JP7205538B2 - Urea-bonded tetrafunctional (meth)acrylate compound and composition containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel urea-bonded tetrafunctional (meth)acrylate compounds and compositions containing the same, which are used as materials for insulating films in electronic parts such as printed wiring boards and semiconductor package substrates.

2. Description of the Related Art In recent years, in order to meet the demand for weight reduction of portable terminals having a display such as a liquid crystal display, changing the raw materials of electronic parts from glass to plastic has been studied. Since plastic is inferior to glass in scratch resistance, a method of preventing scratches by surface treatment with a hard coating agent is widely used. (Meth)acryloyl at both ends of the molecule obtained by reacting an organopolysiloxane having —OH at both ends of the molecule with an isocyanate-containing (meth)acrylate as a compound for improving the scratch resistance of the hard coating agent. (Patent Document 1, Patent Document 2). Also proposed is a radiation-curable organopolysiloxane composition (Patent Document 3) that exhibits excellent adhesiveness to plastic substrates and deep-part curability. However, Patent Documents 1 and 2 are concerned with improving the scratch resistance of a cured film formed from a compound or composition, and do not describe heat resistance. Moreover, Patent Document 3 deals with the adhesiveness of the composition and does not describe heat resistance.

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

JP 2015-196748 A International Patent Application Publication WO2015/152288 JP-A-6-184256 JP 2008-88251 A JP 2007-55993 A

The curable composition described in Patent Document 4 is used for color filters, and is not suitable as a material for insulating films in electronic parts. In addition, in Patent Document 5, for example, a general-purpose curative that can be used for various applications such as resists, sealants, paints, adhesives, printing plates, printing proofreading, lenses, dental materials, surface treatments, battery materials, etc. Although the composition is disclosed, there is no mention of reactivity when cured using a light source such as an LED light source with a small amount of ultraviolet energy, and a material for an insulating film that is particularly required to have heat resistance and electrical insulation. It is not specialized for
Accordingly, an object of the present invention is to provide a novel compound having excellent heat resistance and reactivity suitable as a material for insulating films in electronic parts such as printed wiring boards and semiconductor package substrates, and a composition containing the same. and

The present invention uses a novel urea-bonded tetrafunctional (meth)acrylate compound having a urea bond and (meth)acryloyl to achieve a high reaction rate even when using a light source such as an LED light source with a small amount of ultraviolet energy. It is based on the new knowledge that it can be cured and provides a cured film with excellent heat resistance and electrical insulation, which is suitable as a material for insulating films in electronic parts, etc., and has the following constitution.

（式（１）において、Ａは二価の有機基であり、Ｙは炭素数１～１８の直鎖アルキレンまたは分岐を有するアルキレンであり、該アルキレンの炭素数が２以上である場合は任意のＣ－Ｃ結合間に酸素原子（－Ｏ－）が挿入されていてもよく、末端のＣ－Ｎ結合間に－ＣＯ－が挿入されていてもよく、ｍは０または１であり、Ｘは下記式（２）で示される基である。）

（式（２）において、Ｒ₁およびＲ₂は、独立に水素またはメチルである。） [1] A urea-bonded tetrafunctional (meth)acrylate compound represented by the following formula (1), wherein A in formula (1) is a divalent diamine compound derived from an aromatic diamine compound having 4 or more aromatic rings A urea-bonded tetrafunctional (meth)acrylate compound that is an organic group .

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

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

（式（１）において、Ａは二価の有機基であり、Ｙは炭素数１～１８の直鎖アルキレンまたは分岐を有するアルキレンであり、該アルキレンの炭素数が２以上である場合は任意のＣ－Ｃ結合間に酸素原子（－Ｏ－）が挿入されていてもよく、末端のＣ－Ｎ結合間に－ＣＯ－が挿入されていてもよく、ｍは０または１であり、Ｘは下記式（２）で示される基である。）

（式（２）において、Ｒ ₁ およびＲ ₂ は、独立に水素またはメチルである。）

（式（３）におけるＲ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈はそれぞれ独立して、水素または炭素数１～３０のアルキルであり、Ｚは炭素数１～４のアルキレンであり、ｎは０～１５０の整数である。）
[2] A urea-bonded tetrafunctional (meth)acrylate compound represented by the following formula (1), wherein A in formula (1) is a divalent organic group having a structure represented by formula (3). , a urea -bonded tetrafunctional (meth)acrylate compound.

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

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

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

[3] The urea-bonded tetrafunctional (meth)acrylate compound according to [1] or [2] , wherein m in formula (1) is 0.

[4] Urea-bonded tetrafunctional (meth) according to [2] , wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ in formula (3) are methyl, and Z is trimethylene. Acrylate compound.

[5] A composition comprising the urea-bonded tetrafunctional (meth)acrylate compound of [1] or [2] .
[6] A composition comprising the urea-bonded tetrafunctional (meth)acrylate compound of [2] and a siloxane compound having a three-dimensional crosslinked structure.
[7] The composition according to [6] , comprising 1 to 20 parts by weight of the siloxane compound having a three-dimensional crosslinked structure per 1 part by weight of the urea-bonded tetrafunctional (meth)acrylate compound.

[8] A cured film obtained from the urea-bonded tetrafunctional (meth)acrylate compound according to [1] or [2] .
[9] An electronic component having the cured film according to [8] .

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

（式（１）において、Ａは二価の有機基であり、Ｙは炭素数１～１８の直鎖アルキレンまたは分岐を有するアルキレンであり、該アルキレンの炭素数が２以上である場合は任意のＣ－Ｃ結合間に酸素原子（－Ｏ－）が挿入されていてもよく、末端のＣ－Ｎ結合間に－ＣＯ－が挿入されていてもよく、ｍは０または１であり、Ｘは下記式（２）で示される基である。ここで、ＹのＣ－Ｃ結合間に酸素原子（－Ｏ－）が挿入されたアルキレンとは、例えば、エチレンオキシ構造、プロピレンオキシ構造等のアルキレンオキシ構造を有するものを意味する。）

（式（２）において、Ｒ_１、Ｒ_２は水素またはメチルである。）Embodiments of the present invention will be specifically described below.
[Urea-bonded tetrafunctional (meth)acrylate]
The urea-bonded tetrafunctional (meth)acrylate compound of the present invention (suitably referred to as "urea-bonded tetrafunctional (meth)acrylate") is a compound represented by the following formula (1).

(In the formula (1), A is a divalent organic group, Y is a linear alkylene or branched alkylene having 1 to 18 carbon atoms, and when the alkylene has 2 or more carbon atoms, any An oxygen atom (—O—) may be inserted between the C—C bonds, and —CO— may be inserted between the terminal C—N bonds, m is 0 or 1, and X is It is a group represented by the following formula (2), wherein the alkylene having an oxygen atom (—O—) inserted between the C—C bonds of Y is, for example, an alkylene such as an ethyleneoxy structure or a propyleneoxy structure. means having an oxy structure.)

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

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

A urea-bonded tetrafunctional (meth)acrylate can form a hydrogen bond with —OH, which is a component in the matrix resin, through a urea bond. Therefore, since the matrix resin having no photocurable substituent can be fixed by hydrogen bonding, it is possible to form a cured film by irradiating light such as ultraviolet rays or visible light. Therefore, by using a matrix resin having various properties, a photocurable composition having desired properties can be prepared. The matrix resin used together with the urea-bonded tetrafunctional (meth)acrylate will be described later.

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

（式（３）におけるＲ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８はそれぞれ独立して、水素または炭素数１～３０のアルキルであり、Ｚは炭素数１～４のアルキレンであり、ｎは０～１５０の整数である。）From the viewpoint of obtaining a cured product with good heat resistance, the divalent organic group A included as part of the urea-bonded tetrafunctional (meth)acrylate compound is a divalent organic group having 3 or more aromatic rings. Alternatively, a divalent organic group having a structure represented by formula (3) is preferred. Here, the divalent organic group having an aromatic ring may have a structure in which condensed rings such as naphthalene and anthracene, or aromatic rings such as fluorene are linked via chemical bonds. In the present invention, when one benzene ring is used, naphthalene and fluorene are counted as having two aromatic rings, and anthracene is counted as having three aromatic rings.

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

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

<Synthesis method>
The urea-bonded tetrafunctional (meth)acrylate of the present invention can be synthesized, for example, by synthesis methods 1 to 3 described below.
<Synthesis method 1>
The urea-bonded tetrafunctional (meth)acrylate of the present invention has a diamine compound having —NH ₂ at both ends represented by the following formula (4) and two (meth)acryloyl represented by the following formula (5). Obtained by reacting a monoisocyanate compound.

（式（４）におけるＡは、式（１）と同様の基である。）

（式（５）におけるＲ_１、Ｒ_２は、式（２）と同様の基である。）

(A in formula (4) is the same group as in formula (1).)

(R ₁ and R ₂ in formula (5) are the same groups as in formula (2).)

（式（６）におけるＲ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８はそれぞれ独立して、水素または炭素数１～３０のアルキルであり、Ｚが炭素数１～４のアルキレンであり、ｎは０～１５０の整数である。）The diamine compound represented by formula (4) is an aromatic diamine compound having 3 or more aromatic rings, or A siloxane diamine compound having a structure represented by formula (6) is preferred.

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

When the urea-bonded tetrafunctional (meth)acrylate of the present invention is used as a composition, the n of the silicone chain of the siloxane diamine compound represented by formula (6) is set to 0 to 20. It is preferable because it can improve compatibility with other components inside.

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

Examples of aromatic diamine compounds having four aromatic rings include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-( 3-aminophenoxy)phenyl)sulfone, 4,4′-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)fluorene, 4,4′-(biphenyl-2,5-diylbis oxy)bisaniline, 4,4'-bis(4-aminobenzamido)-3,3'-dihydroxybiphenyl, 4,4'-bis(4-aminophenoxy)benzophenone.

Examples of the siloxane diamine compound represented by formula (6) include 1,3-bis(aminomethyl)tetramethyldisiloxane, 1,3-bis(2-aminoethyl)tetramethyldisiloxane, 1,3-bis( 3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, 1,5-bis(3-aminopropyl)hexamethyltrisiloxane, α,ω-bis(3- aminopropyl)polydimethylsiloxane. As these siloxane diamine compounds, commercially available products and those obtained by synthesis can be used. Examples of commercially available siloxane diamine compounds include Silaplane FM33 series (trade name, manufactured by JNC Corporation), X22 series (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BY16 series (trade name, Dow Corning Toray Co., Ltd.). Co., Ltd.) and the like. As a method for synthesizing a siloxane diamine compound, for example, both end dimethylsilylpolydimethylsiloxane (for example, trade name: Silaplane FM11 series, manufactured by JNC Co., Ltd.) is synthesized by reacting it with allylamine or the like in the presence of a platinum catalyst. method.

A siloxane diamine compound in which R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are all methyl and Z is trimethylene in formula (6) is preferred from the viewpoint of availability.
By this synthesis method, a urea-bonded tetrafunctional (meth)acrylate in which m is 0 in formula (1) can be synthesized.

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

A catalyst may be used for the purpose of increasing the reactivity between the diamine compound represented by formula (4) and the monoisocyanate having (meth)acryloyl represented by formula (5). Examples of catalysts include tin catalysts (e.g. dibutyltin dilaurate), amine catalysts (e.g. triethylenediamine), carboxylate catalysts (e.g. lead naphthenate, potassium acetate), trialkylphosphine catalysts (e.g. triethylphosphine), titanium catalysts (e.g. , trade names: ORGATICS TA-21, ORGATICS TA-30, ORGATICS TC-750, etc., manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium-based catalysts (for example, trade names: ORGATICS ZC-150, Matsumoto Fine Chemical Co., Ltd. ) made) etc. can be used.

（式（４）において、Ａは、式（１）と同様の基である。）

（式（７）において、Ｒ_１、Ｒ_２は、式（２）と同様の基を表し、Ｙ_１は炭素数１～１８の直鎖アルキレンまたは分岐を有するアルキレンであり、該アルキレンの炭素数が２以上である場合は、任意のＣ－Ｃ結合間に酸素原子（－Ｏ－）が挿入されていてもよい。）<Synthesis method 2>
The urea-bonded tetrafunctional (meth)acrylate of the present invention comprises a diamine compound having —NH ₂ at both ends represented by formula (4), and a monomonomer having two (meth)acryloyl groups represented by formula (7) below. It can be obtained by reacting with a carboxylic acid compound.

(In formula (4), A is the same group as in formula (1).)

(In formula (7), R ₁ and R ₂ represent the same groups as in formula (2), Y ₁ is linear alkylene or branched alkylene having 1 to 18 carbon atoms, and the number of carbon atoms in the alkylene is 2 or more, an oxygen atom (-O-) may be inserted between any C-C bonds.)

A monocarboxylic acid compound having two (meth)acryloyl groups represented by the formula (7) is a monocarboxylic acid compound having one —NH ₂ in the molecule represented by the following formula (9), and the following formula ( It can be synthesized by reaction with a monoisocyanate compound having two (meth)acryloyl groups shown in 5).

（式（９）において、Ｙ_１は、式（７）と同様の基である。）

（式（５）において、Ｒ_１およびＲ_２は、式（２）と同様の基である。）

(In formula (9), Y ₁ is the same group as in formula (7).)

(In formula (5), R ₁ and R ₂ are the same groups as in formula (2).)

Examples of monocarboxylic acid compounds having one —NH ₂ in the molecule represented by formula (9) include the following.

In order to increase the reactivity between a monocarboxylic acid compound having one —NH ₂ in the molecule represented by formula (9) and a monoisocyanate compound having two (meth)acryloyl groups represented by formula (5), A condensing agent or catalyst may be used. Examples of condensing agents include N,N'-dicyclohexylcarbodiimide and 1-hydroxybenzotriazole, and examples of catalysts include N,N-dimethyl-4-aminopyridine.

By this synthesis method, a urea-bonded tetrafunctional (meth)acrylate in which m in formula (1) is 1 can be synthesized. By setting m in formula (1) to 1, flexibility can be imparted to the urea-bonded tetrafunctional (meth)acrylate and the reactivity of (meth)acryloyl can be adjusted. That is, the urea-bonded tetrafunctional (meth)acrylate in which m in formula (1) is 1 has a smaller ratio of (meth)acrylate per molecule than that in which m is 0, so flexibility increases and curing The flexibility of the object is improved. In addition, the urea-bonded tetrafunctional (meth)acrylate in which m in formula (1) is 1 has a longer molecular chain that constitutes the backbone of the polymer (polymer) than that in which m is 0. The degree of freedom of molecules increases. In addition, as the number of hydrogen-bonding functional groups (--NH--) in the compound increases, the intermolecular interaction becomes greater, so an aggregation effect is expected. As a result of these, the urea-bonded tetrafunctional (meth)acrylate in which m in formula (1) is 1 has high reactivity in photopolymerization.

（式（４）において、Ａは、式（１）と同様の基である。）

（式（８）において、Ｒ_１およびＲ_２は、式（２）と同様の基を表し、Ｗはハロゲンを表し、Ｙ_２は炭素数１～１８の直鎖アルキレンまたは分岐を有するアルキレンであり、該アルキレンの炭素数が２以上である場合は、任意のＣ－Ｃ結合間に酸素原子（－Ｏ－）が挿入されていてもよい。）<Synthesis method 3>
The urea-bonded tetrafunctional (meth)acrylate of the present invention comprises a diamine compound having —NH ₂ at both ends represented by formula (4) and a monomonomer having two (meth)acryloyl represented by formula (8) below. It can be obtained by reacting with a halogen compound.

(In formula (4), A is the same group as in formula (1).)

(In formula (8), R ₁ and R ₂ represent the same groups as in formula (2), W represents halogen, and Y ₂ is linear alkylene or branched alkylene having 1 to 18 carbon atoms. , When the alkylene has 2 or more carbon atoms, an oxygen atom (—O—) may be inserted between any C—C bonds.)

The monohalogen compound having two (meth)acryloyls represented by the formula (8) is a monohalogen compound having one —NH ₂ in the molecule represented by the following formula (11), and the following formula (5) It can be synthesized by reaction with a monoisocyanate compound having two (meth)acryloyls represented by.

（式（１１）において、Ｙ_２は式（８）と同様の基であり、Ｗはハロゲンである。）

（式（５）において、Ｒ_１およびＲ_２は、式（２）と同様の基である。）

(In formula (11), _Y2 is the same group as in formula (8), and W is halogen.)

(In formula (5), R ₁ and R ₂ are the same groups as in formula (2).)

Examples of monohalogen compounds having one —NH ₂ in the molecule represented by formula (11) include the following.

An inorganic base may be used in combination for the purpose of increasing the reactivity between the monoisocyanate compound having two (meth)acryloyls and the monohalogen compound having one —NH ₂ in the molecule. Inorganic bases include calcium carbonate, sodium hydroxide, potassium hydroxide and sodium hydride.
By this synthesis method, a urea-bonded tetrafunctional (meth)acrylate in which m in formula (1) is 1 can be synthesized.

<Composition>
The composition of the present invention comprising the above-described urea-bonded tetrafunctional (meth)acrylate compound of the present invention is a radical polymerizable compound other than the compound represented by formula (1) within a range that does not impair photocurability and heat resistance. A compound having a double bond, an organic resin, an inorganic resin, a solvent, a polymerization initiator, and the like may be contained.

The compound having a radically polymerizable double bond other than the compound represented by formula (1) includes a (meth)acrylate other than the compound represented by formula (1), and a radically polymerizable double bond other than (meth)acrylate. resins having unsaturated bonds capable of undergoing radical polymerization, such as low-molecular weight compounds, unsaturated polyester resins, polyester (meth)acrylate resins, epoxy (meth)acrylate resins, and urethane (meth)acrylate resins.

Specific examples of (meth)acrylates other than the compound represented by formula (1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, methoxypolyethylene glycol acrylate, polyalkylene glycol acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy Polyethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate Acrylates, tetrahydrofurfuryl alcohol polymeric acrylic acid ester, γ-butyrolactone (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-methyl -2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3,5-dimethyl-7-hydroxyadamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, methacryloyloxy norbornane (meth)acrylate, tetramethylpiperidinyl (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, (meth)acrylate having an imide ring, cyclic trimethylolpropane formal (meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate. i) acrylates, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, tricyclodecanedimethanol diacrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth) Acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenol F ethylene oxide modified di( meth)acrylate, bisphenol F propylene oxide-modified di(meth)acrylate, bisphenol A ethylene oxide-modified di(meth)acrylate, bisphenol A propylene oxide-modified di(meth)acrylate, isocyanuric acid ethylene oxide-modified di(meth)acrylate, isocyanuric acid Propylene oxide-modified di(meth)acrylate, ethylene oxide isocyanurate-modified tri(meth)acrylate, propylene oxide isocyanurate-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)acrylate and the like can be mentioned.

Specific examples of low-molecular-weight compounds having a radically polymerizable double bond other than (meth)acrylate include crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, N-vinylformamide, and 2-allyl. Methyl oxymethyl acrylate, 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.

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

The unsaturated polyester can be produced by polycondensing an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, itaconic acid, or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane Polyhydric alcohol such as 1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A is reacted as an alcohol component, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, Polybasic acids having no polymerizable unsaturated bonds, such as tetrahydrophthalic acid, adipic acid and sebacic acid, or their anhydrides are also added as acid components.

Polyester (meth)acrylate resins include (1) an epoxy compound containing an α,β-unsaturated carboxylic acid ester in a carboxyl-terminated polyester obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol; (Meth) acrylate resin obtained by reacting (2) saturated polybasic acid and / or unsaturated polybasic acid and polyhydric alcohol obtained by reacting a terminal carboxyl polyester with -OH containing acrylate obtained by reacting ( meth)acrylate resins, (3) (meth)acrylate resins obtained by reacting (meth)acrylic acid with a polyester having a terminal —OH obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol; mentioned.

Examples of saturated polybasic acids used as starting materials for polyester (meth)acrylate resins include polybasic acids having no polymerizable unsaturated bonds, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples include basic acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid, or anhydrides thereof. Furthermore, the polyhydric alcohol to be reacted as the alcohol component is the same as the unsaturated polyester.

Epoxy (meth)acrylate resins have polymerizable unsaturated bonds generated by ring-opening reaction between a compound having glycidyl (epoxy) and the carboxyl of a carboxyl compound having a polymerizable unsaturated bond such as (meth)acrylic acid. compound (vinyl ester). Epoxy (meth)acrylate resins dissolved in polymerizable monomers are usually used.

Compounds having glycidyl (epoxy) include bisphenol A diglycidyl ether and its high molecular weight analogs, novolac type glycidyl ethers, and the like. In addition to (meth)acrylic acid, it contains dibasic acid reactants such as bisphenol (for example, type A), adipic acid, sebacic acid, and dimer acid (Haridimer 270S (trade name, manufactured by Harima Kasei Co., Ltd.)). There may be.

As the urethane (meth)acrylate resin, for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, an --OH-containing (meth)acrylic compound and optionally an --OH-containing allyl ether compound are added. A radically polymerizable unsaturated group-containing oligomer obtained by the reaction is mentioned.

Examples of polyisocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Bannock D-750, Crisbon NK (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), Desmodur L (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name, Nippon Polyurethane Industry Co., Ltd.) ), Takenate D102 (trade name, manufactured by Mitsui Takeda Chemicals Co., Ltd.), Isonate 143L (trade name, manufactured by Mitsubishi Chemical Corporation), and the like.

Examples of polyhydroxy compounds include polyester polyols, polyether polyols, polycarbonate polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, etc. Specific examples include glycerin-ethylene oxide adducts, glycerin-propylene oxide adducts, Glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide propylene oxide adduct dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide propylene oxide adduct, etc. .

Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,2-butanediol, bisphenol A and Adduct with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1 ,4-cyclohexane glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, paraxylene glycol, bicyclohexyl-4 ,4-diol, 2,6-decalin glycol, 2,7-decalin glycol and the like.

The —OH-containing (meth)acrylic compound is not particularly limited, but —OH-containing (meth)acrylic acid esters are preferable, and specific examples include, for example, 2-hydroxyethyl (meth)acrylate, 2- Hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, tris(hydroxyethyl)isocyanuric acid mono(meth)acrylate, tris(hydroxyethyl) ) isocyanuric acid di(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like.

Organic resins include thermosetting resins and thermoplastic resins.
Examples of thermosetting resins include phenol resins, alkyd resins, melamine resins, epoxy resins, urea resins, urethane resins, and polyolefin resins such as polyethylene and polypropylene. acid-modified polyolefin resin obtained by modifying with, acid-modified ethylene rubber obtained by modifying each polymer of ethylene rubber with an acid having an unsaturated bond, and each polymer of a styrene elastomer modified with an acid having an unsaturated bond. and an acid-modified styrene-based elastomer formed by The acid used for acid modification is not particularly limited as long as it does not impair the effects of the present invention. Alternatively, a polymerized product of this monomer is added. These monomers and their polymers may be used alone, or may be used in combination.

Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, polymer type epoxy resin, biphenyl type epoxy resin, etc. epoxy resin, methylated melamine resin, butylated melamine resin, methyl etherified melamine resin, butyl etherified melamine resin, methylbutyl mixed etherified melamine resin, etc., polyisocyanate compounds having two or more isocyanates (O=C=N-R-N=C=O) and a polyol compound (HO-R'-OH) having two or more -OH, a polyamine (H ₂ N-R''-NH ₂ ), or Urethane resins and the like which can be obtained by reaction with compounds having active hydrogen ( _--NH.sub.2 , --NH, ---CONH--, etc.) such as water are preferable from the standpoint of workability.

Epoxy resins are excellent in heat resistance, adhesiveness and chemical resistance, melamine resins are excellent in heat resistance, hardness and transparency, and urethane resins are excellent in adhesiveness and low temperature curability. can be selected and used.
Examples of thermoplastic resins include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resins, acrylonitrile-butadiene-styrene resins, poly(meth)acrylate resins, ultra-high molecular weight polyethylene, poly-4- Methylpentene, syndiotactic polystyrene, polyamide (nylon 6: trade name of DuPont, nylon 6,6: trade name of DuPont, nylon 6,10: trade name of DuPont, nylon 6, T: trade name of DuPont, nylon MXD6 : DuPont trade name, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene oxide, fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: trade name of Unitika Ltd., Vectra: trade name of Polyplastics Co., Ltd., etc.), polyimide (Kapton: Toray Industries, Inc. ) trade name, AURUM: trade name of Mitsui Chemicals, Inc.), polyetherimide, polyamideimide, polybenzimidazole, polybenzoxazole, polyvinyl acetate resin, and the like.

Examples of inorganic resins include silicone resins.
Examples of silicone resins include thermosetting silicone resins such as addition-curing silicones and condensation-curing silicones, and modified silicone resins modified with functional groups.
The addition-curable silicone resin can be obtained by hydrosilylation reaction between a silicone having silanol and hydrosilyl and a silicone having alkenyl, or a silicone having hydrosilyl and a silicone having silanol and alkenyl. Catalysts used in the hydrosilylation reaction include transition metal catalysts, and examples of transition metal catalysts used include platinum, rhodium, iridium, ruthenium, palladium, molybdenum, iron, cobalt, nickel and manganese. Among these, platinum catalysts are more preferred. These catalysts can be used as homogeneous catalysts dissolved in a solvent, or as solid catalysts supported on carbon, silica, or the like. A phosphine, an amine, potassium acetate, or the like may be used in the form of coexistence. A preferred amount of the transition metal catalyst to be used is 1×10 ⁻⁶ to 1×10 ⁻² mol as transition metal catalyst atoms per 1 mol of hydrosilyl groups in the silicone resin.

A condensation-curing silicone resin can be obtained by subjecting a silicone containing alkoxysilyl and silanol to a dealcoholization and dehydration reaction. A condensation catalyst can be used in the condensation reaction for the purpose of accelerating the reaction. Examples of the condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, titanium complexes (for example, product names: ORGATICS TA-21, ORGATICS TA-30, ORGATICS TC-750, etc., Matsumoto Fine Chemical Co., Ltd. ), metal complexes such as tin complexes, and metal alkoxides. The amount of the silanol condensation catalyst in 100% by weight of the raw material used for the condensation reaction is, for example, 0.00001 to 0.1% by weight, preferably 0.00002 to 0.01% by weight, more preferably 0.0005 to 0.0005% by weight. 0.001% by weight.

A modified silicone resin modified with a functional group is a silicone in which a part of the organic group of the silicone resin is substituted with a functional group, and the functional groups include —NH ₂ , —OH, epoxy, —SH, —COOH, Vinyl, allyl, styryl, (meth)acryloyl may be mentioned. The substitution position of the functional group may be either the end of the silicone or the side chain.

A siloxane compound having a three-dimensional crosslinked structure can be used as the inorganic resin for the purpose of increasing the surface hardness and glass transition temperature of the cured film. Examples of siloxane compounds having a three-dimensional crosslinked structure include siloxane compounds having at least one type of unit selected from Q units consisting of the structural unit “SiO ₂ ” and T units consisting of the structural unit “RSiO _3/2 ”. can be done. In addition to at least one type of units selected from Q units and T units, the siloxane compound has at least one selected from M units consisting of the structural unit "R ₃ SiO _1/2 " and D units consisting of the structural unit "R ₂ SiO". It may further contain one type of unit. A siloxane compound having such a three-dimensional crosslinked structure can be obtained by hydrolytic condensation of a silane compound having a hydrolyzable group. A siloxane compound having a three-dimensional crosslinked structure is a siloxane compound mainly having a three-dimensional crosslinked structure, and is called a silicone resin or a silicone alkoxy oligomer.

Silane compounds having a hydrolyzable group include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, triphenylmethoxysilane, triphenyl Ethoxysilane, triphenylpropoxysilane, triphenylbutoxysilane, dimethylphenylmethoxysilane, triisopropylmethoxysilane, tricyclohexylmethoxysilane, dimethylethylethoxysilane, dimethylbutylethoxysilane, dimethylphenylethoxysilane, diethylphenylethoxysilane, dimethyldimethoxysilane Silane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane, methylethyldimethoxysilane, methylphenyldiethoxysilane, methylcyclohexyldimethoxysilane, methyltrimethoxysilane Silane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Propoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, propyltriethoxysilane, propyltripropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyl triethoxysilane, phenyltributoxysilane, phenyltriisopropoxysilane, 3-methylphenyltrimethoxysilane, 3-methylphenyltriethoxysilane, 4-methylphenyltriethoxysilane, cyclobutyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, cycloheptyltriethoxysilane, cyclooctyltrimethoxysilane, 4-methylcyclohexyltriethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 2 - Naphthyl trimethoxysilane, 2-naphthyltriethoxysilane, 1,1′-biphenyltriethoxysilane, 4-biphenyltrimethoxysilane, 5-triethoxysilyl-2-norbornene, 2-triethoxysilylnorbornene, tricyclo[3.3 .1.13,7]decane-1- triethoxysilylsilane , tricyclo[3.3.1.13,7]decane-2- triethoxysilylsilane , tetramethoxysilane, partial hydrolysis condensates of tetramethoxysilane (methyl silicate), tetraethoxysilane, partial hydrolysis condensate of tetraethoxysilane (ethyl silicate), polysiloxane compounds having silanol and/or alkoxysilyl (polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane), etc. can be mentioned. Examples of polysiloxane compounds having silanol and/or alkoxysilyl include 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, Silaplane FM99 series (trade name, manufactured by JNC Corporation), and the like. be done. A silane compound having such a hydrolyzable group may be used by being mixed with another siloxane compound having a three-dimensional crosslinked structure without hydrolytic condensation, and a siloxane compound having another three-dimensional crosslinked structure may be used in advance. It may be used by reacting with When used by being mixed with or reacted with another siloxane compound having a three-dimensional crosslinked structure, the reaction using a condensation catalyst proceeds rapidly, which is preferable. Orgaticus TA-21 and Orgaticus TA-30 (both trade names, manufactured by Matsumoto Fine Chemical Co., Ltd.), which are less colored, are suitable for forming a transparent cured film.

A siloxane compound having a three-dimensional crosslinked structure may be a silsesquioxane consisting only of T units. Silsesquioxanes are known to have a ladder structure, a complete condensation structure (cage structure), an incomplete condensation structure (partial cage structure), an amorphous structure (random structure), etc., and are hydrolyzable. It can be synthesized by hydrolytic condensation of a silane compound having three groups.

A siloxane compound having a three-dimensional crosslinked structure can also be used by purchasing a commercially available product. Examples of commercially available siloxane compounds having a three-dimensional crosslinked structure include RSN-0217, RSN-0220, RSN-0223, RSN-0249, RSN-0255, and RSN-6018 (all trade names, manufactured by Dow Corning Toray Co., Ltd.). , KR-220L, KR-220LP, KR-480, KR-216 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SR-21, SR-23, SR-13, SR-33 (all trade names) Name, manufactured by Konishi Chemical Industry Co., Ltd.), SO-1400, SO-1430, SO-1444, SO-1450, SO-1455, SO-1458, SO-1460 (all trade names, manufactured by Hybrid Plastics) can be mentioned.

The amount of the compound having a radically polymerizable double bond other than the compound represented by the formula (1), the organic resin, and the inorganic resin is preferably 1 to 20 parts per part by weight of the urea-bonded tetrafunctional (meth)acrylate. parts by weight, more preferably 2 to 10 parts by weight. If the amount used is 1 part by weight or more, a cured film having sufficient heat resistance and electrical insulation can be obtained. On the other hand, if the amount used is 20 parts by weight or less, the polymerization rate becomes slow and the reaction rate does not decrease.

Organic resins and inorganic resins preferably have —OH as a component. When a resin having —OH is used as the matrix resin, the urea bond of the urea-bonded tetrafunctional (meth)acrylate of the present invention and —OH, which is a component of the matrix resin, can be hydrogen-bonded. Therefore, a resin having no photocurable substituent can be fixed by hydrogen bonding, and a cured film can be formed by irradiating light such as ultraviolet rays or visible light. Thus, by using matrix resins having various properties, photocurable compositions having desired properties can be prepared.

The composition of the invention may contain a solvent.
Solvents that can be used in the present invention include diethyl ether, tetrahydrofuran, diphenyl ether, dimethoxybenzene, acetone, methanol, ethanol, isopropanol, butyl alcohol, t-butyl alcohol, benzyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propio Nitrile, benzonitrile, ethylene carbonate, propylene 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, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-oxy-2-methylpropionate, Ethyl 2-oxy-2-methylpropionate, Methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate , methyl pyruvate, 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 mono Ethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Dipropylene Glycol Monoethyl Ether Acetate, Dipropylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Monobutane Tyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether , tetraethylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.
Among these, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, butyl acetate, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone and propylene glycol monomethyl ether are preferred.
The solvent used in the present invention may be one kind or a mixture of two or more kinds.

The amount of the solvent used is the total amount of the urea-bonded tetrafunctional (meth)acrylate compound, the compound having a radically polymerizable double bond other than the urea-bonded tetrafunctional (meth)acrylate compound, the organic resin, and the inorganic resin. 1 to 80% by weight in 100% by weight of the composition containing

Since the composition of the present invention has (meth)acryloyl as a reactive functional group, it preferably contains a polymerization initiator for forming a cured film. A photopolymerization initiator can be used as the polymerization initiator, and by irradiating with active energy rays such as ultraviolet rays or visible rays, a polymerization reaction of reactive monomers can be caused to obtain a cured product. Such photoinitiators include benzophenone, Michler's ketone, 4,4′-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy- 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl }-2-methyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benz anthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl) benzophenone, 3,3′,4,4′-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3′-di(methoxycarbonyl)-4,4′-di(t-butylperoxycarbonyl)benzophenone, 3, 4'-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(4'-Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine , 2-(2′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2′-methoxystyryl)-4,6-bis(trichloromethyl)-s- triazine, 2-(4'-pentyl-o xystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1, 3-bis(trichloromethyl)-5-(2′-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4′-methoxyphenyl)-s-triazine, 2-(p- dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4 ',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1 ,2′-biimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2 ,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′, 5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n -dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium , bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Among these, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-(dimethylamino)- 2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone is preferred.
The above photopolymerization initiators may be used singly or in combination of two or more.

A cured film can also be obtained by causing a polymerization reaction with heat. That is, a thermosetting composition can be obtained by adding a thermal polymerization initiator. Examples of such thermal polymerization initiators include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyesters, azo compounds and persulfates. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The amount of the polymerization initiator used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, per 100 parts by weight of the urea-bonded tetrafunctional (meth)acrylate. When the amount of the polymerization initiator used is 0.1 parts by weight or more, a sufficient polymerization rate can be obtained and the inhibition of polymerization by oxygen or the like is not likely to occur. On the other hand, if the amount of the polymerization initiator used is 20 parts by weight or less, the residue of the polymerization initiator remains in the cured film, and the adhesion strength and heat resistance of the resulting cured film are not lowered, and sufficient adhesion strength is obtained. A cured film having heat resistance and heat resistance can be obtained. Furthermore, it does not cause coloring.

The composition of the present invention may further contain other components from the viewpoint of adjusting various physical properties and from the viewpoint of curing during subsequent film formation within a range that does not impair heat resistance. Such other components include active energy ray sensitizers, polymerization inhibitors, polymerization initiation aids, leveling agents, surfactants, plasticizers, UV absorbers, light stabilizers, antioxidants, antistatic agents. , and silane coupling agents.

<Hardened film>
The cured film of the present invention is obtained from a urea-bonded tetrafunctional (meth)acrylate compound or a composition containing a urea-bonded tetrafunctional (meth)acrylate compound. The cured film is formed, for example, by applying a urea-bonded tetrafunctional (meth)acrylate compound or composition to the substrate surface and then curing the coating film by irradiating it with light such as ultraviolet light or visible light. By blending a urea-bonded tetrafunctional (meth)acrylate compound, photocurability can be imparted to a composition containing 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 well-balanced adhesion to substrates such as metals and resins. Therefore, the application of the cured film of the present invention is not particularly limited, but it is suitable as an insulating film or the like for protecting the surface of metal wiring forming a predetermined circuit pattern.

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

In addition, as exposure equipment, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, halogen lamp, electrodeless lamp, UV-LED lamp, etc. are installed, and ultraviolet rays and visible rays in the range of 200 to 500 nm are installed. It is preferable that the device is an apparatus for irradiating such as. Since the urea-bonded tetrafunctional (meth)acrylate compound of the present invention has high reactivity, it can be cured at a high reaction rate equivalent to the case of using a high-pressure mercury lamp by using a low-energy UV-LED lamp or the like as a light source. can be made Therefore, according to a composition containing a urea-bonded tetrafunctional (meth)acrylate compound, a cured film having good heat resistance can be produced using a low-energy light source.

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

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

Substrates that can be used in the present invention include polyester resin substrates made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.; polyolefin resin substrates made of polyethylene, polypropylene, etc.; Organic polymer films made of styrene resins, polyamides, polycarbonates, polyimides, etc.; substrates made of cellophane; metal foils; laminated films of resin substrates and metal foils made of polyimide or the like; laminates of glass epoxy resins and metal foils; Glassine paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol, starch, carboxymethyl cellulose (CMC), etc., which have a sealing effect; papers treated with sealing; Silicon-based substrates such as silicon wafers, silicon nitride substrates, and silicon oxide substrates; Glass substrates, such as a glass wafer and a quartz substrate, are mentioned.

These substrates may further contain pigments, dyes, antioxidants, antidegradants, fillers, ultraviolet absorbers, antistatic agents and/or electromagnetic wave inhibitors, etc., as long as they do not adversely affect the effects of the present invention. may contain additives.
At least part of the surface of the substrate may be subjected to surface treatment such as water-repellent treatment, corona treatment, plasma treatment, and/or blasting, if necessary. A coat film may be provided.

The thickness of the cured film of the present invention may be appropriately selected depending on the intended use, preferably 1 μm to 50 μm, more preferably 5 μm to 20 μm.

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

Electronic circuit boards include rigid boards, flexible boards, rigid flexible boards, and the like.
As the flexible substrate, for example, an ink containing the urea-bonded tetrafunctional (meth)acrylate compound of the present invention is applied all over or in a predetermined pattern on a film-like substrate such as a polyimide film on which wiring is formed in advance by an inkjet method or the like. Examples include substrates obtained by coating in a shape (line shape, etc.) to form a coating film, and then curing the coating film.

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

<Electronic parts>
The electronic component of the present invention includes a cured film or a substrate with a cured film. Flexible electronic parts and display elements can be obtained by using a cured film or a substrate with a cured film using a film substrate as the substrate.
For example, IC chips, capacitors, resistors, fuses, etc. are attached to electronic circuit boards manufactured using the cured film of the present invention, which is excellent in heat resistance, electrical insulation, adhesion to substrates, folding endurance and flame retardancy. By mounting, for example, an electronic component for a liquid crystal display element can be produced.

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

<Silicon compound A>

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

<Silicon compound B>

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

<Aromatic compound C>

[Synthesis Example 4]
<Synthesis example of urea-bonded 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 stirred at room temperature under a nitrogen atmosphere. 6.6 g of an aromatic diamine compound (9,9-bis(4-aminophenyl)fluorene, manufactured by Tokyo Kasei Co., Ltd.) diluted with 50.0 g of tetrahydrofuran was added dropwise to the solution over 8 minutes. Stirred for hours. Further, 5.2 g of BEI was added dropwise to the reaction solution, and the mixture was stirred at 50° C. for 1 hour. The resulting reaction solution was extracted with ethyl acetate-water, washed with saturated brine, and the extract was dried over magnesium sulfate. The extract and magnesium sulfate were separated by filtration, and the solvent was removed with an evaporator to obtain a concentrate. A white solid was obtained by allowing it to stand at room temperature for recrystallization. The resulting white solid was washed with ethyl acetate and then vacuum-dried to completely remove the solvent, yielding urea-bonded tetrafunctional acryl-modified aromatic compound D (8.5 g, hereinafter appropriately referred to as “aromatic compound D”). ) was obtained. Aromatic compound D is shown below.

<Aromatic compound D>

[Comparative Synthesis Example 1]
<Synthesis example of urea-bonded bifunctional acryl-modified silicon compound E>
0.85 g of a siloxane diamine compound (trade name: BY16-871, manufactured by Dow Corning Toray Co., Ltd.) and 0.02 g of 4-methoxyphenol were dissolved in 8.00 g of tetrahydrofuran and stirred at room temperature under a nitrogen atmosphere. 1.15 g of 2-acryloyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko K.K., hereinafter referred to as “AOI” as appropriate) was added dropwise to the solution, and the mixture was stirred at 20 to 30° C. for 1 hour. The resulting reaction solution was subjected to solvent removal by an evaporator, then hexane (10.0 g) was added dropwise, and excess AOI was removed by decantation. After removing the supernatant liquid, the solvent was removed from the resulting solution using a vacuum pump to obtain urea-bonded bifunctional acryl-modified silicon compound E (1.6 g, hereinafter referred to as “silicon compound E” as appropriate). . Silicon compound E is shown below.

<Silicon compound E>

[Comparative Synthesis Example 2]
<Synthesis example of urethane-bonded tetrafunctional acrylic-modified silicon compound F>
To a solution containing 8.29 g of a siloxane diol compound (trade name: FM4401, manufactured by JNC Corporation) and 0.2 g of 4-methoxyphenol, 11.72 g of BEI was added dropwise and stirred at 60°C. Subsequently, 0.1 g of zirconium tetraacetylacetonate (trade name: Orgatics ZC-150, manufactured by Matsumoto Fine Chemicals Co., Ltd.) dissolved in 10.00 g of MEK was added dropwise to the solution, and the mixture was stirred at 60° C. for 2 hours. The solvent was removed from the resulting reaction solution using an evaporator. An MEK solution (24.79 g, solid content concentration 84 wt %) of urethane-bonded tetrafunctional acryl-modified silicon compound F (hereinafter referred to as “silicon compound F” as appropriate) was obtained. Silicon compound F is shown below.

<Silicon compound F>

[Synthesis Example 5]
<Synthesis example of urea-bonded tetrafunctional acrylic-modified aromatic compound G>
Dissolve 4.73 g of an aromatic diamine compound (trade name: 4,4-diaminodiphenyl ether, manufactured by Tokyo Kasei Co., Ltd.) and 0.16 g of 4-methoxyphenol in a mixed solvent of 50.00 g of acetonitrile and 50.00 g of acetone, and The mixture was stirred at room temperature under atmosphere. 11.10 g of BEI was added dropwise to the solution and stirred at 60°C. Subsequently, 0.08 g of zirconium tetraacetylacetonate (trade name: Orgatics ZC-150, manufactured by Matsumoto Fine Chemicals 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 was removed from the resulting reaction solution using an evaporator and a vacuum pump. By performing recrystallization at room temperature, urea-bonded tetrafunctional acryl-modified aromatic compound G (15.11 g, hereinafter referred to as “aromatic compound G” as appropriate) was obtained. Aromatic compound G is shown below.

<Aromatic compound G>

<Preparation of composition 1>
1.200 g of the silicon compound A synthesized in Synthesis Example 1, 0.045 g of an alkylphenone photopolymerization initiator (trade name: Irgacure 127, manufactured by BASF, hereinafter referred to as "IC127") as a curing agent, and 2.100 g of MEK as a solvent. and 0.700 g of N-methyl-2-pyrrolidone (hereinafter referred to as “NMP” as appropriate) were mixed at room temperature to obtain composition 1 of the present invention.

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

<Preparation of composition 3>
0.120 g of the silicon compound A synthesized in Synthesis Example 1 and 1.080 g of a siloxane compound having a three-dimensional crosslinked structure (trade name: SR-21, manufactured by Konishi Chemical Industry Co., Ltd., hereinafter referred to as “SR-21” as appropriate); Composition 3 of the present invention was obtained by mixing 0.020 g of IC127 as a curing agent, 2.100 g of MEK and 0.700 g of NMP as solvents.

<Preparation of composition 4>
Composition 4 of the present invention was obtained in the same manner as composition 3, except that silicon compound B was used instead of silicon compound A.

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

<Preparation of composition 6>
Composition 6 of the present invention was obtained in the same manner as Composition 5, except that Irgacure 379EG (trade name, manufactured by BASF, hereinafter referred to as “IC379EG” as appropriate) was used instead of IC127.

<Preparation of composition 7>
0.180 g of the silicon compound A synthesized in Synthesis Example 1, 1.020 g of SR-21, 0.027 g of IC379EG as a curing agent, and 2.100 g of MEK and 0.700 g of NMP as a solvent were mixed to obtain composition 7 of the present invention. rice field.

<Preparation of Composition 8>
Composition 8 of the present invention was obtained in the same manner as for Composition 3, except that Silicon Compound E synthesized in Comparative Synthesis Example 1 was used instead of Silicon Compound A.

Ａ，Ｂ：ケイ素化合物（四官能）、Ｅ：ケイ素化合物（二官能）
ＳＲ－２１：３次元架橋構造を有するシロキサン化合物The components contained in Compositions 1 to 8 described above are shown in Table 1 below (unit: g).

A, B: silicon compound (tetrafunctional), E: silicon compound (difunctional)
SR-21: Siloxane compound having a three-dimensional crosslinked structure

[Example 1]
The composition 1 was applied onto a glass substrate cut to 4 cm×4 cm, and spin-coated at a rotation speed of 300 rpm. Then, after drying for 5 minutes on a hot plate heated to 80 ° C., and further drying for 5 minutes on a hot plate heated to 135 ° C., a high-pressure mercury irradiation device (trade name: 8 kW × 1 conveyor type ultraviolet curing device (manufactured by Eye Graphics Co., Ltd.) under the condition of 1,000 mJ/cm ² to obtain a cured film. The resulting cured film was a non-sticky and colorless transparent film. The exposure dose was measured using an illuminometer (UVPF-A1/PD-365, manufactured by Iwasaki Electric Co., Ltd.).

[Example 2]
A cured film was obtained in the same manner as in Example 1, except that Composition 2 was used instead of Composition 1. The resulting cured film was a non-sticky and colorless transparent film.

[Example 3]
A cured film was obtained in the same manner as in Example 1, except that Composition 3 was used instead of Composition 1 and that the composition was applied onto a glass substrate cut to 10 cm×10 cm.

[Example 4]
A cured film was obtained in the same manner as in Example 3, except that Composition 4 was used instead of Composition 3.

[Comparative Example 1]
A cured film was obtained in the same manner as in Example 3, except that Composition 8 was used instead of Composition 3.

<Evaluation of cured film>
<5% Weight Loss Temperature>
Using a simultaneous differential thermal thermogravimetric analyzer (TG/DTA6200, manufactured by Hitachi High-Tech Science Co., Ltd.), the temperature was measured in the range of 40°C to 550°C. In order to eliminate an error due to moisture absorption of the film, the weight at 100° C. was assumed to be 100%, and the temperature at which the weight was reduced by 5% was defined as the 5% weight loss temperature. Table 2 shows the results.

<Measurement of reaction rate 1>
[Example 5]
The composition 5 was applied onto a glass substrate cut to 4 cm×4 cm and spin-coated at a rotation speed of 300 rpm. After that, it was dried for 5 minutes on a hot plate heated to 80°C, and further dried for 5 minutes on a hot plate heated to 135°C. The reaction rate of acryloyl was measured by changing the range of 2,500 mJ/cm ² . The reaction rate was obtained by the following method.

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

[Example 6]
Same as Example 5 except that composition 6 was used and photocured with a UV-LED irradiation conveying device (trade name: LSS-08A, manufactured by Sun Energy Co., Ltd.) instead of the high-pressure mercury irradiation device of Example 5. The reaction rate of acryloyl was measured by the same method. Table 3 shows the results.

In general, the amount of energy of ultraviolet rays irradiated by the UV-LED irradiation and transport device used in Example 6 is smaller than that of the high-pressure mercury irradiation device, so even if a curing agent suitable for the LED light source is used, the reaction rate is low. going down. However, from the results of Examples 5 and 6, even when the UV-LED irradiation transport device is used, by selecting a curing agent suitable for the light source, the reaction rate is the highest in UV curing of acrylate. It can be seen that a cured film can be produced with a reaction rate comparable to that of As is clear from these evaluation results, by using the composition containing the urea-bonded tetrafunctional (meth)acrylate compound of the present invention, even when using a UV-LED irradiation conveying device, compared to when using a high-pressure mercury irradiation device, A comparable cured film could be formed.

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

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

<Preparation of composition 10>
Composition 10 of the present invention was obtained in the same manner as Composition 9, except that Silicon Compound F synthesized in Comparative Synthesis Example 2 was used instead of Silicon Compound A.

[Example 8]
Composition 9 was applied onto a glass substrate cut to 4 cm×4 cm and spin-coated at a rotation speed of 300 rpm. After that, it is dried for 5 minutes on a hot plate heated to 80 ° C., further dried for 5 minutes on a hot plate heated to 135 ° C., and then 1,000 mJ with the same UV-LED irradiation transport device as in Example 6. / cm ² to obtain a cured film. The resulting cured film was a non-sticky and colorless transparent film.

[Comparative Example 2]
A cured film was obtained in the same manner as in Example 8 except that Composition 10 was used instead of Composition 9.

<Evaluation of cured film>
<Glass transition temperature>
Using a rigid pendulum type viscoelasticity measuring device (manufactured by A&D Co., Ltd., "RPT-3000W"), the temperature was raised from 40°C to 220°C, and the glass transition temperature (Tg) was measured. Table 4 shows the results.

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

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

<Preparation of composition 12>
Composition 12 of the present invention was obtained in the same manner as Composition 11, except that Silicon Compound F synthesized in Comparative Synthesis Example 2 was used instead of Silicon Compound A.

<Measurement of reaction rate 2>
[Example 9]
Composition 11 was applied onto a glass substrate cut to 4 cm×4 cm and spin-coated at a rotation speed of 300 rpm. Then, after drying for 5 minutes on a hot plate heated to 80 ° C. and further drying for 5 minutes on a hot plate heated to 135 ° C., the exposure amount is adjusted with the same UV-LED irradiation transport device as in Example 6. The reaction rate of acryloyl was measured by changing the range from 400 to 1,500 mJ/cm ² . The reaction rate was determined in the same manner as in Example 5.

[Comparative Example 3]
The reaction rate of acryloyl was measured in the same manner as in Example 9, except that composition 12 was used instead of composition 11. Table 5 shows the results.

As is clear from the evaluation results, the cured film obtained by curing the composition containing the (meth)acrylate compound with a urea bond of the present invention is higher than the (meth)acrylate compound with a urethane bond. had reactivity. In particular, at relatively low exposure doses of 1,000 (mJ/cm ² ) or less, the (meth)acrylate compound with a urea bond exhibited remarkably higher reactivity than the (meth)acrylate compound with a urethane bond. .
From this result, it can be said that the reactivity of a compound having a urea bond is affected by the bonding mode of the main chain.

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

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

<Preparation of composition 15>
Composition 15 of the present invention was obtained in the same manner as composition 13, except that aromatic compound G synthesized in Synthesis Example 5 was used instead of aromatic compound C.

[Example 10]
Composition 13 was applied onto a glass substrate cut to 10 cm×10 cm, and spin-coated at 300 rpm. After that, it is dried for 5 minutes on a hot plate heated to 80 ° C., further dried for 5 minutes on a hot plate heated to 135 ° C., and then 1,000 mJ with the same UV-LED irradiation transport device as in Example 6. / cm ² to obtain a cured film. The resulting cured film was a non-sticky and colorless transparent film.

[Example 11]
A colorless and transparent cured film was obtained in the same manner as in Example 10 except that Composition 14 was used instead of Composition 13.

[Example 12]
A cured film was obtained in the same manner as in Example 10, except that Composition 15 was used instead of Composition 13.

<Evaluation of cured film>
<5 to 20% weight loss temperature>
Using the same differential thermal thermogravimetric simultaneous measurement device as in Example 3, the measurement was carried out in the range of 40°C to 550°C. In order to eliminate errors due to moisture absorption of the film, the weight at 100° C. was taken as 100%, and the temperatures at which the weight decreased by 5 to 20% were defined as 5%, 10%, and 20% weight loss temperatures, respectively. Table 6 shows the results.

評価結果から明らかなように、本発明のウレア結合型四官能アクリル変性芳香族化合物を含む組成物は優れた耐熱性を示すことがわかる。また、主鎖に四つ芳香環を有する化合物を含む組成物は、主鎖に二つ芳香環を有する化合物を含む組成物に比べて、組成物を硬化させることによって優れた耐熱性を有する硬化皮膜が得られた。
この結果から、ウレア結合を備えた（メタ）アクリレート化合物は、主鎖に結合している芳香環の数が耐熱性に影響するといえる。主鎖に芳香環を有するウレア結合型（メタ）アクリレート化合物では、芳香環の数を四つにすることにより、ウレア結合型（メタ）アクリレート化合物と光重合開始剤とを含む組成物により形成される硬化皮膜の耐熱性が良好になることが分った。

As is clear from the evaluation results, the composition containing the urea-bonded tetrafunctional acryl-modified aromatic compound of the present invention exhibits excellent heat resistance. In addition, a composition containing a compound having four aromatic rings in its main chain exhibits excellent heat resistance when cured, compared to a composition containing a compound having two aromatic rings in its main chain. A film was obtained.
From this result, it can be said that the heat resistance of (meth)acrylate compounds with urea bonds is affected by the number of aromatic rings bonded to the main chain. A urea-bonded (meth)acrylate compound having an aromatic ring in the main chain is formed by a composition containing a urea-bonded (meth)acrylate compound and a photopolymerization initiator by setting the number of aromatic rings to four. It was found that the heat resistance of the cured film was improved.

[Synthesis Example 6]
<Synthesis example of a siloxane compound having a silanol-containing three-dimensional crosslinked structure>
31.8 g of phenyltrimethoxysilane, 33.5 g of tetraethoxysilane, 4.9 g of dimethyldimethoxysilane and 34 g of diethylene glycol ethyl methyl ether were placed in a 200 ml three-necked flask equipped with a dropping funnel, a reflux condenser and a thermometer. 0.3 g was charged and sealed with dry nitrogen. After stirring at room temperature for 30 minutes while stirring with a magnetic stirrer, 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, the mixture was heated in an oil bath at 90° C. for 1.5 hours, 100° C. for 1 hour, and 140° C. for 2.5 hours to stop distillation of the generated methanol and ethanol. was confirmed to terminate the reaction. The mixture was allowed to cool to room temperature, mixed with 100 g of ethyl acetate, and then washed with water using a separating funnel until the pH became neutral. Thereafter, the solution was concentrated at room temperature using an evaporator until the weight of the solution reached 50 g, to prepare a siloxane compound solution (matrix A) having a solid concentration of 44% by weight and a silanol-containing three-dimensional crosslinked structure.

Using the same Fourier transform infrared spectrophotometer as in Example 5, the IR spectrum of matrix A was measured. Due to the presence of a peak at 920 cm ⁻¹ attributed to silanol, silanol ( 920 cm ⁻¹ ) was included. Further, the weight average molecular weight (Mw) of matrix A determined by GPC analysis was 41,300, and the molecular weight distribution (Mw/Mn) was 5.2. GPC analysis was performed under the conditions shown below.
<GPC>
Apparatus: LC-2000Plus series manufactured by JASCO Corporation (detector: differential refractometer)
Solvent: THF/DMF = 1/1 (v/v)
Flow rate: 0.5ml/min
Column temperature: 40°C
Column used: Showa Denko KK, Asahipak GF-1G 7B (guard column) + Asahipak GF-7M HQ, exclusion limit molecular weight (PEG) = 10,000,000)
Standard sample for calibration curve: PSt

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

[Example 13]
Composition 16 was applied onto a glass substrate cut to 4 cm×4 cm and spin-coated at a rotation speed of 300 rpm. Then, it was dried on a hot plate heated to 80° C. for 5 minutes, and further dried on a hot plate heated to 135° C. for 5 minutes to prepare two uncured films. Only one of the uncured films was photocured under the condition of 1,000 mJ/cm ² with the same high-pressure mercury irradiation apparatus as in Example 1 to obtain a cured film, and the remaining one was used as an uncured film. The exposure amount was measured using the same illuminometer as in Example 1. Solvent resistance of the prepared uncured film and cured film was evaluated under the following conditions.

<Solvent resistance evaluation>
The uncured film and cured film obtained in Example 13 were immersed in NMP for 15 minutes at room temperature together with the glass substrate, the weight of the film before and after immersion was measured, and the residual film ratio was calculated using the following formula. , the residual film ratio of the uncured film was 4%, and the residual film ratio of the cured film was 83%.
Remaining film ratio = (W1-W2)/W1
(W1: film weight before immersion, W2: film weight after immersion)

This result indicates that the cured film obtained by reaction with acryloyl exhibits solvent resistance even though the silicon compound A is contained in an amount of only 10% by weight. This result suggests that the silicon compound A and the siloxane compound having a three-dimensional crosslinked structure contained in the matrix A form hydrogen bonds.

ＳＲ－２３（小西化学工業（株）製）：３次元架橋構造を有するシロキサン化合物
ＤＭＤＭＳ（東京化成（株）製）：ジメチルジメトキシシラン
ＴＡ－３０（マツモトファインケミカル（株）製）：オルガチックスＴＡ－３０[Examples 14 to 16]
Compositions 17 to 19 were prepared according to the formulations shown in Table 7, and cured films were produced in the same manner as in Example 8.
<Evaluation of heat-resistant adhesion>
The adhesiveness of each cured film prepared using Compositions 17 to 19 before and after the heating test at 200° C. for 30 minutes was evaluated by a cross-cut peel test. The tape for evaluation was No. 3M manufactured by 3M. 610 was used. A sample with no peeling was evaluated as "○", and a sample with 1 to 100 peels was evaluated as "X". As a result, as shown in Table 7, all the cured films showed good adhesion before and after the heating test. Since no cracks were generated in any of the cured films after the heating test, the photocurable resin composition of the present invention can be suitably used as an insulating film for semiconductors requiring a heating process.

SR-23 (manufactured by Konishi Chemical Industry Co., Ltd.): a siloxane compound having a three-dimensional crosslinked structure DMDMS (manufactured by Tokyo Kasei Co., Ltd.): dimethyldimethoxysilane TA-30 (manufactured by Matsumoto Fine Chemicals Co., Ltd.): ORGATICS TA- 30

The compound of the present invention has excellent reactivity even in an LED light source, and can be used as a protective film for optical device materials that pose a problem of deterioration due to ultraviolet rays. Moreover, since the composition of the present invention has excellent heat resistance and electrical insulating properties, it can be used as an insulating film for electronic parts such as semiconductors.

Claims (9)

A urea-bonded tetrafunctional (meth)acrylate compound represented by the following formula (1),
A urea-bonded tetrafunctional (meth)acrylate compound in which A in formula (1) is a divalent organic group derived from an aromatic diamine compound having 4 or more aromatic rings .

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

(In formula (2), R ₁ and R ₂ are independently hydrogen or methyl.) A urea-bonded tetrafunctional (meth)acrylate compound represented by the following formula (1),
A urea -bonded tetrafunctional (meth)acrylate compound in which A in formula (1) is a divalent organic group having a structure represented by formula (3).

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

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

(R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ in formula (3) are each independently hydrogen or alkyl having 1 to 30 carbon atoms, and Z is alkylene having 1 to 4 carbon atoms. and n is an integer from 0 to 150.) 3. The urea-bonded tetrafunctional (meth)acrylate compound according to claim 1 or 2 , wherein m in formula (1) is 0. 3. The urea-linked tetrafunctional (meth)acrylate compound according to claim 2 _, wherein R3, _R4 , R5, R6, _R7 and R8 _{in formula} ( ₃ ) are methyl and Z is trimethylene. A composition comprising the urea-bonded tetrafunctional (meth)acrylate compound according to claim 1 or 2 . A composition comprising the urea-bonded tetrafunctional (meth)acrylate compound according to claim 2 and a siloxane compound having a three-dimensional crosslinked structure. 7. The composition according to claim 6 , comprising 1 to 20 parts by weight of the siloxane compound having a three-dimensional crosslinked structure with respect to 1 part by weight of the urea-bonded tetrafunctional (meth)acrylate compound. A cured film obtained from the urea-bonded tetrafunctional (meth)acrylate compound according to claim 1 or 2 . An electronic component having the cured film according to claim 8 .