-bonded tetrafunctional (meth)acrylate, when using a UV-LED irradiation conveying device whose ultraviolet energy is lower than that of a high-pressure mercury irradiation device, a cured film (cured material) can also be produced with a high reaction rate. Therefore, the energy efficiency at the time of manufacturing the hardened film is improved.

（式（5）中，R₃ 、R₄ 、R₅ 、R₆ 、R₇ 及R₈ 分別獨立地為氫或碳數1～30的烷基，Z為碳數1～4的伸烷基，n為0～150的整數）From the viewpoint of obtaining a cured product having good heat resistance, the divalent organic group A included as part of the urea-bonded tetrafunctional (meth)acrylate compound is preferably a divalent organic group having three or more aromatic rings Or a divalent organic group of the structure represented by formula (5). Here, regarding the number of aromatic rings, when one benzene ring is used, the naphthalene ring count is two, the fluorene ring count is two, and the anthracene ring count is three. [化7]

(In formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or an alkyl group having 1 to 30 carbon atoms, and Z is an alkylene group having 1 to 4 carbon atoms. , N is an integer from 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 described below. In addition, as an example of the divalent organic group represented by the formula (5), a divalent organic group in which R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are methyl groups, and Z is a propyl group can be given. .

<synthesis method> The urea bond type tetrafunctional (meth)acrylate contained in the resin composition of the present invention can be synthesized by, for example, Synthesis Method 1 to Synthesis Method 3 described below. <Synthesis Method 1> The urea bond type tetrafunctional (meth)acrylate can be obtained by using a diamine compound having amine groups at both ends represented by the following formula (6) and having two (meth) groups represented by the following formula (7) ) Acryloyl monoisocyanate compound obtained by reaction.

（式（6）中，A與式（1）為相同的基） [化9]

（式（7）中，R₁ 及R₂ 為與式（2）相同的基）[Chem 8]

(In formula (6), A and formula (1) are the same group)

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

（式（8）中，R₃ 、R₄ 、R₅ 、R₆ 、R₇ 及R₈ 分別獨立地為氫或碳數1～30的烷基，Z為碳數1～4的伸烷基，n為0～150的整數）From the viewpoint of improving the heat resistance of the cured film obtained by using a resin composition containing a urea bond-type tetrafunctional (meth)acrylate, the diamine compound represented by formula (6) preferably has three or more aromatic compounds A cyclic aromatic diamine compound or a siloxane diamine compound having a structure represented by the following formula (8). [化10]

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

Furthermore, in the case of using the urea bond type tetrafunctional (meth)acrylate as the resin composition, by setting n of the silicone chain of the siloxane diamine compound represented by formula (8) to 0 to 20 is preferable because it can improve the compatibility with other components in the resin composition.

Hereinafter, specific examples of the diamine compound represented by the formula (6) used as the raw material of the urea bond type tetrafunctional (meth)acrylate are shown. 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-tert-butylbenzene, 1,4-bis(4-aminophenoxy)-2,3,5-trimethylbenzene , N,N-bis(4-aminophenyl)p-xylylenediamine, 1,3-bis(3-aminophenoxy)benzene, α,α'-bis(4-aminophenyl) )-1,4-diisopropylbenzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene.

Examples of the aromatic diamine compound having four aromatic rings include 2,2-bis(4-(4-aminophenoxy)phenyl)propane and bis(4-(4-aminophenoxy )Phenyl) satin, bis(4-(3-aminophenoxy)phenyl) satin, 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis(4 -Aminophenyl)fluorene, 4,4'-(biphenyl-2,5-diylbisoxy)bisaniline, 4,4'-bis(4-aminobenzylamide)-3, 3'-dihydroxybiphenyl, 4,4'-bis(4-aminophenoxy)benzophenone.

Examples of the siloxane diamine compound represented by formula (8) include 1,3-bis(aminomethyl)tetramethyldisilaxane and 1,3-bis(2-aminoethyl) Tetramethyldisilaxane, 1,3-bis(3-aminopropyl)tetramethyldisilaxane, 1,3-bis(4-aminobutyl)tetramethyldisilaxane, 1,5-bis(3-aminopropyl)hexamethyltrisiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane. As these siloxane diamine compounds, commercially available products or compounds obtained by synthesis can be used. As a commercially available product of the siloxane diamine compound, for example, Silaplane (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 (share)), etc. As a method of synthesizing the siloxane diamine compound, for example, dimethylsilyl polydimethylsiloxane at both ends (for example, trade name: Silaplane FM11 series, manufactured by JNC Corporation) can be cited. ) Synthesis method by reaction with allylamine etc. in the presence of platinum catalyst.

In terms of ease of acquisition, in formula (8), it is preferred that R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 are} all methyl groups, and Z is a propyl group. Diamine compounds. By this synthesis method, a urea bond type tetrafunctional (meth)acrylate in which m in formula (1) is 0 can be synthesized.

As the monoisocyanate compound having two (meth)acryloyl groups represented by formula (7), commercially available products or compounds obtained by synthesis can be used. For example, Japanese Patent Laid-Open No. 2007-55993 (Patent Document 5) discloses a method for obtaining the compound. In addition, as a commercially available product, for example, Karenz (Karenz) BEI (trade name, manufactured by Showa Denko Co., Ltd.) can be cited.

In order to improve the reactivity of the diamine compound represented by Formula (6) and the monoisocyanate having (meth)acryloyl group represented by Formula (7), a catalyst may also be used. As the catalyst, tin catalyst (for example, dibutyltin dilaurate), amine catalyst (for example, triethylenediamine), carboxylate catalyst (for example, lead naphthenate, potassium acetate), trialkylphosphine Catalysts (such as triethylphosphine), titanium catalysts (such as trade name: ORGATIX TA-21, ORGATIX TA-30, ORGATIX TC-750, etc., Matsumoto Fine Chemical (manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium-based catalysts (for example, trade name: ORGATIX ZC-150, Matsumoto Fine Chemical (manufactured by Matsumoto Fine Chemical)), etc.

（式（6）中，A為與式（1）相同的基） [化12]

（式（9）中，R₁ 及R₂ 表示與式（2）相同的基，Y₁ 為碳數1～18的直鏈伸烷基或具有分支的伸烷基，於所述伸烷基的碳數為2以上的情況下，亦可於任意的C-C鍵間插入氧原子（-O-））<Synthesis Method 2> The urea bond type tetrafunctional (meth)acrylate contained in the resin composition of the present invention can be obtained by using a diamine compound having amine groups at both ends represented by formula (6) and the following formula (9) The obtained monocarboxylic acid compound having two (meth)acryloyl groups reacted. [Chem 11]

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

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

The monocarboxylic acid compound having two (meth)acryloyl groups represented by the formula (9) can be represented by the following formula (1), a monocarboxylic acid compound having one amine group in the molecule, and the following It is synthesized by the reaction of a monoisocyanate compound having two (meth)acryloyl groups represented by formula (7).

（式（10）中的Y₁ 為與式（9）相同的基） [化14]

（式（7）中，R₁ 及R₂ 為與式（2）相同的基）[Chem 13]

(Y ₁ in formula (10) is the same group as formula (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 amine group in the molecule represented by formula (10) include the following compounds.

[化15]

[Chem 16]

[化17]

[Chemical 18]

[Chem 19]

[化20]

[化21]

[化22]

[化23]

In order to improve the reactivity of the monocarboxylic acid compound represented by formula (10) having one amine group in the molecule and the monoisocyanate compound represented by formula (7) having two (meth)acryloyl groups, it can also be used Condensation agent or catalyst. Examples of the condensing agent include N,N′-dicyclohexylcarbodiimide or 1-hydroxybenzotriazole, and examples of the catalyst include N,N-dimethyl-4-aminopyridine.

By this synthesis method, a urea-bonded tetrafunctional (meth)acrylate having m of 1 in formula (1) can be synthesized. By setting m of formula (1) to 1, flexibility can be provided to the urea bond type tetrafunctional (meth)acrylate, and the reactivity of the (meth)acryloyl group can be adjusted. That is, the urea-bonded tetrafunctional (meth)acrylate having m of 1 in formula (1) has a smaller ratio of (meth)acrylate per molecule as compared to the one having m of 0, so the flexibility increases , The flexibility of the hardened material is improved. In addition, the urea-bonded tetrafunctional (meth)acrylate of m (1) in formula (1) has a longer molecular chain than the m (zero) constituting the backbone of the polymer (polymer), so the degree of freedom of the molecule Get bigger. Furthermore, as the hydrogen-bonding functional group (NH group) in the compound increases, the interaction between the molecules becomes larger, so it is expected to exert an aggregation effect. As a result of these results, the reactivity of photopolymerization of the urea bond type tetrafunctional (meth)acrylate having m of 1 in formula (1) is high.

（式（6）中，A為與式（1）相同的基） [化25]

（式（11）中，R₁ 及R₂ 表示與式（2）相同的基，W表示鹵素，Y₂ 為碳數1～18的直鏈伸烷基或具有分支的伸烷基，於所述伸烷基的碳數為2以上的情況下，亦可於任意的C-C鍵間插入氧原子（-O-））<Synthesis Method 3> The urea bond type tetrafunctional (meth)acrylate of the present invention can be represented by the following formula (11) by using a diamine compound represented by formula (6) having amine groups at both ends It is obtained by reacting a monohalogen compound having two (meth)acryloyl groups. [化24]

(In formula (6), A is the same group as formula (1)) [Chem. 25]

(In formula (11), R ₁ and R ₂ represent the same group as formula (2), W represents halogen, and Y ₂ is a straight-chain alkylene group having 1 to 18 carbon atoms or a branched alkylene group. When the carbon number of the alkylene group is 2 or more, an oxygen atom (-O-) may be inserted between arbitrary CC bonds)

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

（式（12）中，Y₂ 為與式（11）相同的基，W為鹵素） [化27]

（式（7）中，R₁ 及R₂ 為與式（2）相同的基）[化26]

(In formula (12), Y ₂ is the same group as formula (11), and W is halogen) [Chem 27]

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

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

[Chem 28]

[Chem 29]

[化30]

[化31]

[化32]

[化33]

[化34]

In order to improve the reactivity of the monoisocyanate compound having two (meth)acryloyl groups and the monohalogen compound having one amine group in the molecule, an inorganic base may be used in combination. Examples of inorganic bases include calcium carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride. By this synthesis method, a urea-bonded tetrafunctional (meth)acrylate having m of 1 in formula (1) can be synthesized.

<Resin with hydrogen bonding group (b)> In this specification, the resin (b) having a hydrogen-bonding group refers to a resin other than the compound (a) and has a substituent capable of hydrogen bonding with the compound (a). The substituent capable of hydrogen bonding to the compound (a) refers to a group that hydrogen bonds to the urea bond contained in the compound (a), and examples include atoms having a large electronegativity with nitrogen, oxygen, sulfur, etc. A group of covalently bonded hydrogen atoms (active hydrogen) and a group that is hydrogen bonded to active hydrogen.

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

Examples of the resin having a hydroxyl group include polyether polyol, polyester polyol, polycarbonate polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, and phenol resin.

Examples of polyether polyols include glycerin-ethylene oxide adducts, glycerin-propylene oxide adducts, glycerin-tetrahydrofuran adducts, glycerin-ethylene oxide propylene oxide adducts, and trihydroxy Methylpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide propylene oxide adduct Products, dipentaerythritol-ethylene oxide adducts, dipentaerythritol-propylene oxide adducts, dipentaerythritol-tetrahydrofuran adducts, dipentaerythritol-ethylene oxide propylene oxide adducts, etc.

Examples of the polyester polyol include polycondensates obtained by reacting a polyfunctional alcohol and 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, and 1,6. -Hexanediol, 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-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedione Ethylene oxide adducts of alcohol, p-xylene glycol, dicyclohexyl-4,4-diol, 2,6-decalindiol, 2,7-decalindiol, bisphenol A, Propylene oxide adduct of bisphenol A, etc.

Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3 -Methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, other saturated aliphatic dicarboxylic acids (carbon number 11 to 13), such as maleic acid, fumaric acid, itaconic acid, other Saturated aliphatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalene dicarboxylic acid, other aromatic dicarboxylic acids, such as hexahydrophthalic acid, other fatty acids Cyclic dicarboxylic acids, such as dimer acids, hydrogenated dimer acids, HET acids, and other carboxylic acids, as well as anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, equine Phthalic anhydride, phthalic anhydride, 2-alkyl (C12 to 18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, etc. For example, oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride, etc.

Examples of the polycarbonate polyol include one or two or more ring-opening polymers such as ε-caprolactone, γ-butyrolactone, and γ-valerolactone, 1,4-butanediol, and 1,5 -Copolymers of diols such as pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and ring-opening polymers.

Examples of epoxy polyols include epoxy polyols obtained by reacting the polyfunctional alcohol with polyfunctional halohydrin such as epichlorohydrin and β-methylepichlorohydrin. Examples of vegetable oil polyols include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. For example, castor oil polyol, or ester-modified castor oil polyol obtained by the reaction of castor oil fatty acid and polyoxypropylene polyol, etc. are mentioned.

Examples of polyolefin polyols include polybutadiene polyols, partially saponified ethylene-vinyl acetate copolymers, and the like. Examples of the acrylic polyol include copolymers obtained by copolymerizing a hydroxyl-containing (meth)acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl-containing (meth)acrylate.

Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (meth)acrylic acid 2, 2-Dihydroxymethylbutyl ester, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc.

Examples of the copolymerizable vinyl monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, ( Alkyl (meth)acrylate (carbon number 1-12) such as hexyl meth), isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, for example Aromatic vinyl such as styrene, vinyl toluene, α-methylstyrene, cyanide vinyl such as (meth)acrylonitrile, such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid Carboxyl group-containing vinyl monomers, or alkyl esters thereof, such as ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, oligomer Alkyl polyol poly(meth)acrylates such as polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, for example 3-(2-isocyanate-2-propyl)-α-methylstyrene and other isocyanate-containing vinyl monomers, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propylpropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-propenyloxy 3-propyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, Silaplane (Silaplane) FM0711 (trade name, manufactured by JNC), Silaplane (Silaplane) FM0721 ( Silicone compounds with ethylenically unsaturated groups, vinylidene fluoride (VdF), such as trade names, JNC (product), Silaplane FM0725 (trade name, JNC) , Tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), vinylfluoride (VF), perfluoro (alkyl vinyl ether), etc.

The phenol resin is a resin having a phenolic hydroxyl 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 a carboxyl group 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 each polymer using ethylene rubber Acid-modified ethylene rubber modified with an acid having an unsaturated bond, and acid-modified styrene elastomer modified with an acid having an unsaturated bond for each polymer of a styrene elastomer. The acid used for acid modification is not particularly limited as long as the effect of the present invention is not impaired. For example, an unsaturated carboxylic acid or its derivative can be used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, rosin acid, neo-rosin acid and palustric acid, etc., as unsaturated carboxylic acids Examples of derivatives include: maleic acid monoester, maleic anhydride, itaconic acid monoester, itaconic anhydride, fumaric acid monoester, fumaric anhydride, pimaric acid, isopimaric acid, dehydroabietic acid and the like.

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

Examples of the polyfunctional amine having a primary amine group include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1 , 7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine and other straight-chain aliphatic alkylene diamines, 1-butyl-1,2 -Ethylenediamine, 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-butanediamine, 2,3-dimethyl-1,4-butanediamine, etc. Aliphatic alkylene diamine, cyclohexane diamine, methyl cyclohexane diamine, isophorone diamine, norbornane dimethylamine, tricyclodecane dimethylamine, menthenediamine (menthenediamine ) Aromatic diamines such as alicyclic diamine, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, benzene tris Triamines such as amine, melamine, 2,4,6-triaminopyrimidine, and tetraamines such as 2,4,5,6-tetraaminopyrimidine, etc.

Examples of polyfunctional isocyanates include 2,4-toluene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. , Xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Banok D-750, Crisvon NK (trade name, Dainippon Ink Chemical Industry Co., Ltd.), Desmodur L (trade name, Sumitomo Bayer Carbamate Co., Ltd.), CORONATE L (trade name, Japanese polyamine) Formate Industry Co., Ltd.), Takenate D102 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name, manufactured by Mitsubishi Chemical Co., Ltd.), etc. .

Examples of the unsaturated double bond compound having an amide group include (meth)acrylamide, N-methyl(meth)acrylamide, N,N-diethyl(meth)acrylamide , N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl Polymerization of (meth)acrylamide, N,N-methylenebis(meth)acrylamide, N-isopropylacrylamide, N,N-dimethylaminopropylacrylamide And copolymers of compounds copolymerizable with unsaturated double bond compounds having these amide groups.

As the resin having an amide bond containing active hydrogen, commercially available products 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 (all are trade names, manufactured by DuPont).

Examples of the resin having a urea bond include polyurea which reacts the polyfunctional isocyanate with the polyfunctional primary amine or reacts the polyfunctional isocyanate with water to cause the amine group generated by the hydrolysis of the isocyanate and The residual isocyanate is obtained by reaction.

Examples of the resin having a urethane bond include polyurethane obtained by reacting the polyfunctional isocyanate with the resin having a hydroxyl group. In order to promote the hardening reaction of forming a resin having a urethane bond, a urethane catalyst can be used as a hardening reaction initiator. Examples of the urethane catalyst include organometallic urethane catalysts and tertiary amine urethane catalysts.

Examples of organometallic urethane catalysts include tin acetate, tin octoate, tin oleate, tin laurate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dichloride, lead octoate, Lead metal naphthenate, nickel naphthenate, cobalt naphthenate and other organometallic carbamate catalysts.

Examples of tertiary amine-based carbamate catalysts include triethylenediamine, N,N,N',N',N'-pentamethyldipropylenetriamine, N,N,N', N',N'-pentamethyldiethylenetriamine, 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 , Methylene bis(dimethylcyclohexyl)amine, triethylamine, N,N-dimethylacetamide, N,N-dimethyldodecylamine, N,N-dimethyldecyl Hexaalkylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethyl Morpholine, N-(2-dimethylaminoethyl)morpholine, 4,4'-oxydivinyl dimorpholine, N,N'-dimethylpiperazine, N,N'-di Ethylpiperazine, N,-methyl-N'-dimethylaminoethylpiperazine, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, 3-di Methylamino-N,N-dimethylpropylamide, N,N,N',N'-tetra(3-dimethylaminopropyl)methandiamine, N,N-dimethylamine Ethanol, 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-diaza Bicyclic (5,4,0)-undecene-7, N-methyl-N-hydroxyethylpiperazine, etc. 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 hydrolyzing a resin having a hydrolyzable silane group such as an alkoxy group at the terminal or side chain.

Examples of the silicone resin include thermosetting silicone resins such as addition-curing silicones containing silanol, condensation-curing silicones containing silanol, and modified silicones modified with organic functional groups having silanol. Ketone resin or silanol-containing silicone compound having a three-dimensional cross-linked structure.

The addition-hardening silicone resin with silanol can be made of silicone with silanol and hydrogenated silane and silicone with alkenyl group, or silicone with hydrogenated silane and silicone with silanol and alkenyl group Obtained by hydrogenation. The catalyst used in the hydrosilation reaction may include a transition metal catalyst. Examples of the transition metal catalyst used are platinum, rhodium, iridium, ruthenium, palladium, molybdenum, iron, cobalt, nickel, and manganese. Among these, platinum catalyst is more preferable. These catalysts can be used as homogeneous catalysts dissolved in solvents, solid catalysts carried on carbon or silicon dioxide, etc. It can be used in a form in which phosphine, amine, potassium acetate, etc. coexist. The preferred usage amount of the transition metal catalyst is 1×10 ⁻⁶ mol to 1×10 ⁻² mol in terms of transition metal catalyst atoms relative to 1 mole of hydrogenated silane in the silicone resin.

The condensation-hardening type silicone resin having silanol can be obtained by partially remaining silanol during the dealcoholization and dehydration reaction of the silicone having alkoxysilyl group and silanol. In the condensation reaction, in order to accelerate the reaction, a condensation catalyst can be used. 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 name: ORGATIX TA-21, ORGATIX TA-30, and OGA ORGATIX TC-750, etc., Matsumoto Fine Chemical (Matsumoto Fine Chemical Co., Ltd.) or tin complexes and other metal complexes or metal alkoxides. The amount of the silanol condensation catalyst in 100% by weight of the raw materials 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 0.001% by weight.

The modified silicone resin modified with an organic functional group having a silanol is a silicone in which a part of the organic group of the silicone resin having a silanol is substituted with an organic functional group. Examples of the organic functional group include: amine groups , Hydroxyl, epoxy, mercapto, carboxyl, vinyl, allyl, styryl, (meth)acryloyl. The substitution position of the organic functional group can be any position of the end of the silicone and the side chain.

In order to increase the surface hardness or glass transition temperature of the hardened film, the resin (b) having a hydrogen bonding group contained in the resin composition of the present invention is particularly preferably a silicon having a three-dimensional cross-linked structure containing silanol in the silicone resin Oxane compounds. Examples of the siloxane compound having a three-dimensional cross-linked structure include a siloxane compound having a Q unit structure or a T unit structure, and the Q unit structure includes a structural unit "SiO ₂ "having no organic substituent R on silicon The T unit structure includes a structural unit "RSiO _3/2 " with an organic substituent R on silicon. The Q unit structure is represented by the following formula (3), and the T unit structure is represented by the following formula (4), for example.

（式（4）中，R₉ 為選自碳數1～22的直鏈烷基或具有分支的烷基、碳數1～9的芳基或碳數7～21的芳基烷基中的基，該些基中任意的氫可經鹵素取代，於烷基的碳數為2以上的情況下，可於任意的C-C鍵間插入氧原子（-O-）、伸環烷基、伸環烯基、伸苯基、萘。其中，R₉ 的總碳數不超過30）[化35]

(In formula (4), R ₉ is selected from linear alkyl having 1 to 22 carbons or branched alkyl, aryl having 1 to 9 carbons or aryl alkyl having 7 to 21 carbons. In these groups, any hydrogen in these groups may be substituted with halogen. When the carbon number of the alkyl group is 2 or more, an oxygen atom (-O-), a cycloalkyl group, or a ring extension may be inserted between any CC bonds. Alkenyl, phenylene, naphthalene. Among them, the total carbon number of R ₉ does not exceed 30)

The siloxane compound having a three-dimensional cross-linked structure can be obtained by hydrolyzing and condensing a silane compound having a hydrolyzable group and partially remaining silanol. Furthermore, the silicone compound having a three-dimensional cross-linked structure is mainly a silicone compound containing a three-dimensional cross-linked structure, and is called a silicone resin or a silicone alkoxy oligomer.

Specific examples of silane compounds having hydrolyzable groups are shown below. Examples of the silane compound having a Q unit structure having a hydrolyzable group that can obtain the structure represented by formula (3) include tetramethoxysilane and a partially hydrolyzed condensate of tetramethoxysilane (methyl silicate), Tetraethoxysilane, partially hydrolyzed condensate of tetraethoxysilane (ethyl silicate), for example, ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, methyl silicate 51, Commercial products such as methyl silicate 53A (all are trade names, manufactured by COLCOAT (share)). Examples of the silane compound having a T unit structure having a hydrolyzable group that can obtain the structure represented by formula (4) include methyltrimethoxysilane, methyltriethoxysilane, and methyltripropoxysilane , Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, propylene Trimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, propyltripropoxysilane, isopropyltrimethoxysilane, isopropyl Triethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, 1,1-dimethylethyltrimethoxysilane, 1,1-dimethyl Ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane Silane, heptyl trimethoxy silane, heptyl triethoxy silane, octyl trimethoxy silane, nonyl trimethoxy silane, decyl trimethoxy silane, dodecyl trimethoxy silane, fourteen Alkyl trimethoxy silane, pentadecyl trimethoxy silane, hexadecyl trimethoxy silane, heptadecyl trimethoxy silane, octadecyl trimethoxy silane, behenyl triethyl Oxysilane, methoxymethyltrimethoxysilane, methoxymethyltriethoxysilane, methoxypropyltrimethoxysilane, ethoxymethyltriethoxysilane, ethoxyethane Triethoxysilane, butoxyethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenyltriisopropoxysilane, Phenylmethyltrimethoxysilane, phenylmethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxy Silane, 3-phenylpropyltriethoxysilane, 4-phenylbutyltrimethoxysilane, 2-methylphenyltrimethoxysilane, 2-methylphenyltriethoxysilane, 3 -Methylphenyltrimethoxysilane, 3-methylphenyltriethoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 3,5-di Methylphenyltrimethoxysilane, 1-cyclohexyl-4-trimethoxysilylbenzene, 3-(4-methylphenyl)propyltrimethoxysilane, 3-methoxyphenyltrimethoxy Silane, 3-methoxyphenyltrimethoxysilane, 3-methoxyphenyltriethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-methoxyphenyltriethoxy Silane, phenoxymethyltrimethoxysilane, phenoxymethyltriethoxysilane, 3-phenoxypropyltrimethoxysilane, cyclobutyltriethoxysilane, cyclopentyltrimethoxy Silane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cycloheptyltrimethoxysilane, cycloheptyltriethoxysilane, cyclooctyltrimethoxysilane , Cyclooctyltriethoxysilane, 4-methylcyclohexyltriethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltriethoxysilane, (bicyclo[2.2 . 1]hept-5-en-2-yl)trimethoxysilane, (bicyclo[2.2.1]hept-5-en-2-ylethyl)trimethoxysilane, (bicyclo[2.2.1]heptan 5-en-2-ylethyl) triethoxysilane, bicyclo[2.2.1]hepta-2,5-diene-7-triethoxysilane, 1-naphthyltrimethoxysilane, 1- Naphthyltriethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltriethoxysilane, 1-naphthylmethyltrimethoxysilane, 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-triethoxysilyl Norbornane, 3-methacryloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, trifluoroethyltrimethoxysilane, trifluoropropyltrimethoxysilane, Trifluoropropyltriethoxysilane, 3-fluorophenyltrimethoxysilane, 4-fluorophenyltrimethoxysilane, 3-fluorophenyltriethoxysilane, 4-fluorophenyltriethoxy Silane, pentafluorophenyl trimethoxysilane. Among them, from the viewpoint that the obtained resin composition exhibits excellent heat resistance, methyl trimethoxysilane and methyltriethoxysilane in which R ₉ of the formula (4) is methyl or phenyl are preferred , Phenyltrimethoxysilane, Phenyltriethoxysilane.

The siloxane compound may further include at least one unit structure selected from an M unit structure and a D unit structure in addition to at least one unit structure of a Q unit structure and a T unit structure, and the M unit structure is included on the silicon The structural unit "R ₃ SiO _1/2 "with three organic substituents R, and the D unit structure includes the structural unit "R ₂ SiO" with two organic substituents R on silicon. Specific examples of the silane compound having a hydrolyzable group that can obtain the above structure are shown below.

Examples of the silane compound having a M unit structure with a hydrolyzable group include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, and triethyl Methoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylpropane Oxysilane, triphenylbutoxysilane, dimethylphenylmethoxysilane, triisopropylmethoxysilane, tricyclohexylmethoxysilane, dimethylethylethoxysilane, dimethacrylate Methylbutylethoxysilane, dimethylphenylethoxysilane, diethylphenylethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, 3-methyl Acryloyl propyl propyl methyl dimethoxy silane.

Examples of the silane compound having a D unit structure having a hydrolyzable group include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxy Silane, dipropyldimethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane, methylethyldimethoxysilane, methylphenyldiethoxysilane, methyl Cyclocyclohexyldimethoxysilane, polysiloxane compound having silanol and/or alkoxysilane group (polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane Alkanes) etc. Examples of polysiloxane compounds having silanol and/or alkoxysilane groups include 1,3-diethoxy-1,1,3,3-tetramethyldisilaxane and cerapre (Silaplane) FM99 series (trade name, manufactured by JNC).

The silane compound having a hydrolyzable group may be mixed with other siloxane compounds having a three-dimensional cross-linked structure without being hydrolyzed and condensed, or may be used in advance by reacting with other siloxane compounds having a three-dimensional cross-linked structure. In the case of mixing or reacting with other siloxane compounds having a three-dimensional cross-linked structure, the reaction using the condensation catalyst proceeds quickly, which is preferable. When a transparent hardened film is to be formed, ORGATIX TA-21 and ORGATIX TA-309 (both trade names, Matsumoto Fine Chemical) (shares) with less coloration Manufacturing) suitable.

The siloxane compound having a three-dimensional cross-linked structure may also be a silsesquioxane containing silanol and containing only the T unit structure. The structure of sesquisiloxane is known as trapezoidal structure, fully condensed structure (cage structure), incompletely condensed structure (partial cage structure), amorphous structure (random structure), etc. Three hydrolyzable silane compounds are synthesized by hydrolysis and condensation.

Siloxane compounds with a three-dimensional cross-linked structure can also be purchased for use on the market. Examples of commercially available siloxane compounds having a three-dimensional cross-linked structure include: RSN-0217, RSN-0220, RSN-0223, RSN-0249, RSN-0255, RSN-6018 (all are trade names, Toray Dow Corning) (Made by Toray Dow Corning), 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 trade names, manufactured by Konishi Chemical Industry Co., Ltd.), SO-1400, SO-1430, SO-1444, SO-1450, SO-1455, SO-1458, SO-1460 (all (Trade name, made by Hybrid Plastics). Among them, from the viewpoint that the obtained resin composition shows excellent heat resistance, RSN-0217, SR-21, SR-23, and formula (4) in which R ₉ in the formula (4) is a phenyl group are preferred ) In which R ₉ is methyl KR-220L, KR-220LP, SR-13, R ₉ in formula (4) contains phenyl and methyl RSN-0220, RSN-0223, RSN-0249, RSN- 0255, RSN-6018, KR-480, SR-33, SO-1458, SO-1460.

In addition, since the compound (a) has active hydrogen, a resin having a substituent capable of hydrogen bonding with the active hydrogen is also included in the resin (b) having a hydrogen bonding group. Examples of the substituent include nitrogen-containing heterocyclic rings such as lactamyl ring, pyridyl group, imidazole, and triazine ring, carbonyl-containing groups such as amide, amide imine, lactone ring, and carboxyl group. Even if these substituents do not contain active hydrogen, they can form a hydrogen bond with the compound (a).

Examples of the resin having a nitrogen-containing heterocyclic ring include polyimide (trade name: Kapton, Toray Co., Ltd.), trade name: AURUM, Mitsui Chemical Co., Ltd. Etc.), polyamidimide, polyetherimide, polybenzimidazole, polybenzoxazole, methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified Melamine resins such as melamine resin and methylbutyl mixed etherified melamine resin. Examples of the carbonyl group-containing resin include polyvinyl acetate resin, urea resin, polycarbonate resin, and polyester resin (polyethylene terephthalate, polybutylene terephthalate, and polyethylene 2,6). -Naphthalene dicarboxylate, etc.), polyarylate (trade name: U polymer, manufactured by Unitika), alkyd resin, etc. A monomer that can constitute these resins or a polymer of the monomer can be added to the resin composition of the present invention. These monomers or their polymers may be used alone or in combination.

The use amount (content in the resin composition) of the resin (b) having a hydrogen bonding group is preferably 1 part by weight to 20 parts by weight with respect to 1 part by weight of the compound (a) represented by the formula (1), More preferably, it is 2-10 weight part. If the amount used is 1 part by weight or more, a cured film having sufficient heat resistance or electrical insulation can be obtained. On the other hand, if 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 a hydrogen bonding group can hydrogen bond with the compound (a) represented by formula (1). Therefore, even a resin that does not have a photocurable substituent can be fixed in the resin composition by hydrogen bonding, and by irradiating light such as ultraviolet rays or visible rays or heating, it can be formed to contain hydrogen bonding. A hardened film of immobilized resin. In this manner, by using resins having various properties as the resin (b) having a hydrogen bonding group, a photo-curable or thermo-curable resin composition having desired properties can be prepared.

<polymerization initiator (c)> As the polymerization initiator (c) of the resin composition of the present invention, a photopolymerization initiator can be used. The photopolymerization initiator is a compound that causes the polymerization reaction of the reactive monomer by irradiating active energy rays such as ultraviolet rays or visible rays. Specific examples of the photopolymerization initiator include benzophenone and rice. Ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethyl Anthraquinone, acetophenone, 2-hydroxy-2-methyl acetone, 2-hydroxy-2-methyl-4'-isopropyl benzene acetone, 2-hydroxy-1-{4-[4-( 2-hydroxy-2-methyl-propionyl)-benzyl]phenyl)-2-methyl-propane-1-one, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl Benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 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-dimethyl Ethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-di (third butyl carbonyl peroxide) benzophenone, 3,4,4'-tri( Third butyl carbonyl peroxide) benzophenone, 3,3',4,4'-tetra (third butyl carbonyl peroxide) benzophenone, 3,3',4,4'-tetra ( Third hexyl carbonyl peroxide) benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-di(third butyl carbonyl peroxide) benzophenone, 3,4'- Bis(methoxycarbonyl)-4,3'-bis(third butyl carbonyl peroxide) benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-di(third Butyl peroxycarbonyl) 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(tris Chloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyrene Group)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-all Triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxy Phenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole , 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxy Carbonylcarbonylphenyl)-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'-biimidazole, 3-(2-methyl-2-dimethylaminopropyl amide) Group) carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(η5-2 ,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium, bis(2,4,6-trimethyl (Benzyl) phenylphosphine oxide and 2,4,6-trimethylbenzyl diphenylphosphine oxide, etc. Among these, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1- is preferred Ketone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. One type of the photopolymerization initiator may be used alone, or two or more types may be used in combination.

In addition, as the polymerization initiator (c) of the resin composition of the present invention, a thermal polymerization initiator can be used. When a thermal polymerization initiator is used, the polymerization reaction is caused by heat to obtain a cured film of the resin composition. That is, by adding a thermal polymerization initiator as a polymerization initiator (c), the resin composition of the present invention can be made into a thermosetting composition. Examples of the thermal polymerization initiator include diacyl peroxides, ketone peroxides, hydrogen peroxides, dialkyl peroxides, peroxyesters, azo compounds, and persulfuric acid. Salt etc. These may be used alone or in combination of two or more.

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

The resin composition of the present invention may contain the compound (a) represented by the formula (1), the resin (b) having a hydrogen bonding group, and the polymerization initiator (c) within a range that does not impair curability and heat resistance. Other ingredients. Examples of these components include compounds other than the compound (a) represented by the formula (1) having radically polymerizable double bonds, resins other than the resin (b) having hydrogen bonding groups, and solvents.

The compound having a radically polymerizable double bond other than the compound (a) represented by the formula (1) includes (meth)acrylate and (meth)acrylic acid other than the compound (a) represented by the formula (1) Low-molecular compounds with radical polymerizable double bonds other than esters, unsaturated polyester resins, polyester (meth)acrylate resins, (meth)acrylic epoxy ester resins, urethane (methyl) Resins having unsaturated bonds capable of radical polymerization, such as acrylate resins.

Specific examples of (meth)acrylates other than the compound (a) represented by formula (1) include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate , Butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-(2-ethoxy acrylate) Ethyl ethoxy) ethyl ester, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol acrylate, polyalkylene glycol acrylate, 2-hydroxyethyl (meth)acrylate, (meth) 2-Hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, benzyl (meth)acrylate, phenoxy (meth)acrylate Ethyl ethyl ester, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, 4-butyl (meth) acrylate Cyclohexyl, cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone modified tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl alcohol Polymer acrylate, γ-butyrolactone (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate Ethyl ester, (meth)acrylic acid 2-methyl-2-adamantyl ester, (meth)acrylic acid 2-ethyl-2-adamantyl ester, (meth)acrylic acid 3,5-dimethyl- 7-hydroxyadamantyl ester, 3-hydroxy-1-adamantyl (meth)acrylate, methacryloxynorbornene (meth)acrylate, tetramethylpiperidine (meth)acrylate Ester, pentamethyl piperidine (meth)acrylate, (meth)acrylate with an amide imide ring, cyclic trimethylolpropane formal (meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylenedioxide Alcohol di(meth)acrylate, butanediol di(meth)acrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, tri Hydroxymethylpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth) Base) acrylate, dipentaerythritol hexa(meth)acrylate, ε-caprolactone addition trimethylolpropane tri(meth)acrylate, ε-caprolactone addition di-trimethylolpropane tetra (Meth)acrylate, ε-caprolactone addition pentaerythritol tetra(meth)acrylate, ε-caprolactone addition dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylic acid Ester, polypropylene glycol di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acrylate, bisphenol F propylene oxide modified di(meth)acrylate, bisphenol A epoxy Ethane modification di(meth)acrylate, bisphenol A propylene oxide modification Quality di(meth)acrylate, isocyanurate ethylene oxide modified di(meth)acrylate, isocyanurate propylene oxide modified di(meth)acrylate, isocyanurate Acid ethylene oxide modified tri(meth)acrylate, isocyanuric acid propylene oxide modified tri(meth)acrylate, hydrogenated bisphenol F ethylene oxide modified di(meth)acrylate , Hydrogenated bisphenol F propylene oxide modified di (meth) acrylate, hydrogenated bisphenol A ethylene oxide modified di (meth) acrylate, hydrogenated bisphenol A propylene oxide modified di (meth) Acrylic esters, etc.

Specific examples of the low-molecular compound having a radically polymerizable double bond other than (meth)acrylate include crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, and N-vinyl group. Formamide, 2-allyloxymethyl methacrylate, polymethyl methacrylate 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.

Examples of unsaturated polyester resins include those in which a condensation product (unsaturated polyester) obtained by esterification reaction of a polyol with an unsaturated polybasic acid (and optionally a saturated polybasic acid) is dissolved in a polymerizable monomer substance.

The unsaturated polyester can be produced by polycondensation of unsaturated acids such as maleic anhydride and glycols such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, itaconic acid, or an anhydride thereof can be cited as the acid component, and it can be combined with 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- Polyols such as dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A react as alcohol components In addition, polyacids or anhydrides thereof that do not have a polymerizable unsaturated bond, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc., are added as necessary The manufacturer of the acid component.

Examples of the polyester (meth)acrylate resin include: (1) an epoxy compound containing α,β-unsaturated carboxylic acid ester and a terminal obtained from a saturated polybasic acid and/or unsaturated polybasic acid and a polyol The (meth)acrylate resin obtained by reacting a carboxyl group with a polyester, (2) obtained by reacting a hydroxyl-containing acrylate and a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and/or unsaturated polybasic acid with a polyol (Meth)acrylate resin, (3) (meth)acrylic acid ester obtained by reacting (meth)acrylic acid and polyester with hydroxyl end groups obtained from saturated polyacid and/or unsaturated polyacid and polyol Resin.

Examples of saturated polybasic acids used as raw materials for polyester (meth)acrylate resins include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and decane A polyacid or its anhydride having no polymerizable unsaturated bond such as a diacid, and a polymerizable unsaturated polybasic acid or its anhydride such as fumaric acid, maleic acid, itaconic acid and the like. Furthermore, the polyol which reacts as an alcohol component is the same as the unsaturated polyester.

The (meth)acrylic epoxy resin is produced by the ring-opening reaction of a compound having a glycidyl group (epoxy group) and a carboxyl compound having a polymerizable unsaturated bond such as (meth)acrylic acid. Unsaturated bond compound (vinyl ester). Generally, an epoxy (meth)acrylate resin dissolved in a polymerizable monomer can be used.

Examples of the compound having a glycidyl group (epoxy group) include bisphenol A diglycidyl ether and its high molecular weight homologues, novolac type glycidyl ethers, and the like. It may also contain bisphenol (such as type A), adipic acid, sebacic acid, and dimer acid (trade name: HARIDIMER) 270S, Harima in addition to (meth)acrylic acid Chemicals (manufactured by stocks) and other reactants of dibasic acids.

Examples of urethane (meth)acrylate resins include oligomers containing radical polymerizable unsaturated groups: after reacting a polyfunctional isocyanate with a resin having a hydroxyl group, the hydroxyl group-containing It is obtained by reacting (meth)acrylic acid compound and optionally hydroxyl-containing allyl ether compound. The resin having a polyfunctional isocyanate and a hydroxyl group is the same as the resin having a urethane bond.

The hydroxy-containing (meth)acrylic compound is not particularly limited, but is preferably a hydroxy-containing (meth)acrylate, specifically, for example, 2-hydroxyethyl (meth)acrylate, (meth ) 2-hydroxypropyl acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, tri(hydroxyethyl) heterotrimer Mono(meth)acrylate of cyanic acid, di(meth)acrylate of tri(hydroxyethyl)isocyanuric acid, pentaerythritol tri(meth)acrylate, etc.

Examples of the resin other than the resin (b) having a hydrogen bonding group include thermosetting resins and thermoplastic resins. Examples of the thermosetting resin include epoxy resins, and specific examples include bisphenol A epoxy resin, bisphenol F epoxy resin, multifunctional epoxy resin, flexible epoxy resin, and brominated Epoxy resins such as epoxy resins, glycidyl ester epoxy resins, polymer epoxy resins, and biphenyl epoxy resins. Epoxy resins are excellent in heat resistance, adhesion, and chemical resistance, and can be used as needed. Examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, and poly(methyl) Acrylic resin, ultra-high molecular weight polyethylene, poly-4-methylpentene, syndiotactic polystyrene, polyacetal, polyphenylene ether, fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polybenzene Thioether, poly lanthanum, polyether lanolin, etc.

The resin composition of the present invention may contain a solvent. Examples of solvents usable in the present invention include diethyl ether, tetrahydrofuran, diphenyl ether, dimethoxybenzene, acetone, methanol, ethanol, isopropanol, butanol, tertiary butanol, benzyl alcohol, and methyl Ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, ethyl carbonate, propyl carbonate, ethyl acetate, isobutyl acetate, butyl acetate, butyl propionate, ethyl lactate , Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Ester, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2 -Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2-methylpropionic acid Methyl ester, ethyl 2-oxy-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate, methyl pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, methyl 2-hydroxyisobutyrate , Dioxane, ethylene glycol, diethylene glycol, triethylene 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, ethyl acetate Glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether ether Ester, 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-pyrrolidine Ketones and dimethylimidazolidinone. Among these, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, butyl acetate, N,N-dimethylacetamide, N,N-dimethyl Carboxamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether. The solvent usable in the present invention may be one kind or a mixture of two or more kinds.

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

From the viewpoint of adjusting various physical properties and the subsequent curing at the time of film formation, the composition of the present invention may further contain other components within a range that does not impair heat resistance. Examples of the other ingredients include active energy ray sensitizer, polymerization inhibitor, polymerization initiation aid, leveling agent, surfactant, plasticizer, ultraviolet absorber, light stabilizer, antioxidant, antistatic agent , Silane coupling agent.

<hardened film> The hardened film of the present invention is obtained from a resin composition containing a urea bond type tetrafunctional (meth)acrylate compound. The cured film is formed, for example, by applying a resin composition containing a urea bond-type tetrafunctional (meth)acrylate compound to the surface of the substrate and then irradiating light such as ultraviolet rays or visible rays to harden the coating film. By blending a urea bond type tetrafunctional (meth)acrylate compound, it is possible to impart photocurability 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 excellent in balance such as adhesion of metal or resin to the substrate. Therefore, the application of the hardened film of the present invention is not particularly limited, and it can be preferably used as an insulating film or the like for protecting the surface of a metal wiring forming a predetermined circuit pattern or the like.

When the resin composition is irradiated with ultraviolet light, visible light, etc., the irradiation amount (exposure amount) may be appropriately selected according to the composition of the composition, preferably about 100 mJ/cm ² to 5,000 mJ/cm ² , and more preferably It is about 150 mJ/cm ² to 2,000 mJ/cm ² , and more preferably about 180 mJ/cm ² to 1,000 mJ/cm ² . In addition, the wavelength of ultraviolet rays or visible rays irradiated is preferably 200 nm to 500 nm, and more preferably 250 nm to 450 nm. In addition, in the present invention, the exposure amount is a value measured by a cumulative light meter UIT-201 (trade name) equipped with a light receiver UVD-365PD (trade name) manufactured by a oxtail (USHIO) motor (share).

Furthermore, as the exposure machine, it is preferable to mount 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., and irradiate ultraviolet rays in the range of 200 nm to 500 nm Or visible light, etc. Since the urea-bonded tetrafunctional (meth)acrylate compound has high reactivity, by using a low-energy UV-LED lamp or the like as a light source, it can be cured at the same high reaction rate as when using a high-pressure mercury lamp. Therefore, according to the resin composition containing a urea bond type tetrafunctional (meth)acrylate compound, a light source with low energy can be used to produce a cured film with good heat resistance.

In addition, if necessary, the cured film cured by the irradiation of light may be further heated and calcined. For example, by heating and calcining at 80° C. to 250° C. for about 10 minutes to 120 minutes, the hardened film can be hardened more firmly.

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

The substrate that can be used in the present invention is not particularly limited, and examples thereof include those containing polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Polyester resin substrate; Polyolefin resin substrate including polyethylene and polypropylene; Polyvinyl chloride, fluororesin, acrylic resin, styrene resin, polyamide, polycarbonate and polyimide etc. Organic polymer film; substrate containing cellophane; metal foil; laminate film of resin substrate containing polyimide and metal foil; laminate of glass epoxy resin and metal foil; cellophane, imitation with caulking effect Parchment paper, polyethylene, clay binder, polyvinyl alcohol, paper using starch or Carboxymethyl Cellulose (CMC) for caulking; silicon wafers, silicon nitride substrates, silicon oxide substrates and other silicon systems Substrate; glass substrates such as glass wafers and quartz substrates.

Furthermore, these substrates may further contain pigments, dyes, antioxidants, deterioration inhibitors, fillers, ultraviolet absorbers, antistatic agents, and/or anti-electromagnetic wave agents in a range that does not adversely affect the effects of the present invention. additive. In addition, at least a part of the surface of the substrate may be subjected to surface treatments such as waterproof treatment, corona treatment, plasma treatment, and/or sandblasting treatment as necessary, or an easy adhesion layer or a protective film for color filters or hard Coated film.

The thickness of the hardened film of the present invention can be appropriately selected according to the intended use, and is preferably 1 μm to 50 μm, and more preferably 5 μm to 20 μm.

The hardened film formed on the substrate can be peeled off the substrate and used as a material for electronic parts, etc., and can be used as a substrate with a hardened film such as an electronic circuit board or the like as an electronic part without peeling off the substrate according to the use or the substrate used Other materials.

Examples of electronic circuit boards include rigid boards, flexible boards, rigid flexible boards, and the like. As a flexible substrate, for example, a substrate obtained as follows: a film-shaped substrate such as a polyimide film in which wiring is formed in advance by an inkjet method or the like will contain a urea bond type tetrafunctional (methyl ) The ink of the acrylate compound is applied to the entire surface or a predetermined pattern (line, etc.) to form a coating film, and then the coating film is cured.

The metal forming the wiring (circuit) is not particularly limited, and is preferably gold, silver, copper, aluminum, or indium tin oxid (ITO). On the substrate on which these wirings are formed, an ink containing a urea bond-type tetrafunctional (meth)acrylate compound is applied in a predetermined pattern, and the hardened film obtained by curing it functions as an insulating film for protecting wirings and the like.

<Electronic parts> The electronic component of the present invention includes a hardened film or a substrate with a hardened film. According to the cured film or the substrate with a cured film using a film substrate as the substrate, flexible electronic parts and display elements can be obtained. For example, IC chips, capacitors, resistors, fuses, etc. are mounted on electronic circuit boards manufactured by using the cured film of the present invention that is excellent in heat resistance, electrical insulation, adhesion to a substrate, folding resistance, and flame retardancy. For example, electronic parts for liquid crystal display elements can be produced. [Example]

[Synthesis Example 1] <Synthesis example of urea bond type tetrafunctional acrylic modified silicon compound A> 1,1-(bisacryloyloxymethyl)ethyl isocyanate (trade name: manufactured by Karenz BEI, Showa Denko (Co., Ltd.), hereinafter appropriately referred to as "BEI") 7.0 g and 4-methoxy 0.1 g of phenol was dissolved in 27.9 g of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.), and the obtained solution was stirred at room temperature under a nitrogen atmosphere. In 10 minutes, 3.0 g of a disiloxane compound (trade name: BY16-871, manufactured by Toray Dow Corning (stock)) diluted with 12.1 g of tetrahydrofuran was added dropwise to the solution. The reaction liquid was obtained by stirring at -30°C for 1 hour. The solvent of the obtained reaction liquid was removed by an evaporator, and then hexane (10.0 g) was added dropwise, and the excess amount of BEI was removed 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"). The silicon compound A (compound (a)) is shown below.

<Silicon Compound A> [Chem 36]

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

<Silicon Compound B> [Chem 37]

[Synthesis Example 3] <Synthesis example of urea bond type tetrafunctional acrylic modified aromatic compound C> 7.41 g of aromatic diamine compound (trade name: 2,2-bis(4-(4-aminophenoxy)phenyl)propane, manufactured by Wakayama Chemical Industry Co., Ltd.) and 4-methoxyphenol 0.16 g was dissolved in 20.0 g of methyl ethyl ketone (hereinafter, appropriately referred to as "MEK"), and the mixture was stirred at room temperature under a nitrogen atmosphere. 8.61 g of BEI was added dropwise to the solution and stirred at 60°C. Then, 0.10 g of zirconium tetraacetone (trade name: ORGATIX ZC-150, Matsumoto Fine Chemical Co., Ltd.) dissolved in MEK 5.00 g was added dropwise to the solution. And stirred at 60°C for 2 hours. The solvent of the obtained reaction liquid was removed by an evaporator. A MEK solution of urea-bonded tetrafunctional acrylic modified aromatic compound C (25.58 g, solid content concentration 81 wt%, hereinafter appropriately referred to as "aromatic compound C") was obtained. The aromatic compound C (compound (a)) is shown below.

<Aromatic Compound C> [Chemical 38]

[Synthesis Example 4] <Synthesis example of urea bond type 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 at room temperature under a nitrogen atmosphere. To the solution, 6.6 g of an aromatic diamine compound (9,9-bis(4-aminophenyl)fluorene) diluted with 50.0 g of tetrahydrofuran was added dropwise over 8 minutes, and stirred at 50°C for 1 hour. Furthermore, after 5.2 g of BEI was added dropwise to the reaction solution, it was stirred at 50°C for 1 hour. After the obtained reaction liquid was extracted with ethyl acetate-water, it was washed with saturated saline and the extract was dried with magnesium sulfate. The extraction liquid and magnesium sulfate were filtered and separated, and the solvent was removed by an evaporator to obtain a concentrated liquid. It was left at room temperature and recrystallized, thereby obtaining a white solid. After washing the obtained white solid with ethyl acetate, the solvent was completely removed by vacuum drying. With this, a urea-bonded tetrafunctional acrylic modified aromatic compound D (8.5 g, hereinafter appropriately referred to as "aromatic compound D") was obtained. The aromatic compound D (compound (a)) is shown below.

<Aromatic compound D> [Chem 39]

[Comparative Synthesis Example 1] <Synthesis example of urea bond type bifunctional acrylic modified silicon compound E> Dissolve 0.85 g of siloxane diamine compound (trade name: BY16-871, manufactured by Toray Dow Corning (share)) and 0.02 g of 4-methoxyphenol in 8.00 g of tetrahydrofuran under a nitrogen atmosphere , Stir at room temperature. To the solution is added dropwise 1.15 g of 2-propenyloxyethyl isocyanate (trade name: Karenz AOI, Showa Denko (hereinafter referred to as "AOI"), at 20°C to 30 Stir for 1 hour at ℃. The solvent of the obtained reaction liquid was removed by an evaporator, and then hexane (10.0 g) was added dropwise, and the excess amount of AOI was removed by decantation. After removing the supernatant, the solvent was removed from the obtained solution using a vacuum pump to obtain a urea-bonded difunctional acrylic modified silicon compound E (1.6 g, hereinafter appropriately referred to as "silicon compound E"). The silicon compound E is shown below. Regarding the silicon compound E, since X in formula (1) is not a group represented by formula (2), it is not equivalent to compound (a).

<Silicon Compound E> [Chem. 40]

[Comparative Synthesis Example 2] <Synthesis example of urethane bond type tetrafunctional acrylic modified silicon compound F> To a solution containing 8.29 g of a siloxane compound (trade name: FM4401, manufactured by JNC Co., Ltd.) and 0.2 g of 4-methoxyphenol, 11.72 g of BEI was added dropwise and stirred at 60°C. Then, 0.10 g of zirconium tetraacetoacetone (trade name: ORGATIX ZC-150, Matsumoto Fine Chemical Co., Ltd.) dissolved in MEK 10.00 g was added dropwise to the solution. And stirred at 60°C for 2 hours. The solvent of the obtained reaction liquid was removed by an evaporator. A MEK solution (24.79 g, solid content concentration 84 wt%, hereinafter appropriately referred to as "silicon compound F") of a urethane bond type tetrafunctional acrylic modified silicon compound F was obtained. The silicon compound F is shown below. Since the silicon compound F has an urethane bond instead of a urea bond in the main chain, it is not equivalent to the compound (a).

<Silicon compound F> [Chem. 41]

[Synthesis Example 5] <Synthesis example of urea bond type tetrafunctional acrylic modified aromatic compound G> Aromatic diamine compound (trade name: 4,4-diaminodiphenyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.) 4.73 g and 4-methoxyphenol 0.16 g were dissolved in acetonitrile 50.00 g and acetone 50.00 g The mixed solvent was stirred at room temperature under a nitrogen atmosphere. 11.10 g of BEI was added dropwise to the solution and stirred at 60°C. Next, 0.08 g of zirconium tetraacetoacetone (trade name: ORGATIX ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) dissolved in 5.00 g of acetonitrile was added dropwise to the solution. And stirred at 60°C for 3 hours. The solvent of the obtained reaction liquid 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") is obtained. The aromatic compound G (compound (a)) is shown below.

<Aromatic compound G> [Chemical 42]

<Preparation of composition 1> 1.200 g of the silicon compound A synthesized in Synthesis Example 1, a phenalkone-based photopolymerization initiator (trade name: Irgacure 127, manufactured by BASF), which is appropriately referred to below as a hardener "IC127") 0.045 g, MEK 2.100 g as a solvent, and N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as "NMP") 0.700 g were mixed at room temperature to obtain a composition 1.

<Preparation of composition 2> By the same method as Composition 1, the silicon compound B synthesized in Synthesis Example 2 was used instead of the silicon compound A, and Composition 2 was obtained.

<Preparation of composition 3> 0.120 g of the silicon compound A synthesized in Synthesis Example 1, a siloxane compound having a three-dimensional cross-linked structure (trade name: SR-21, manufactured by Konishi Chemical Industry Co., Ltd., hereinafter appropriately referred to as "SR-21") 1.080 g. IC127 0.020 g as a hardener, 2.100 g MEK as a solvent and 0.700 g NMP (manufactured by Mitsubishi Chemical Corporation) 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 the silicon compound B instead of the silicon compound A by the same method as the composition 3.

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

<Preparation of composition 6> By using the same method as Composition 5, Irgacure 379EG (trade name, manufactured by BASF Corporation, hereinafter referred to as "IC379EG" as appropriate) was used instead of IC127 to obtain the composition (resin composition of the present invention) Things) 6.

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

<Preparation of composition 8> By the same method as Composition 3, using Silicon Compound E synthesized in Comparative Synthesis Example 1 instead of Silicon Compound A, Composition 8 was obtained.

[Reference Example 1] The composition 1 was applied on a glass substrate cut into 4 cm×4 cm, and spin coating was performed at a rotation speed of 300 rpm. After that, it was dried on a hot plate heated at 80°C for 5 minutes, and then dried on a hot plate heated at 135°C for 5 minutes, and then used a high-pressure mercury irradiation device (trade name: 8 kW×1 conveyor type ultraviolet rays) A curing device, manufactured by Eye Graphics (stock), was light-cured under conditions of 1,000 mJ/cm ² to obtain a cured film (1). The hardened film (1) is a colorless and transparent film without stickiness. The exposure amount was measured using an illuminance meter (UVPF-Al/PD-365, manufactured by Iwasaki Electric Co., Ltd.).

[Reference example 2] Except for using Composition 2 instead of Composition 1, a hardened film (2) was obtained by the same method as Reference Example 1. The hardened film (2) is a colorless and transparent film without stickiness.

[Example 1] A cured film (3) was obtained by the same method as Reference Example 1 except that Composition 3 was used instead of Composition 1, and applied to a glass substrate cut into 10 cm×10 cm.

[Example 2] A cured film (4) was obtained by the same method as in Example 1, except that Composition 4 was used instead of Composition 1.

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

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

根據評價結果明確，與使包含脲鍵型二官能丙烯酸改質矽化物的樹脂組成物硬化而獲得的硬化皮膜相比，使包含脲鍵型四官能丙烯酸改質矽化合物的本發明的樹脂組成物硬化而獲得的硬化皮膜具有更優異的耐熱性。 根據所述結果，可以說鍵結於具備脲鍵的(甲基)丙烯酸酯化合物的末端的(甲基)丙烯酸酯的數量會影響使包含所述化合物的樹脂組成物硬化而獲得的硬化皮膜的耐熱性。可知於具有兩個脲鍵的脲鍵型(甲基)丙烯酸酯化合物中，藉由將官能基數設為四個，由包含脲鍵型(甲基)丙烯酸酯化合物與具有三維交聯結構的矽氧烷化合物的樹脂組成物形成的硬化皮膜的耐熱性變得良好。就形成耐熱性良好的硬化皮膜的觀點而言，相對於脲鍵型(甲基)丙烯酸酯化合物1重量份，樹脂組成物中的具有三維交聯結構的矽氧烷化合物的含量較佳為1重量份～20重量份，更佳為5重量份～15重量份。[Table 1] Table 1

It is clear from the evaluation results that the resin composition of the present invention containing the urea-bonded tetrafunctional acrylic modified silicon compound is harder than the cured film obtained by hardening the resin composition containing the urea-bonded bifunctional acrylic modified silicide. The cured film obtained by curing has more excellent heat resistance. From the results, it can be said that the number of (meth)acrylates bonded to the end of the (meth)acrylate compound having a urea bond affects the cured film obtained by hardening the resin composition containing the compound Heat resistance. It can be seen that in a urea bond type (meth)acrylate compound having two urea bonds, by setting the number of functional groups to four, a urea bond type (meth)acrylate compound and a silicon having a three-dimensional cross-linked structure are included. The cured film formed of the resin composition of the oxane compound has good heat resistance. From the viewpoint of forming a cured film with good heat resistance, the content of the siloxane compound having a three-dimensional cross-linked structure in the resin composition is preferably 1 relative to 1 part by weight of the urea bond type (meth)acrylate compound. Part by weight to 20 parts by weight, more preferably 5 parts by weight to 15 parts by weight.

化合物A、化合物B：矽化合物A、矽化合物B（四官能）（化合物（a）） 化合物E：矽化合物E（二官能） 化合物SR-21：具有式（4）所表示的三維交聯結構（R₉ ：苯基）的矽氧烷化合物（樹脂（b）） 硬化劑IC127：豔佳固（Irgacure）127（聚合起始劑（c）） 硬化劑IC379EG：豔佳固（Irgacure）379EG（聚合起始劑（c））The components contained in the above-mentioned Compositions 1 to 8 are shown in Table 2 below (unit: g). [Table 2] Table 2

Compound A, Compound B: Silicon compound A, Silicon compound B (tetrafunctional) (Compound (a)) Compound E: Silicon compound E (bifunctional) Compound SR-21: has a three-dimensional cross-linked structure represented by formula (4) (R ₉ : phenyl) siloxane compound (resin (b)) Hardener IC127: Irgacure 127 (polymerization initiator (c)) Hardener IC379EG: Irgacure 379EG ( Polymerization initiator (c))

<Measurement 1 of reaction rate> [Example 3] The composition 5 was applied on a glass substrate cut into 4 cm×4 cm, and spin coating was performed at a rotation speed of 300 rpm. After that, it was dried on a hot plate heated at 80°C for 5 minutes, and then dried on a hot plate heated at 135°C for 5 minutes, and the exposure amount was set to 500 using a high-pressure mercury irradiation device in the same manner as in Reference Example 1. The range of mJ/cm ² to 2,500 mJ/cm ² was changed, and the reaction rate of the propylene amide group was measured. The reaction rate is determined by the following method.

<Reaction rate> A Fourier conversion infrared spectrophotometer (FT/IR-6700, manufactured by Nippon Spectroscopy Co., Ltd.) was used, and the reaction rate was calculated using the following formula. Response rate (%)={(X1-X2)/X1}×100 (X1: peak area ratio before exposure P-2/P-1, X2: peak area ratio after exposure P-2/P-1, P-1: peak area of silicon-phenyl bond (1440 cm ^-1 ), P-2: peak area of acrylic acid terminal CH bond (1410 cm ^-1 ))

[Example 4] Instead of the high-pressure mercury irradiation device of Example 3, the composition 6 was used instead of the high-pressure mercury irradiation device of Example 3 using a UV-LED irradiation conveying device (trade name: LSS-08A, manufactured by Sunenergy), except for this Otherwise, the reaction rate of the propylene amide group was measured by the same method as in Example 3. Table 3 shows the results. [Table 3] Table 3

In general, the energy of ultraviolet rays irradiated by the UV-LED irradiation conveying device used in Example 4 is smaller than that of the high-pressure mercury irradiation device, so even if a curing agent suitable for an LED light source is used, the reaction rate decreases. However, according to the results of Example 3 and Example 4, it can be seen that in the case of using the UV-LED irradiation and transport device, by selecting a curing agent suitable for the light source, the reaction rate with UV curing of the acrylate is the highest The high-pressure mercury produces a hardened film in comparison with an inferior reaction rate. Based on these evaluation results, it is clear that by using the resin composition of the present invention containing a urea bond-type tetrafunctional (meth)acrylate compound as the compound (a), it is possible to form and use a high voltage even using a UV-LED irradiation conveyor Compared with the hardened film of mercury irradiation device.

[Example 5] The composition 7 was applied to a chromium substrate cut into 9 cm×7 cm, and spin coating was performed at a rotation speed of 300 rpm. Thereafter, it was dried on a hot plate heated at 80°C for 5 minutes, and further dried on a hot plate heated at 135°C for 5 minutes, and then carried out in the same manner as in Example 4 using a UV-LED irradiation conveyor at 1,000 mJ/ Light curing was performed under the condition of cm ² to obtain a colorless and transparent cured film (6). Thereafter, aluminum was vapor-deposited using a vacuum vapor deposition device (VE-2030, vacuum device (product)). The volume resistivity measured using an ultra-high resistance meter (DSM-810, manufactured by Agilent) was 1.9×10 ¹⁵ (Ω·cm) and had excellent electrical insulation.

<Preparation of composition 9> The 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 hardener, 3.150 g of MEK as a solvent, and 1.050 g of NMP.

<Preparation of composition 10> By the same method as composition 9, the acrylic modified silicon compound F synthesized in Comparative Synthesis Example 2 was used instead of the silicon compound A to obtain the composition 10. The components contained in the composition 9 to the composition 10 are shown in Table 4 below (unit: g). [Table 4] Table 4

[Reference Example 3] The composition 9 was applied on a glass substrate cut into 4 cm×4 cm, and spin coating was performed at a rotation speed of 300 rpm. Thereafter, it was dried on a hot plate heated at 80°C for 5 minutes, and further dried on a hot plate heated at 135°C for 5 minutes, and then carried out in the same manner as in Example 4 using a UV-LED irradiation conveyor at 1,000 mJ/ Light curing was performed under the condition of cm ² to obtain a cured film (7). The obtained hardened film (7) is a colorless and transparent film without stickiness.

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

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

It is clear from the evaluation results that the (meth)acrylate compound having the urea bond is obtained by curing the (meth)acrylate compound having the urethane bond as compared to the cured film (8) obtained by hardening the (meth)acrylate compound having the urethane bond The hardened film (7) has more excellent heat resistance. From the above results, it can be said that regarding the compound having a urea bond, the bonding method of the main chain affects the heat resistance of the hardened product obtained by hardening the compound.

<Preparation of composition 11> The silicon compound A synthesized in Synthesis Example 1 0.300 g, SR-21 0.900 g, IC379EG 0.045 g as a hardener, MEK 2.100 g as a solvent, and NMP 0.700 g were mixed to obtain the composition (resin composition) of the present invention 11.

<Preparation of composition 12> The silicon compound F synthesized in Comparative Synthesis Example 2 was used instead of the silicon compound A, and the composition 12 of the present invention was obtained by the same method as the composition 11 except that the silicon compound A was used. The components contained in the composition 11 to the composition 12 are shown in Table 6 below (unit: g). [Table 6] Table 6

<Measurement 2 of reaction rate> [Example 6] The composition 11 was applied on a glass substrate cut into 4 cm×4 cm, and spin coating was performed at a rotation speed of 300 rpm. After that, it was dried on a hot plate heated at 80°C for 5 minutes, and further dried on a hot plate heated at 135°C for 5 minutes, and the transport device was irradiated with a UV-LED in the same manner as in Example 4 to expose the amount of light The reaction rate was changed within the range of 400 mJ/cm ² to 1,500 mJ/cm ² to measure the propylene amide group. In addition, the reaction rate was obtained by the same method as Example 5.

[Comparative Example 2] The reaction rate of the propylene amide group was measured in the same manner as in Example 6, except that the composition 12 was used instead of the composition 11. Table 7 shows the results. [Table 7] Table 7

It is clear from the evaluation results that the cured film obtained by hardening the composition containing the (meth)acrylate compound having a urea bond in the present invention has a (meth)acrylate compound having a urethane bond, Higher reactivity. Especially at a lower exposure amount of 1,000 (mJ/cm ² ) or less, the (meth)acrylate compound having a urea bond shows significantly higher than the (meth)acrylate compound having a urethane bond Reactivity. According to the results, it can be said that the bonding mode of the main chain of the tetrafunctional acrylic modified silicon compound affects the reactivity.

<Preparation of composition 13> 0.540 g of the aromatic compound C synthesized in Synthesis Example 3, 0.081 g of IC379EG as a hardener, 3.150 g of MEK as a solvent, and 1.050 g of NMP were mixed to obtain Composition 13.

<Preparation of composition 14> Except that the aromatic compound D synthesized in Synthesis Example 4 was used instead of the aromatic compound C, the composition 14 was obtained by the same method as the composition 13.

化合物C、化合物D：芳香族化合物C、芳香族化合物D（主鏈的芳香環4、化合物（a）） 化合物G：芳香族化合物G（主鏈的芳香環2、化合物（a））<Preparation of composition 15> The aromatic compound G synthesized in Synthesis Example 5 was used instead of the aromatic compound C, and the composition 15 was obtained by the same method as the composition 13 except that the aromatic compound C was used. The components contained in the above-mentioned composition 13 to composition 15 are shown in Table 8 below (unit: g). [Table 8] Table 8

Compound C, Compound D: aromatic compound C, aromatic compound D (aromatic ring 4 in the main chain, compound (a)) Compound G: aromatic compound G (aromatic ring 2 in the main chain, compound (a))

[Reference Example 4] The composition 13 was applied on a glass substrate cut into 10 cm×10 cm, and spin coating was performed at a rotation speed of 300 rpm. Thereafter, it was dried on a hot plate heated at 80°C for 5 minutes, and further dried on a hot plate heated at 135°C for 5 minutes, and then carried out in the same manner as in Example 4 using a UV-LED irradiation conveyor at 1,000 mJ/ Light curing was performed under the condition of cm ² to obtain a cured film. The obtained hardened film is a colorless and transparent film without stickiness.

[Reference Example 5] Except for using the composition 14 instead of the composition 13, a colorless and transparent hardened film was obtained by the same method as in Reference Example 4.

[Reference Example 6] A cured film was obtained by the same method as Reference Example 4 except that Composition 15 was used instead of Composition 13.

<Evaluation of hardened film> ＜5%～20% weight loss temperature＞ In the same manner as in Example 1, the measurement was carried out in the range of 40°C to 550°C using a differential thermogravimetric simultaneous measurement device. In order to eliminate errors caused by the moisture absorption of the film, the weight at 100° C. is set to 100%, and the temperature at which the weight is reduced by 5% to 20% is set to 5%, 10%, and 20% weight reduction temperature, respectively. Table 9 shows the results.

根據評價結果明確，與包含在主鏈具有兩個芳香環的化合物的組成物相比，包含在主鏈具有四個芳香環的化合物的組成物藉由使組成物硬化，可獲得具有更優異的耐熱性的硬化皮膜。 根據所述結果，可以說具備脲鍵的(甲基)丙烯酸酯化合物中，鍵結於主鏈的芳香環的數量會影響耐熱性。可知於主鏈具有四個以上的芳香環的脲鍵型(甲基)丙烯酸酯化合物中，藉由將芳香環的數量設為四個，由包含脲鍵型(甲基)丙烯酸酯化合物與光聚合起始劑的組成物形成的硬化皮膜的耐熱性變得良好。[Table 9] Table 9

It is clear from the evaluation results that the composition containing the compound having four aromatic rings in the main chain can be obtained by curing the composition more excellently than the composition containing the compound having two aromatic rings in the main chain. Heat-resistant hardened film. From the above results, it can be said that in the (meth)acrylate compound having a urea bond, the number of aromatic rings bonded to the main chain affects heat resistance. It can be seen that in the urea bond type (meth)acrylate compound having four or more aromatic rings in the main chain, by setting the number of aromatic rings to four, the urea bond type (meth)acrylate compound and light The heat resistance of the hardened film formed by the composition of the polymerization initiator becomes good.

[Synthesis Example 6] <Synthesis example of silanol-containing siloxane compound having a three-dimensional cross-linked structure> A three-necked flask equipped with a dropping funnel, a reflux cooler, and a thermometer with a volume of 200 ml was charged with 31.8 g of phenyltrimethoxysilane, 33.5 g of tetraethoxysilane, and 4.9 g of dimethyldimethoxysilane And diethylene glycol ethyl methyl ether 34.3 g, sealed with dry nitrogen. While stirring with a magnetic stirrer, while stirring at room temperature for 30 minutes, a mixture 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, using an oil bath, it was heated at 90°C for 1.5 hours, at 100°C for 1 hour, and at 140°C for 2.5 hours. It was confirmed that the distillation and removal of methanol and ethanol produced stopped Then make the reaction end. After leaving to cool to room temperature, after mixing 100 g of ethyl acetate, a separatory funnel was used to wash with water until the pH became neutral. Thereafter, it was concentrated at room temperature using an evaporator until the weight of the solution became 50 g, and a silanol-containing siloxane compound solution having a three-dimensional cross-linked structure (substrate A) having a solid content concentration of 44% by weight was prepared.

Using the Fourier transform infrared spectrophotometer in the same manner as in Example 3, the IR spectrum of the matrix A was measured, and the presence of a peak of 920 cm ^-1 attributed to silanol confirmed that the siloxane compound having a three-dimensional cross-linked structure Contains silanol (920 cm ^-1 ). In addition, the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) analysis of the 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> Device: LC-2000Plus series (detector: differential refractive index meter) manufactured by Japan Spectroscopy Co., Ltd. Solvent: THF/DMF=1/1 (v/v) Flow rate: 0.5 ml/min Column temperature: 40 ℃ Use of columns: Showa Denko Co., Ltd., Asahipak GF-1G 7B (protection column) + Asahipak GF-7M HQ, exclusion limit molecular weight (PEG) = 10,000,000) for calibration curve Standard sample: PSt

<Preparation of composition 16> The compound of the present invention was obtained by mixing 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 cross-linked structure), IC127 0.027 g and 2.147 g of NMP as a solvent.组合物16。 16. Composition 16.

[Example 7] The composition 16 was applied to a glass substrate cut into 4 cm×4 cm, and spin coating was performed at a rotation speed of 300 rpm. Thereafter, it was dried on a hot plate heated at 80°C for 5 minutes, and further dried on a hot plate heated at 135°C for 5 minutes to produce two uncured films. In the same manner as in Reference Example 1, only one uncured film was photocured under the condition of 1,000 mJ/cm ² using a high-pressure mercury irradiation device, and the cured film (9) was used, and the remaining one was referred to as the uncured film (1). In the same manner as in Reference Example 1, the exposure amount was measured using an illuminance meter. The solvent resistance of the produced uncured film (1) and cured film (9) was evaluated under the following conditions.

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

The results indicate that although the resin composition contains only 10% by weight of the urea-bonded tetrafunctional acrylic modified silicon compound A, the cured film obtained by the reaction of the acryl group in the resin composition exhibits solvent resistance . The above situation indicates that the urea bond type tetrafunctional acrylic modified silicon compound A forms a hydrogen bond with the siloxane compound having a three-dimensional cross-linked structure contained in the matrix A.

[Example 8 to Example 10] The components 17 to 19 were prepared by mixing the ingredients at the formulation amounts (unit: g) shown in Table 10, and the cured film (10) to the cured film (12) were produced in the same manner as in Example 4. <Evaluation of heat-resistant adhesion> The adhesiveness before and after the heating test at 200° C. for 30 minutes at 200° C. of the cured film (10) to the cured film (12) was evaluated by a checkerboard peel test (cross cut test). No. 610 manufactured by 3M was used for the evaluation tape. The person who did not peel at all was set to "○", and those who observed 1 to 100 peels were set to "×". The results are shown in Table 10, and all the cured films showed good adhesion before and after the heating test. No cracks occurred in the cured film after the heating test, so the resin composition of the present invention can be preferably used as an insulating film for semiconductors requiring a heating step.

化合物SR-23（小西化學工業（股）製造）：具有式（4）所表示的三維交聯結構（R₉ ：苯基）的矽氧烷化合物（樹脂（b）） 化合物DMDMS（東京化成（股）製造）：二甲基二甲氧基矽烷 縮合觸媒TA-30（松本精細化工（Matsumoto Fine Chemical）（股）製造）：歐陸泰斯（ORGATIX）TA-30 [產業上之可利用性][Table 10] Table 10

Compound SR-23 (manufactured by Konishi Chemical Industry Co., Ltd.): Siloxane compound (resin (b)) having a three-dimensional cross-linked structure (R ₉ : phenyl) represented by formula (4) Compound DMDMS (Tokyo Chemical ( Co., Ltd.): dimethyldimethoxysilane condensation catalyst TA-30 (Matsumoto Fine Chemical Co., Ltd.): ORGATIX TA-30 [Industry availability ]

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

Claims (9)

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

In formula (1), A is a divalent organic group, and Y is a linear alkylene group having 1 to 18 carbon atoms or a branched alkylene group. When the carbon number of the alkylene group is 2 or more, An oxygen atom (-O-) can be inserted between any CC bonds, and -CO- can also be inserted between the CN bonds at the end, m is 0 or 1, and X is a group represented by the following formula (2);

In formula (2), R ₁ and R ₂ are each independently hydrogen or methyl. The resin composition as described in item 1 of the patent application range, wherein the hydrogen-bonding group in the resin (b) is a group having active hydrogen. The resin composition as described in item 1 or item 2 of the patent application scope, wherein the resin (b) contains a three-dimensional cross-linked structure represented by the following formula (3) or the following formula (4) in the structure At least one of the silicone compounds;

In formula (4), R ₉ is a group selected from a linear alkyl group having 1 to 22 carbon atoms or a branched alkyl group, an aryl group having 1 to 9 carbon atoms or an arylalkyl group having 7 to 21 carbon atoms , Any hydrogen in these groups may be substituted with halogen, and when the carbon number of the alkyl group is 2 or more, an oxygen atom (-O-), cycloalkylene, cycloalkylene can be inserted between any CC bonds Base, phenylene, naphthalene; wherein, the total carbon number of R ₉ does not exceed 30. The resin composition as described in item 3 of the patent application, wherein R ₉ in formula (4) is methyl or phenyl. The resin composition according to any one of items 1 to 4 of the patent application scope, wherein A in formula (1) is a structure represented by formula (5);

In formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or an alkyl group having 1 to 30 carbon atoms, and Z is an alkylene group having 1 to 4 carbon atoms. n is an integer of 0-150. The resin composition as described in item 5 of the patent application, wherein m in formula (1) is 0. The resin composition as described in item 5 or 6 of the patent application scope, wherein in formula (5), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are methyl groups, and Z is propylene base. A hardened film obtained from the resin composition according to any one of claims 1 to 7 of the patent application. An electronic component having a hardened film as described in item 8 of the patent application scope.