CN111448224A

CN111448224A - Urea-bonded tetrafunctional (meth) acrylate compound and composition containing same

Info

Publication number: CN111448224A
Application number: CN201980006338.9A
Authority: CN
Inventors: 养王田昌昭; 安井平; 及川尚夫; 山广干夫
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2018-04-06
Filing date: 2019-03-29
Publication date: 2020-07-24
Also published as: JP7205538B2; JPWO2019194108A1; KR20200140789A; WO2019194107A1; TW201943693A; WO2019194108A1; TW202003449A; JPWO2019194107A1

Abstract

The invention provides a novel compound which can be preferably used as a material of an insulating film in an electronic component and has excellent heat resistance, and a composition containing the same. A urea-bonded tetrafunctional (meth) acrylate compound represented by the following formula (1). (in the formula (1), A is a divalent organic group, Y is a C1-18 linear alkylene or branched alkylene, in the case of the carbon number of the alkylene is 2 or more, can insert an oxygen atom (-O-) between arbitrary C-C bonds, can also insert-CO-between terminal C-N bonds, m is 0 or 1, X is the following formula (2) expressed by the group) (in the formula (2), R₁And R₂Independently is hydrogen or methyl)

Description

Urea-bonded tetrafunctional (meth) acrylate compound and composition containing same

Technical Field

The present invention relates to a novel urea-bonded tetrafunctional (meth) acrylate compound useful as a material for an insulating film in electronic parts such as printed wiring boards and semiconductor package substrates, and a composition containing the same.

Background

In recent years, in response to a demand for weight reduction of a portable terminal including a display portion such as a liquid crystal, it has been studied to change a material of a member of an electronic component from glass to plastic. Since plastics have inferior scratch resistance compared to glass, a method of preventing scratches by surface treatment with a hard coating agent is widely used. As a compound for improving scratch resistance of a hard coating agent, a curable organopolysiloxane having (meth) acryloyl groups at both molecular terminals, which is obtained by reacting an isocyanate-containing (meth) acrylate with an organopolysiloxane having — OH groups at both molecular terminals, has been proposed (patent documents 1 and 2). Further, a radiation-curable organopolysiloxane composition having excellent adhesion to a plastic substrate and excellent deep-part curing properties has also been proposed (patent document 3). However, patent documents 1 and 2 have a problem in that the scratch resistance of a cured film formed from a compound or a composition is improved, and there is no description about heat resistance. Patent document 3 has a problem in adhesion of the composition, and does not describe heat resistance.

A curable composition containing a polyfunctional acrylate compound has been proposed, which aims to provide excellent 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 adhesion, high heat resistance, good chemical resistance, and the like (patent document 5).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2015-196748

Patent document 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

Disclosure of Invention

Problems to be solved by the invention

The curable composition described in patent document 4 is used for a color filter, and is not preferable as a material of an insulating film in an electronic component, and patent document 5 discloses a general-purpose curable composition that can be used for various applications such as a resist, a seal, a paint, an adhesive, a printing plate, a printing correction, a lens, a dental material, a surface treatment, a battery material, and the like, and does not describe reactivity when curing is performed using a light source with low energy of ultraviolet rays such as a light emitting diode (L ED) light source, and in particular, does not specify a material of an insulating film that requires heat resistance and electrical insulation.

Accordingly, an object of the present invention is to provide a novel compound having excellent heat resistance and reactivity, which is preferable as a material for an insulating film in an electronic component such as a printed wiring board or a semiconductor package substrate, and a composition containing the same.

Means for solving the problems

The present invention is based on a novel finding that a novel urea-bonded tetrafunctional (meth) acrylate compound having a urea bond and a (meth) acryloyl group is used, whereby a cured film having excellent heat resistance and electrical insulation properties, which is preferable as a material for an insulating film in an electronic component, can be obtained by curing the compound at a high reaction rate even with a light source having low energy of ultraviolet rays such as an L ED light source, and the like.

[1] A urea-bonded tetrafunctional (meth) acrylate compound represented by the following formula (1);

[ solution 1]

(in the formula (1), A is a divalent organic group, Y is a C1-18 linear alkylene or branched alkylene, in the alkylene carbon number is more than 2 cases, can be arbitrary C-C bond inserted between oxygen atoms (-O-), can also be in the terminal C-N bond inserted between-CO-, m is 0 or 1, X is the following formula (2) expressed as the group)

[ solution 2]

(in the formula (2), R₁And R₂Independently hydrogen or methyl).

[2] The urea bond type tetrafunctional (meth) acrylate compound according to [1], wherein A in the formula (1) is a divalent organic group having three or more aromatic rings.

[3] The urea bond type tetrafunctional (meth) acrylate compound according to [1], wherein A in the formula (1) is a divalent organic group having a structure represented by the formula (3);

[ solution 3]

(R in the formula (3))₃、R₄、R₅、R₆、R₇And R₈Each independently represents hydrogen or an alkyl group having 1 to 30 carbon atoms, Z represents an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 to 150).

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

[5]According to [3]Or [4]]The urea-bonded tetrafunctional (meth) acrylate compound, wherein R in the formula (3)₃、R₄、R₅、R₆、R₇And R₈Is methyl and Z is trimethylene.

[6] A composition comprising the urea-bonded type tetrafunctional (meth) acrylate compound according to any one of [1] to [5 ].

[7] A composition comprising the urea-bonded type tetrafunctional (meth) acrylate compound according to [3], and a siloxane compound having a three-dimensional crosslinking structure.

[8] The composition according to [7], wherein the siloxane compound having a three-dimensional crosslinking structure is contained in an amount of 1 to 20 parts by weight relative to 1 part by weight of the urea-bonded tetrafunctional (meth) acrylate compound.

[9] A cured coating film obtained from the urea-bonded tetrafunctional (meth) acrylate compound according to any one of [1] to [5] or the composition according to any one of [6] to [8 ].

[10] An electronic component having the cured coating film according to [9 ].

ADVANTAGEOUS EFFECTS 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 L ED light source having a small energy and cure the compound at a high reaction rate, and by using a composition containing the urea-bond type tetrafunctional (meth) acrylate compound, it is possible to obtain a cured film having excellent heat resistance and electrical insulation which is preferable as a material for an insulating film or the like of an electronic component such as a printed wiring board or a semiconductor package substrate, and further, by optimizing the structure of the urea-bond type tetrafunctional (meth) acrylate compound, it is possible to adjust the compatibility of the composition and the flexibility of the cured film.

Detailed Description

The 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).

[ solution 4]

(in the formula (1), A is a divalent organic group, Y is a C1 ~ 18 linear alkylene or branched alkylene, in the above-mentioned alkylene carbon number is more than 2 cases, can be arbitrary C-C bond inserted between oxygen atom (-O-), can also be in the terminal C-N bond inserted between-CO-, m is 0 or 1, X is the following formula (2) represents the group

[ solution 5]

(in the formula (2), R₁、R₂Is hydrogen or methyl)

In the present specification, "(meth) acrylate" is used to indicate both or either of acrylate and methacrylate.

In the reaction of the (meth) acrylate, the double bond of the (meth) acryloyl group undergoes radical polymerization, and thus the "functional" moiety is a (meth) acryloyl group. The urea-bonded tetrafunctional (meth) acrylate means the following (meth) acrylate: the divalent organic group A has a structure represented by the formula (2) with urea bonds or connecting groups containing urea bonds interposed between both sides thereof, and has a total of four (meth) acryloyl groups.

The urea-bonded tetrafunctional (meth) acrylate may be hydrogen-bonded to-OH of the component in the matrix resin through a urea bond. Therefore, since the matrix resin having no photo-curable substituent can be immobilized by hydrogen bonding, a cured film can be formed by irradiation with light such as ultraviolet light or visible light. Therefore, by using a resin having various properties as a matrix resin, 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 urea-linked tetrafunctional (meth) acrylate, a cured film (cured product) can be produced at a high reaction rate even when a transfer device for irradiation with ultraviolet light is used, which has a lower energy than that of a high-pressure mercury irradiation device (UV-L ED).

The divalent organic group a included as a part of the urea-linked tetrafunctional (meth) acrylate compound is preferably a divalent organic group having three or more aromatic rings or a divalent organic group having a structure represented by formula (3), from the viewpoint of obtaining a cured product having good heat resistance. Here, the divalent organic group having an aromatic ring may have a structure in which an aromatic ring such as naphthalene or anthracene is condensed or connected via a chemical bond. In the present invention, regarding the number of aromatic rings, when a benzene ring is set to one, naphthalene and fluorene are counted as two aromatic rings, and anthracene is counted as three aromatic rings.

[ solution 6]

(R in the formula (3))₃、R₄、R₅、R₆、R₇And R₈Each independently hydrogen or alkyl group having 1 to 30 carbon atoms, Z is alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 to 150)

Examples of the divalent organic group having three or more aromatic rings include divalent organic groups derived from an aromatic diamine compound having three or four aromatic rings, which will be described later. Further, as an example of the divalent organic group represented by the formula (3), R is exemplified₃、R₄、R₅、R₆、R₇And R₈A divalent organic group wherein Z is a propylene group.

< synthetic method >

The urea-bonded tetrafunctional (meth) acrylate of the present invention can be synthesized, for example, by the following synthetic methods 1 to 3.

< synthetic method 1 >

The urea-linked tetrafunctional (meth) acrylate of the present invention can be produced by allowing a compound represented by the following formula (4) to have-NH at both ends₂The diamine compound of (3) is obtained by reacting a monoisocyanate compound having two (meth) acryloyl groups represented by the following formula (5).

[ solution 7]

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

[ solution 8]

R in (formula (5))₁、R₂Is the same as formula (2)

The diamine compound represented by formula (4) is preferably an aromatic diamine compound having three or more aromatic rings or a siloxane diamine compound having a structure represented by formula (6) below, from the viewpoint of improving the heat resistance of a cured film obtained using a urea-bonded tetrafunctional (meth) acrylate.

[ solution 9]

R in (formula (6)₃、R₄、R₅、R₆、R₇And R₈Each independently hydrogen or alkyl group having 1 to 30 carbon atoms, Z is alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 to 150)

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

Specific examples of the diamine compound represented by the formula (4) used as a raw material of the urea-linked tetrafunctional (meth) acrylate are shown below.

Examples of the aromatic diamine compound having three aromatic rings include 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) -2, 5-di-tert-butylbenzene, 1, 4-bis (4-aminophenoxy) -2,3, 5-trimethylbenzene, N-bis (4-aminophenyl) terephthalamide, 1, 3-bis (3-aminophenoxy) benzene, α' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, and 1, 3-bis [1- (4-aminophenyl) -1-methylethyl ] benzene.

As the aromatic diamine compound having four aromatic rings, there can be mentioned: 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 4' -bis (4-aminophenoxy) biphenyl, 9-bis (4-aminophenyl) fluorene, 4' - (biphenyl-2, 5-diylbutoxy) dianiline, 4' -bis (4-aminobenzamide) -3,3' -dihydroxybiphenyl, 4' -bis (4-aminophenoxy) benzophenone.

Examples of the siloxane diamine compound represented BY the 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,. omega. -bis (3-aminopropyl) polydimethylsiloxane, commercially available products thereof or compounds obtained BY synthesis thereof, examples of commercially available products of siloxane diamine compounds include Silaplane FM33 series (trade name, JNC (Strand products), X22 series (trade name, manufactured BY Beacon chemical industries), BY16 series (trade name, manufactured BY Toray Corning (Dow Corning) (Dow) and the like, and examples of synthetic methods of siloxane diamine compounds include a method in which Silaplane alkyl dimethylsiloxanes (trade name, product name) are reacted with platinum (FM 11) in the presence of a platinum catalyst such as Silaplace (FM and FM 11).

In the formula (6), R is preferable from the viewpoint of easiness of acquisition₃、R₄、R₅、R₆、R₇、R₈And a siloxane diamine compound in which all of methyl groups and Z are propylene groups.

By the synthesis method, urea-bonded type tetrafunctional (meth) acrylate in which m in formula (1) is 0 can be synthesized.

The monoisocyanate compound having two (meth) acryloyl groups represented by formula (5) may be a commercially available compound or a compound obtained by synthesis. For example, Japanese patent laid-open No. 2007-55993 (patent document 5) discloses a method for obtaining the compound. Further, examples of commercially available products include kalien (Karenz) BEI (trade name, manufactured by showa electrician).

In order to improve the reactivity of the diamine compound represented by the formula (4) with the monoisocyanate having a (meth) acryloyl group represented by the formula (5), a catalyst may also be used. As the catalyst, a tin catalyst (e.g., dibutyltin dilaurate), an amine catalyst (e.g., triethylenediamine), a carboxylate catalyst (e.g., lead naphthenate, potassium acetate), a trialkylphosphine catalyst (e.g., triethylphosphine), a titanium catalyst (e.g., trade name: Ortolis (ORGATIX) TA-21, Ortolis (ORGATIX) TA-30, Ortolis (ORGATIX) TC-750, etc., manufactured by Matsumoto Fine Chemical Co., Ltd.), a zirconium catalyst (e.g., trade name: Ortolis (ORGATIX) ZC-150, Matsumoto Fine Chemical Co., Ltd.), and the like can be used.

< Synthesis method 2 >

The urea-linked tetrafunctional (meth) acrylate of the present invention can be produced by allowing formula (4) to have-NH at both ends₂The diamine compound of (4) is obtained by reacting a monocarboxylic acid compound having two (meth) acryloyl groups represented by the following formula (7).

[ solution 10]

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

[ solution 11]

(in the formula (7), R₁、R₂Represents the same group as formula (2), Y₁Is a linear alkylene group or an alkylene group having a branch and having 1 to 18 carbon atoms, and when the number of carbon atoms in the alkylene group is 2 or more, an oxygen atom (-O-) may be inserted between any of the C-C bonds

The monocarboxylic acid compound having two (meth) acryloyl groups represented by formula (7) can be produced by reacting a monocarboxylic acid compound having one-NH group in the molecule represented by formula (9)₂And a monoisocyanate compound having two (meth) acryloyl groups represented by the following formula (5).

[ solution 12]

(in the formula (9), Y₁Is the same as formula (7)

[ solution 13]

(in the formula (5), R₁And R₂Is the same as formula (2)

Having one-NH in the molecule represented by formula (9)₂Examples of the monocarboxylic acid compound of (3) include the following compounds.

[ solution 14]

[ solution 15]

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

[ solution 22]

To increase the number of-NH groups in the molecule represented by formula (9)₂The reactivity of the monocarboxylic acid compound of (2) with the monoisocyanate compound having two (meth) acryloyl groups represented by formula (5) may also be a condensing agent or a catalyst. The condensing agent may be N, N' -dicyclohexylcarbodiimide or 1-hydroxybenzotriazole, and the catalyst may be N, N-dimethyl-4-aminopyridine.

By the synthesis method, urea-bonded type tetrafunctional (meth) acrylate in which m in formula (1) is 1 can be synthesized. When m in formula (1) is 1, the urea-bonded tetrafunctional (meth) acrylate can be provided with flexibility and the reactivity of the (meth) acryloyl group can be adjusted. That is, the urea-linked tetrafunctional (meth) acrylate of formula (1) in which m is 1 has a smaller proportion of (meth) acrylate per molecule than the urea-linked tetrafunctional (meth) acrylate in which m is 0, and therefore, flexibility is increased and flexibility of the cured product is improved. In addition, the urea-linked tetrafunctional (meth) acrylate of formula (1) in which m is 1 has a longer molecular chain constituting the backbone portion of the polymer (high polymer) than the urea-linked tetrafunctional (meth) acrylate in which m is 0, and thus the degree of freedom of the molecule is increased. Further, the increase of the hydrogen bonding functional group (-NH-) in the compound increases the intermolecular interaction, and therefore, the aggregation effect is expected to be exhibited. As a result, the photopolymerization reactivity of the urea-linked tetrafunctional (meth) acrylate of formula (1) in which m is 1 becomes high.

< Synthesis method 3 >

The urea-bonded tetrafunctional (meth) acrylate of the present invention may beBy having-NH at both ends represented by formula (4)₂The diamine compound of (2) is obtained by reacting a monohalogen compound having two (meth) acryloyl groups represented by the following formula (8).

[ solution 23]

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

[ solution 24]

(in the formula (8), R₁And R₂Represents the same group as formula (2), W represents halogen, Y₂Is a linear alkylene group or an alkylene group having a branch and having 1 to 18 carbon atoms, and when the number of carbon atoms in the alkylene group is 2 or more, an oxygen atom (-O-) may be inserted between any of the C-C bonds

The monohalogen compound having two (meth) acryloyl groups represented by formula (8) can be represented by formula (11) below, which has one-NH group in the molecule₂With a monoisocyanate compound having two (meth) acryloyl groups represented by the following formula (5).

[ solution 25]

(in formula (11), Y₂Is the same group as formula (8), W is halogen)

[ solution 26]

(in the formula (5), R₁And R₂Is the same as formula (2)

Having one-NH in the molecule represented by formula (11)₂Examples of the monohalogen compounds of (2) includeThe following compounds are provided.

[ solution 27]

[ solution 28]

[ solution 29]

[ solution 30]

[ solution 31]

[ solution 32]

[ solution 33]

To improve the reaction of a monoisocyanate compound having two (meth) acryloyl groups with a compound having one-NH group in the molecule₂The reactivity of the monohalogen compound (2) may be combined with an inorganic base. Examples of the inorganic base include calcium carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.

By the synthesis method, urea-bonded type tetrafunctional (meth) acrylate in which m in formula (1) is 1 can be synthesized.

< composition >

The composition of the present invention containing the urea-linked tetrafunctional (meth) acrylate compound of the present invention may contain a compound having a radical polymerizable double bond other than the compound represented by formula (1), an organic resin, an inorganic resin, a solvent, a polymerization initiator, and the like within a range not impairing the photocurability and the heat resistance.

The compound having a radical polymerizable double bond other than the compound represented by formula (1) includes a resin having a radical polymerizable unsaturated bond such as a (meth) acrylate other than the compound represented by formula (1), a low-molecular compound having a radical polymerizable double bond other than (meth) acrylate, an unsaturated polyester resin, a polyester (meth) acrylate resin, a (meth) acrylate resin, and a urethane (meth) acrylate resin.

Specific examples of (meth) acrylates other than the compounds 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, phenoxypolyethylene glycol (meth) acrylate, and mixtures thereof, Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, tetrahydrofurfuryl alcohol acrylate polymer 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, and mixtures thereof, Methacryloyloxynorbornane (meth) acrylate, tetramethylpiperidine (meth) acrylate, pentamethylpiperidine (meth) acrylate, a (meth) acrylate having an imide ring, cyclic trimethylolpropane formal (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene glycol di (meth) acrylate, and mixtures thereof, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, -caprolactone-added trimethylolpropane tri (meth) acrylate, -caprolactone-added ditrimethylolpropane tetra (meth) acrylate, -caprolactone-added pentaerythritol tetra (meth) acrylate, -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, isocyanurate ethylene oxide-modified di (meth) acrylate, bisphenol a propylene oxide-modified di (meth) acrylate, and mixtures thereof, Propylene oxide isocyanurate-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.

Specific examples of the low-molecular-weight compound having a radically polymerizable double bond other than (meth) acrylate include crotonic acid, α -chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, N-vinylformamide, 2-allyloxymethylmethacrylate, polymethyl methacrylate macromonomer, N-cyclohexylmaleimide, N-phenylmaleimide, styrene, (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.

The unsaturated polyester resin may be obtained by dissolving a condensation product (unsaturated polyester) obtained by esterification of a polyhydric alcohol and an unsaturated polybasic acid (and optionally a saturated polybasic acid) in a polymerizable monomer.

The unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, there can be mentioned, as the acid component, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid or itaconic acid or an acid anhydride thereof, and reacting the resulting mixture with a polyhydric alcohol such as 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-dimethyl-1, 3-propanediol, cyclohexane-1, 4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A as an alcohol component, and further optionally a polybasic acid having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid or sebacic acid or an acid anhydride thereof as an acid component.

Examples of the polyester (meth) acrylate resin include (1) a (meth) acrylate resin obtained by reacting an epoxy compound containing α -unsaturated carboxylic acid ester with a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol, (2) a (meth) acrylate resin obtained by reacting an-OH-containing acrylate with a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol, and (3) a (meth) acrylate resin obtained by reacting a (meth) acrylic acid with a polyester having a terminal-OH group obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and a polyhydric alcohol.

Examples of the saturated polybasic acid used as a raw material of the polyester (meth) acrylate resin include: polybasic acids having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid, or anhydrides thereof, and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid, and itaconic acid, or anhydrides thereof. Further, the polyol to be reacted as the alcohol component is the same as the unsaturated polyester.

The (meth) acrylic epoxy ester resin is a compound (vinyl ester) having a polymerizable unsaturated bond, which is generated by a ring-opening reaction of a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as (meth) acrylic acid. In general, 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, and novolak-type glycidyl ethers. In addition to (meth) acrylic acid, a compound containing a reactant of a dibasic acid such as bisphenol (e.g., type a) or adipic acid, sebacic acid, dimer acid (saligema (HARIDIMER)270S (trade name, manufactured by Harima chemical synthesis)).

Examples of the urethane (meth) acrylate resin include the following oligomers containing a radical polymerizable unsaturated group: a polyisocyanate and a polyol or a polyol, and then reacting an-OH-containing (meth) acrylic compound and, if necessary, an-OH-containing allyl ether compound.

Examples of the polyisocyanate include 2, 4-tolylene diisocyanate and isomers thereof, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Panoko (Burnock) D-750, Crisvon NK (trade name, manufactured by Dainippon ink chemical industry Co., Ltd.), Desmodur (Desmodur) L (trade name, manufactured by Sumitomo Bayer urethane Co., Ltd.), Colonet (CORONATE) L (trade name, manufactured by Nippon polyurethane industry Co., Ltd.), Tagedde (Takenate) D102 (trade name, manufactured by Mitsui wara chemical Co., Ltd.), Stister (Isonate) 143L (trade name, manufactured by Mitsubishi chemical Co., Ltd.), and the like.

As the polyol, there may be mentioned: polyester polyols, polyether polyols, polycarbonate polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and the like, and specific examples thereof include: glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, 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, and the like.

Examples of the 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, an adduct of bisphenol a with propylene oxide or ethylene oxide, 1,2,3, 4-tetrahydroxybutane, glycerol, trimethylolpropane, 1, 3-butanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, cyclohexane-1, 4-dimethanol, p-xylene glycol, dicyclohexyl-4, 4-diol, 2, 6-decahydronaphthalene diol, 2, 7-decahydronaphthalene diol, and the like.

the-OH-containing (meth) acrylic compound is not particularly limited, and is preferably an-OH-containing (meth) acrylate, and specific examples thereof include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, mono (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, and the like.

The organic resin includes thermosetting resins and thermoplastic resins.

Examples of the thermosetting resin include: phenol resins, alkyd resins, melamine resins, epoxy resins, urea resins, urethane resins, acid-modified polyolefin resins obtained by modifying each polymer of polyolefin resins such as polyethylene and polypropylene with an acid having an unsaturated bond, acid-modified ethylene rubbers obtained by modifying each polymer of ethylene rubbers with an acid having an unsaturated bond, and acid-modified styrene elastomers obtained by modifying each polymer of styrene elastomers with an acid having an unsaturated bond. The acid used for the acid modification is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include unsaturated carboxylic acids or derivatives thereof, and thermosetting polyimides, and monomers constituting these thermosetting resins or polymers of the monomers can be added. These monomers or polymers thereof may be used alone, or a plurality thereof may be used in combination.

Specifically, in terms of processing suitability, epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester type epoxy resin, high molecular type epoxy resin, biphenyl type epoxy resin, melamine resins such as methylated melamine resin, butylated melamine resin, and methylbutyl mixed etherified melamine resin, urethane resins, and the like are preferable, the urethane resin may be prepared by reacting a polyisocyanate compound having two or more isocyanates (O ═ C ═ N-R-N ═ C ═ O) with a polyol compound having two or more-OH groups (HO-R' -OH) or a polyamine (H).₂N-R”-NH₂) Or water or the like having active hydrogen (-NH)₂NH, -CONH-, etc.) and the like.

Epoxy resins are excellent in heat resistance, adhesion and chemical resistance, melamine resins are excellent in heat resistance, hardness and transparency, and urethane resins are excellent in adhesion and low-temperature curability, and these resins can be suitably selected and used.

Examples of the thermoplastic resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultra-high molecular weight polyethylene, poly-4-methylpentene, syndiotactic polystyrene, polyamide (nylon 6: trade name of DuPont, nylon 6, 10: trade name of DuPont, nylon 6, T: trade name of DuPont, Nylon MXD 6: trade name of DuPont, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2, 6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene ether, fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: Unitika) (trade name), potalika (Vectra) (POP L), YPPTRA (PO L) (ASTICS), polyimide (AU, polyimide (AUM, polyimide, polyoxamide, polyimide, etc.), polyamide (Kapton, polyetherimide, etc.

As the inorganic resin, silicone resin is exemplified.

Examples of the silicone resin include a thermosetting silicone resin such as an addition curing silicone and a condensation curing silicone, and a modified silicone resin modified with a functional group.

The addition-curable silicone resin can be obtained by a hydrosilylation reaction between a silicone having a silanol and a hydrosilane and a silicone having an alkenyl group, or between a silicone having a hydrosilane and a silicone having a silanol and an alkenyl group. Examples of the catalyst used in the hydrosilylation reaction include transition metal catalysts, and examples of the transition metal catalysts used include platinum, rhodium, iridium, ruthenium, palladium, molybdenum, iron, cobalt, nickel, and manganese. Of these, a platinum catalyst is more preferable. These catalysts can be used as homogeneous catalysts dissolved in a solvent, solid catalysts supported on carbon, silica or the like. The compound can be used in the form of a mixture of phosphine, amine, potassium acetate, etc. TransitionThe amount of the metal catalyst used is preferably 1 × 10 in terms of transition metal catalyst atoms per 1 mol of hydrosilyl groups in the silicone resin^-6Mole-1 × 10^-2And (3) mol.

The condensation-curable silicone resin can be obtained by dealcoholizing and dehydrating a silicone having an alkoxysilyl group or a silanol group. In the condensation reaction, a condensation catalyst may be used in order to accelerate the reaction. Examples of the condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, metal complexes such as titanium complexes (for example, trade names: Orgitax (ORGATIX) TA-21, Orgitax (ORGATIX) TA-30, Orgitax (ORGATIX) TC-750, manufactured by Matsumoto Fine Chemical, inc.) and tin complexes, and metal alkoxides. The amount of the silanol condensation catalyst in 100 wt% of the raw material used in the condensation reaction is, for example, 0.00001 wt% to 0.1 wt%, preferably 0.00002 wt% to 0.01 wt%, and more preferably 0.0005 wt% to 0.001 wt%.

The modified silicone resin modified with a functional group may be a silicone resin in which a part of the organic groups of the silicone resin is modified with a functional group, and examples of the functional group include-NH₂OH, -epoxy, -SH, -COOH, vinyl, allyl, styryl and (methyl) acryloyl. The substituted position of the functional group can be any position of the terminal or side chain of the silicone.

In order to increase the surface hardness or glass transition temperature of the cured film, a siloxane compound having a three-dimensional crosslinked structure may be used as the inorganic resin. As the siloxane compound having a three-dimensional crosslinked structure, there may be mentioned a siloxane compound having a structure selected from the group consisting of "SiO" which is a structural unit containing₂"Q unit of, including the structural unit" RSiO_3/2"at least one unit of the T unit of (1). The siloxane compound may further contain at least one unit selected from the group consisting of Q unit and T unit, and may further contain a structural unit "R₃SiO_1/2"M Unit, containing the structural unit" R₂At least one unit of D units of SiO'. The siloxane compound having a three-dimensional crosslinked structure can be produced by reacting a silane compound having a hydrolyzable groupIs obtained by hydrolytic condensation. Further, the siloxane compound having a three-dimensional crosslinked structure is mainly a siloxane compound containing a three-dimensional crosslinked structure, and is called a silicone resin or a silicone alkoxy oligomer.

Examples of the silane compound having a hydrolyzable group include: trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylpropoxysilane, triphenylbutoxysilane, dimethylphenylmethoxysilane, triisopropylmethoxysilane, tricyclohexylmethoxysilane, dimethylethylethoxysilane, dimethylbutylethoxysilane, dimethylphenylethoxysilane, diethylphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane, methylethyldimethoxysilane, methyldimethoxysilane, Methylphenyldiethoxysilane, methylcyclohexyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, propyltriethoxysilane, propyltripropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenyltriisopropoxysilane, 3-methylphenyltrimethoxysilane, 3-methylphenyltriethoxysilane, methyltrimethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltrimethoxysilane, 4-methylphenyltriethoxysilane, cyclobutyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, cycloheptyltriethoxysilane, cyclooctyltrimethoxysilane, 4-methylcyclohexyltriethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltriethoxysilane, 1' -biphenyltriethoxysilane, 4-biphenyltrimethoxysilane, 5-triethoxysilyl-2-norbornene, 2-triethoxysilylnorbornene, tricyclo [3.3.1.13,7] decane-1-triethoxysilane, tricyclo [3.3.1.13,7] decane-2-triethoxysilane, cyclopentyltrimethoxysilyl, Tetramethoxysilane, a partial hydrolysis condensate of tetramethoxysilane (methyl silicate), tetraethoxysilane, a partial hydrolysis condensate of tetraethoxysilane (ethyl silicate), a polysiloxane compound having a silanol and/or an alkoxysilane group (polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane), and the like. Examples of the polysiloxane compound having a silanol and/or an alkoxysilane group include 1, 3-diethoxy-1, 1,3, 3-tetramethyldisiloxane and selaprrey (Silaplane) FM99 series (product name, manufactured by JNC corporation). The silane compound having a hydrolyzable group may be used in a mixture with another siloxane compound having a three-dimensional crosslinked structure without undergoing hydrolytic condensation, or may be used by reacting with another siloxane compound having a three-dimensional crosslinked structure in advance. When used in admixture with or reacted with another siloxane compound having a three-dimensional crosslinking structure, the reaction using a condensation catalyst proceeds rapidly, which is preferred. When a transparent hardened coating is to be formed, European Tetris (ORGATIX) TA-21 and European Tetris (ORGATIX) TA-30 (both trade name and product of Matsumoto Fine Chemical) are suitable, which are less colored.

The siloxane compound having a three-dimensional crosslinking structure may also be a silsesquioxane containing only T units. The silsesquioxane has a known structure such as a ladder structure, a completely condensed structure (cage structure), an incompletely condensed structure (partially cage structure), an amorphous structure (random structure), and can be synthesized by hydrolytic condensation of a silane compound having 3 hydrolyzable groups.

Commercially available silicone compounds having a three-dimensional crosslinked structure are also commercially available, and examples of commercially available silicone compounds having a three-dimensional crosslinked structure include RSN-0217, RSN-0220, RSN-0223, RSN-0249, RSN-0255, RSN-6018 (all trade names, manufactured by Toray Dow Corning (Inc.), KR-220L, KR-220L P, KR-480, KR-216 (all trade names, manufactured by shin-Etsu chemical industries, Inc.), SR-21, SR-23, SR-13, SR-33 (all trade names, manufactured by Xiao West chemical industries, Inc.), SO-1400, SO-1430, SO-1444, SO-1450, SO-1455, SO-1458, and SO-1460 (all trade names, manufactured by Hybrid Plastics, Inc.).

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

The organic resin or the inorganic resin preferably has-OH as a component. If a resin having-OH is used as the matrix resin, the urea bond of the urea-linked tetrafunctional (meth) acrylate of the present invention and-OH, which is a component of the matrix resin, may undergo hydrogen bonding. Therefore, a resin having no photo-curable substituent can be immobilized by hydrogen bonding, and a cured film can be formed by irradiation with light such as ultraviolet light or visible light. By using a resin having various properties as the matrix resin in this manner, a photocurable composition having desired properties can be prepared.

The compositions of the present invention may also contain a vehicle.

Examples of the solvent usable in the present invention include: diethyl ether, tetrahydrofuran, diphenyl ether, dimethoxybenzene, acetone, methanol, ethanol, isopropanol, butanol, tert-butanol, benzyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, ethylene carbonate, propylene carbonate, ethyl acetate, isobutyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-oxopropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl isopropyl alcohol, butanol, tert-butanol, benzyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, ethylene carbonate, propylene carbonate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, methyl 2-hydroxyisobutyrate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, ethylene glycol monoisopropyl ether, propylene glycol, propylene, Ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 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, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.

Of these, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, butyl acetate, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, and propylene glycol monomethyl ether are preferable.

The solvent used in the present invention may be one kind or a mixture of two or more kinds.

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

The composition of the present invention has a (methyl) acryloyl group as a reactive functional group, and therefore, in order to form a hardened coating film, it is preferable to use a photopolymerization initiator which can cause a polymerization reaction of a reactive monomer by irradiation with active energy rays such as ultraviolet rays or visible rays, thereby obtaining a compound, examples of the photopolymerization initiator include benzophenone, michelson, 4,4 '-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4' -isopropylphenylacetone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propane-1-one, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2-diethoxyphenone, 2-dimethoxy-2-benzoylacetophenone, bis- (4 '-phenylcarbamoyl) -2-4-trichloro-4- (2,4, 4' -dichloromethyl-benzoylphenyl) -2, 4-bis (2,4, 4 '-dichloromethyl-phenyl) -benzophenone, 2, 4-bis (2,4, 4' -dichloromethyl-2, 4-phenyl) -2, 4-methyl-phenyl-propiophenone, 2,4, 5-bis (4, 4-dichlorobenzophenone), bis (4, 5-dichloromethyl-4, 5-dichloromethyl-phenyl) -2, 4-methyl-phenyl) -benzophenone, 2-4-methyl-4-phenyl-4-methyl-phenyl-4-phenyl-methyl-4-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-propiophenone, 2-4-methyl-2, 2-4-methyl-phenyl-methyl-4-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-2, 2-4, 2-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-methyl-phenyl-2-phenyl-methyl-1-methyl-phenyl-methyl-phenyl-2-phenyl-1-2, 2-methyl-phenyl-methyl-4, 2-methyl-phenyl-4, 2-methyl-phenyl-methyl-phenyl-methyl-phenyl.

Of 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 are preferred.

The photopolymerization initiator may be used alone or in combination of two or more.

Alternatively, a cured coating may be obtained by thermally inducing a polymerization reaction. That is, a thermosetting composition can be prepared by adding a thermal polymerization initiator. Examples of the thermal polymerization initiator include: diacyl peroxides, ketone peroxides, hydrogen peroxides, dialkyl peroxides, peroxyesters, azo compounds, persulfates, and the like. These may be used alone or in combination of two or more.

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, based on 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, the polymerization rate is sufficient and polymerization inhibition by oxygen or the like is not easily caused. On the other hand, when the amount of the polymerization initiator used is 20 parts by weight or less, the residue of the polymerization initiator does not remain in the cured film, and the adhesion strength or heat resistance of the resulting cured film does not decrease, and a cured film having sufficient adhesion strength or heat resistance can be obtained. Further, it does not cause coloring.

From the viewpoint of adjusting the physical properties and the viewpoint of curing at the time of forming a subsequent coating, the composition of the present invention may further contain other components within a range not impairing the heat resistance. The other components may be exemplified by: an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a surfactant, a plasticizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, and a silane coupling agent.

< hard coating >

The hardened coating 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 coating film is formed, for example, by applying a urea-bonded tetrafunctional (meth) acrylate compound or composition to the surface of a substrate, and then irradiating the substrate with light such as ultraviolet light or visible light to cure the coating film. By blending the urea-bonded tetrafunctional (meth) acrylate compound, photocurability can be imparted to a composition containing other components (organic resin, inorganic resin, and the like).

The cured film of the present invention has excellent heat resistance and electrical insulation properties, and has excellent balance such as adhesion of a metal, a resin, or the like to a substrate. Therefore, the application of the cured film of the present invention is not particularly limited, and the cured film is preferably used as an insulating film or the like for protecting the surface of a metal wiring or the like on which a predetermined circuit pattern is formed.

When the composition is irradiated with ultraviolet rays or visible rays, the amount of the light to be irradiated may be appropriately selected depending on the composition of the composition, and is preferably 100mJ/cm²～5,000mJ/cm²About, more preferably 150mJ/cm²～2,000mJ/cm²About, more preferably 180mJ/cm²～1,000mJ/cm²Left and right. The wavelength of the ultraviolet light, visible light, or the like to be irradiated is preferably 200nm to 500nm, more preferably 250nm to 450 nm.

In the present invention, the exposure amount is a value measured by an integrated light quantity meter UIT-201 (trade name) equipped with a light receiver UVD-365PD (trade name) manufactured by a oxtail (USHIO) motor (stock).

Further, as the exposure machine, it is preferable to mount a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a halogen lamp, an electrodeless lamp, a UV-L ED lamp, or the like, and irradiate ultraviolet light, visible light, or the like in a range of 200nm to 500 nm.

Further, the cured coating film cured by irradiation with light may be further heated and fired as necessary. For example, the hardened coating can be more firmly hardened by heating and baking at 80 to 250 ℃ for about 10 to 120 minutes.

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

Examples of the substrate usable in the present invention include: a polyester resin substrate including polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like; a polyolefin resin substrate containing polyethylene, polypropylene, and the like; organic polymer films including polyvinyl chloride, fluororesin, acrylic resin, styrene resin, polyamide, polycarbonate, polyimide, and the like; a substrate comprising cellophane; a metal foil; a laminated film of a resin substrate containing polyimide or the like and a metal foil; a laminate of glass epoxy and metal foil; cellophane, parchment, polyethylene, clay binder, polyvinyl alcohol, paper subjected to joint filling treatment by using starch or Carboxymethyl Cellulose (CMC), etc., having a joint filling effect; silicon-based substrates such as silicon wafers, silicon nitride substrates, and silicon oxide substrates; glass substrates such as glass wafers and quartz substrates.

These substrates may further contain additives such as pigments, dyes, antioxidants, deterioration prevention agents, fillers, ultraviolet absorbers, antistatic agents and/or electromagnetic shielding agents, within a range that does not adversely affect the effects of the present invention.

Further, at least a part of the surface of the substrate may be subjected to a surface treatment such as a water repellent treatment, a corona treatment, a plasma treatment, and/or a blast treatment, or an easy-to-adhere layer, a protective film for a color filter, or a hard coat film may be provided on the surface.

The thickness of the cured coating of the present invention can be suitably selected depending on the intended use, and is preferably 1 μm to 50 μm, more preferably 5 μm to 20 μm.

The cured film formed on the substrate can be peeled off from the substrate and used as a material for electronic components and the like, and can be used as a substrate with a cured film such as an electronic circuit substrate and the like, or as a material for electronic components and the like without being peeled off from the substrate, depending on the application or the substrate used.

Examples of the electronic circuit board include a rigid board, a flexible board, and a rigid flexible board.

Examples of the flexible substrate include substrates obtained as follows: the ink containing a urea-linked tetrafunctional (meth) acrylate compound of the present invention is applied to the entire surface or in a predetermined pattern (linear shape or the like) on a film-like substrate such as a polyimide film on which wiring has been formed in advance by an ink jet method or the like 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 Oxide (ITO). An ink containing a urea-bonded tetrafunctional (meth) acrylate compound is applied in a predetermined pattern on a substrate on which these wirings are formed, and the cured film obtained by curing the ink functions as an insulating film or the like for protecting the wirings.

< electronic part >

The electronic component of the present invention includes a cured film or a substrate with a cured film. A flexible electronic component and a display element can be obtained from the cured film or a substrate with a cured film using a film substrate as a substrate.

For example, an electronic component for a liquid crystal display element can be produced by mounting an Integrated Circuit (IC) chip, a capacitor, a resistor, a fuse, or the like on an electronic Circuit substrate manufactured using the cured film of the present invention having excellent heat resistance, electrical insulation, adhesion to a substrate, folding resistance, and flame retardancy.

Examples

[ Synthesis example 1]

< Synthesis example of Urea-bonded tetrafunctional acrylic-modified silicon Compound A >

7.0g of 1,1- (bisacryloxymethyl) ethyl isocyanate (trade name: Karenz BEI, manufactured by Showa Denko K.K., hereinafter referred to as "BEI" where appropriate) and 0.1g of 4-methoxyphenol were dissolved in 27.9g of tetrahydrofuran, and the obtained solution was stirred at room temperature under a nitrogen atmosphere. 3.0g of a siloxane diamine compound (trade name: BY16-871, manufactured BY Toray Dow Corning, Ltd.) diluted with 12.1g of tetrahydrofuran was dropped into the solution over 10 minutes, and the mixture was stirred at 20 to 30 ℃ for 1 hour to obtain a reaction solution. The obtained reaction solution was subjected to solvent removal by an evaporator, followed by dropwise addition of hexane (10.0g) and removal of excess BEI 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 a (7.6g, hereinafter referred to as "silicon compound a" as appropriate). The following shows the silicon compound a.

< silicon Compound A >

[ chemical 34]

[ Synthesis example 2]

< Synthesis example of urea-bonded tetrafunctional acrylic-modified silicon Compound B >

6.1g of a siloxane diamine compound (trade name: FM3311, manufactured by JNC Co., Ltd.) and 0.1g of 4-methoxyphenol were dissolved in 24.6g of tetrahydrofuran, and the mixture was stirred at room temperature under a nitrogen atmosphere. 3.9g of BEI diluted with 15.4g of tetrahydrofuran was added dropwise to the solution over 10 minutes, and the mixture was stirred at 20 ℃ to 30 ℃ for 1 hour. The obtained reaction solution was subjected to solvent removal by an evaporator, followed by dropwise addition of hexane (10.0g) and removal of excess BEI 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 (9.5g, hereinafter referred to as "silicon compound B" as appropriate). The following shows the silicon compound B.

< silicon Compound B >

[ solution 35]

[ Synthesis example 3]

< Synthesis example of Urea-bonded tetrafunctional acrylic-modified aromatic Compound C

7.41g of an aromatic diamine compound (trade name: 2, 2-bis (4- (4-aminophenoxy) phenylpropane, manufactured by Hill Seisakusho Kogyo industries, Ltd.) and 0.16g of 4-methoxyphenol were dissolved in 20.0g of methyl ethyl ketone (hereinafter, appropriately referred to as "MEK" (methyl ethyl ketone) ") under stirring at room temperature under a nitrogen atmosphere, BEI8.61g was added dropwise to the solution, followed by stirring at 60 ℃, then, zirconium tetraacetylacetonate (trade name: Ortolis (ORGATIX) ZC-150, manufactured by Songbo Fine Chemical industries, Ltd.) was added dropwise to the solution, followed by stirring at 60 ℃ for 2 hours, and the reaction solution obtained was subjected to solvent removal by an evaporator to obtain a urea bond type tetrafunctional acrylic modified aromatic compound C methyl ethyl ketone solution (25.58 g), a urea bond type tetrafunctional acrylic modified aromatic compound C, a methyl ethyl ketone solution (25.58 g) was obtained, The solid content concentration is 81 wt%, and hereinafter referred to as "aromatic compound C" as appropriate). The aromatic compound C is shown below.

< aromatic Compound C >

[ solution 36]

[ Synthesis example 4]

< Synthesis example of Urea-bonded tetrafunctional acrylic-modified aromatic Compound D >

13.5g of BEI and 0.2g of 4-methoxyphenol were dissolved in 37.0g of tetrahydrofuran, and the mixture was stirred at room temperature under a nitrogen atmosphere. 6.6g of an aromatic diamine compound (9, 9-bis (4-aminophenyl) fluorene, manufactured by tokyo chemical synthesis) diluted with 50.0g of tetrahydrofuran was dropped into the solution over 8 minutes, and the solution was stirred at 50 ℃ for 1 hour. Further, 5.2g of BEI was added dropwise to the reaction mixture, followed by stirring at 50 ℃ for 1 hour. The obtained reaction solution was extracted with ethyl acetate-water, washed with saturated saline, and the extract was dried over magnesium sulfate. The extract was separated from magnesium sulfate by filtration, and the solvent was removed by an evaporator to obtain a concentrated solution. It was left at room temperature and recrystallized, thereby obtaining a white solid. The obtained white solid was washed with ethyl acetate, and then the solvent was completely removed by vacuum drying, thereby obtaining urea-bonded tetrafunctional acrylic-modified aromatic compound D (8.5g, hereinafter, appropriately referred to as "aromatic compound D"). The aromatic compound D is shown below.

< aromatic Compound D >

[ solution 37]

[ comparative Synthesis example 1]

< Synthesis example of Urea-bonded difunctional acrylic-modified silicon Compound E >

0.85g of a siloxane diamine compound (trade name: BY16-871, manufactured BY Toray Dow Corning) and 0.02g of 4-methoxyphenol were dissolved in 8.00g of tetrahydrofuran and stirred at room temperature under a nitrogen atmosphere. 1.15g of 2-acryloyloxyethyl isocyanate (trade name: Carlen (Karenz) AOI, Showa Denko K.K., hereinafter referred to as "AOI") was added dropwise to the solution, and the mixture was stirred at 20 to 30 ℃ for 1 hour. The obtained reaction solution was subjected to solvent removal by an evaporator, followed by dropwise addition of hexane (10.0g), and excess AOI removal by decantation. After removing the supernatant, the solvent was removed from the obtained solution using a vacuum pump, to obtain urea-bonded bifunctional acrylic-modified silicon compound E (1.6g, hereinafter referred to as "silicon compound E" as appropriate). The silicon compound E is shown below.

< silicon Compound E >

[ solution 38]

[ comparative Synthesis example 2]

< Synthesis example of urethane-bonded tetrafunctional acrylic-modified silicon Compound F >

A solution of 8.29g of a silicone diol compound (trade name: FM4401, manufactured by JNC (stock Co.)) and 0.2g of 4-methoxyphenol was added dropwise to a solution of 11.72g of BEI, and the mixture was stirred at 60 ℃. Then, 0.10g of zirconium tetraacetylacetonate (trade name: Ortolis (ORGATIX) ZC-150, manufactured by MatsumotoFine chemical Co., Ltd.) dissolved in MEK10.00g was added dropwise to the solution, and stirred at 60 ℃ for 2 hours. The obtained reaction solution was subjected to solvent removal by an evaporator. A MEK solution (24.79g, solid content concentration 84 wt%) of a urethane bond-type tetrafunctional acrylic-modified silicon compound F (hereinafter referred to as "silicon compound F" as appropriate) was obtained. The silicon compound F is shown below.

< silicon Compound F >

[ solution 39]

[ Synthesis example 5]

< Synthesis example of urea-bonded tetrafunctional acrylic-modified aromatic Compound G >

4.73g of an aromatic diamine compound (trade name: 4, 4-diaminodiphenyl ether, manufactured by Tokyo Kasei Co., Ltd.) and 0.16g of 4-methoxyphenol were dissolved in a mixed solvent of 50.00g of acetonitrile and 50.00g of acetone, and the mixture was stirred at room temperature under a nitrogen atmosphere. 11.10g of BEI was added dropwise to the solution, followed by stirring at 60 ℃. Then, 0.08g of zirconium tetraacetylacetonate (trade name: Ortolis (ORGATIX) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) dissolved in 5.00g of acetonitrile was added dropwise to the solution, and stirred at 60 ℃ for 3 hours. The solvent of the obtained reaction solution is removed by an evaporator and a vacuum pump. The urea-bonded tetrafunctional acrylic-modified aromatic compound G (15.11G, hereinafter referred to as "aromatic compound G" as appropriate) was obtained by recrystallization at room temperature. The aromatic compound G is shown below.

< aromatic compound G >

[ solution 40]

< preparation of composition 1 >

Composition 1 of the present invention was obtained by mixing 1.200g of the silicon compound synthesized in synthesis example 1, 0.045g of a phenylalkylketone photopolymerization initiator (trade name: Irgacure 127, manufactured by BASF corporation, hereinafter referred to as "IC 127" where appropriate) as a curing agent, 2.100g of MEK as a solvent, and 0.700g of N-methyl-2-pyrrolidone (hereinafter referred to as "NMP (N-methyl-2-pyrrolidone" where appropriate)) at room temperature.

< preparation of composition 2 >

Composition 2 was obtained by using the silicon compound B synthesized in synthesis example 2 in place of the silicon compound a in the same manner as in composition 1.

< preparation of composition 3 >

Composition 3 of the present invention was obtained by mixing 0.120g of the silicon compound A synthesized in Synthesis example 1, 1.080g of a silicone compound having a three-dimensional crosslinked structure (trade name: SR-21, manufactured by Seikagaku chemical industries, hereinafter referred to as "SR-21" where appropriate), 0.020g of IC1270.020g of a hardener, 2.100g of MEK as a solvent, and 0.700g of NMP.

< preparation of composition 4 >

Composition 4 of the present invention was obtained using the same method as composition 3, using silicon compound B instead of silicon compound a.

< preparation of composition 5 >

Composition 5 of the present invention was obtained by mixing 0.300g of the silicon compound A synthesized in Synthesis example 1, SR-210.900 g, IC1270.050g as the hardener, MEK 2.100g as the solvent, and NMP 0.700 g.

< preparation of composition 6 >

Composition 6 of the present invention was obtained in the same manner as in composition 5 except that gorgeous good solids (Irgacure)379EG (trade name, manufactured by BASF corporation, hereinafter referred to as "IC 379 EG" where appropriate) was used in place of IC 127.

< preparation of composition 7 >

A composition 7 of the present invention was obtained by mixing 0.180g of the silicon compound A synthesized in Synthesis example 1, SR-211.020 g, IC379EG0.027g as a hardener, 2.100g of MEK as a solvent, and 0.700g of NMP.

< preparation of composition 8 >

The silicon compound E synthesized in comparative synthesis example 1 was used in place of the silicon compound a in the same manner as in composition 3 to obtain composition 8 of the present invention.

The components contained in the compositions 1 to 8 are shown in the following Table 1 (unit: g).

[ Table 1]

TABLE 1

(unit: g)

A. B: silicon compound (tetrafunctional), E: silicon compound (difunctional)

SR-21: silicone compound having three-dimensional crosslinking structure

[ example 1]

The composition 1 was applied to a glass substrate cut to 4cm × 4cm, spin-coated at a rotation speed of 300rpm, dried on a hot plate heated at 80 ℃ for 5 minutes, further dried on a hot plate heated at 135 ℃ for 5 minutes, and then irradiated with high-pressure mercury (trade name: 8kW × 1 conveyor type ultraviolet curing apparatus, manufactured by Egal Graphs) (Strand) at 1,000mJ/cm²And (3) photo-curing under the conditions to obtain a cured coating. The obtained hardened coating was a non-sticky, colorless and transparent coating. The exposure amount was measured using an illuminometer (UVPF-Al/PD-365, manufactured by Kawasaki gas (Strand)).

[ 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 obtained hardened coating was a non-sticky, colorless and transparent coating.

[ 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 the film was coated on a glass substrate cut to 10cm × 10 cm.

[ example 4]

A cured coating 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 coating was obtained in the same manner as in example 3, except that composition 8 was used instead of composition 3.

< evaluation of hardened coating >

< 5% weight minus temperature >

The measurement was carried out at a temperature in the range of 40 ℃ to 550 ℃ using a differential thermal gravimetric simultaneous measurement apparatus (TG/DTA6200, manufactured by Hitachi high-Tech Science, Inc.). In order to eliminate errors caused by moisture absorption of the film, the weight at 100 ℃ was set to 100%, and the temperature at which 5% of the weight was reduced therefrom was set to 5% weight-reduced temperature. The results are shown in table 2.

[ Table 2]

TABLE 2

	Example 3	Example 4	Comparative example 1
				5% weight by weight temperature (. degree.C.)	394	405	351

As is clear from the evaluation results, the cured film obtained by curing the composition containing the compound of the present invention has more excellent heat resistance than the bifunctional compound.

From the above results, it can be said that the amount of the (meth) acrylate compound bonded to the terminal in the (meth) acrylate compound having a urea bond affects the heat resistance. It is found that, in the urea bond type (meth) acrylate compound having two urea bonds, the heat resistance of the cured film formed from the composition containing the urea bond type (meth) acrylate compound and the siloxane compound having a three-dimensional crosslinking structure is improved by setting the number of functional groups to four. From the viewpoint of forming a cured coating film having good heat resistance, the content of the silicone compound having a three-dimensional crosslinked structure in the composition is preferably 1 part by weight to 20 parts by weight, and more preferably 5 parts by weight to 15 parts by weight, relative to 1 part by weight of the urea-bonded (meth) acrylate compound.

< measurement of reaction Rate 1 >

[ example 5]

Composition 5 was applied to a glass substrate cut to 4cm × 4cm, spin-coated at a rotation speed of 300rpm, dried on a hot plate heated at 80 ℃ for 5 minutes, further dried on a hot plate heated at 135 ℃ for 5 minutes, and then exposed to an exposure of 500mJ/cm by a high-pressure mercury irradiation apparatus in the same manner as in example 1²～2,500mJ/cm²The reaction rate of acryloyl group was measured while varying within the range of (2). The reaction rate was determined by the following method.

< reaction Rate >

The reaction rate was calculated by the following formula using a Fourier transform infrared spectrophotometer (FT/IR-6700, manufactured by Nippon Kagaku Kogyo Co., Ltd.).

Reaction rate (%) { (X1-X2)/X1} × 100

(X1: the peak area ratio before exposure P-2/P-1, X2: the 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 terminal C-H bond (1410 cm)^-1))

[ example 6]

The reactivity of acryloyl groups was measured in the same manner as in example 5 except that the composition 6 was used and photo-cured using a UV-L ED irradiation conveyer (trade name: L SS-08A, manufactured by Sun, Ltd.) in place of the high pressure mercury irradiation apparatus of example 5, and the results are shown in Table 3.

[ Table 3]

TABLE 3

However, from the results of example 5 and example 6, it was found that a cured film could be produced at a reaction rate comparable to that of high-pressure mercury, which has the highest reaction rate in UV curing of acrylic esters, by selecting a curing agent suitable for a light source even when a UV-L ED irradiation transport apparatus was used, and from these evaluation results, it was found that a cured film having a reaction rate comparable to that of high-pressure mercury, which has the highest reaction rate in UV curing of acrylic esters, could be formed even when a UV-L ED irradiation transport apparatus was used.

[ example 7]

Composition 7 was applied to a chromium substrate cut to 9cm × 7cm, spin-coated at 300rpm, dried on a hot plate heated to 80 ℃ for 5 minutes, further dried on a hot plate heated to 135 ℃ for 5 minutes, and then irradiated with UV-L ED using a UV-L ED irradiation conveyer at 1,000mJ/cm in the same manner as in example 6²Then, aluminum was deposited by using a vacuum deposition apparatus (VE-2030, manufactured by vacuum instruments (Ltd.)) and the volume resistivity measured by using an ultra-high resistance meter (DSM-810, manufactured by Agilent) was 1.9 × 10¹⁵(omega cm) and has excellent electrical insulation properties.

< preparation of composition 9 >

Composition 9 of the present invention was obtained by mixing 1.800g of the silicon compound synthesized in synthesis example 1, 0.270g of IC379EG 0.270g as a curing agent, 1.050g of MEK 3.150g and NMP as a solvent.

< preparation of composition 10 >

The silicon compound F synthesized in comparative synthesis example 2 was used instead of the silicon compound a in the same manner as in composition 9 to obtain composition 10 of the present invention.

[ example 8]

The composition 9 was applied to a glass substrate cut to 4cm × 4cm, spin-coated at a rotation speed of 300rpm, dried on a hot plate heated at 80 ℃ for 5 minutes, further dried on a hot plate heated at 135 ℃ for 5 minutes, and then irradiated with UV-L ED using a UV-L ED irradiation conveyer at 1,000mJ/cm in the same manner as in example 6²And (3) photo-curing under the conditions to obtain a cured coating. The obtained hardened skin film is colorless and free of stickinessA transparent coating.

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 hardened coating >

< glass transition temperature >

The glass transition temperature (Tg) was measured by raising the temperature from 40 ℃ to 220 ℃ using a rigid oscillator viscoelasticity measuring apparatus (manufactured by A & D, "RPT-3000W"). The results are shown in table 4.

[ Table 4]

TABLE 4

	Example 8	Comparative example 2
			Glass transition temperature (. degree. C.)	111	80

As is clear from the evaluation results, the cured film obtained by curing the composition containing the (meth) acrylate compound having a urea bond of the present invention has more excellent heat resistance than the (meth) acrylate compound having a urethane bond.

From the above results, it can be said that, regarding the compound having a urea bond, the bonding mode of the main chain affects the heat resistance of a cured product obtained by curing a composition containing the compound.

< preparation of composition 11 >

Composition 11 of the present invention was obtained by mixing 0.300g of the silicon compound A synthesized in Synthesis example 1, SR-210.900 g, IC379EG0.045g as a curing agent, 2.100g of MEK as a solvent, and 0.700g of NMP.

< preparation of composition 12 >

Composition 12 of the present invention was obtained in the same manner as in composition 11 except that the silicon compound F synthesized in comparative synthesis example 2 was used instead of the silicon compound a.

< measurement of reaction Rate 2 >

[ example 9]

The composition 11 was applied to a glass substrate cut into 4cm × 4cm, spin-coated at a rotation speed of 300rpm, dried on a hot plate heated at 80 ℃ for 5 minutes, further dried on a hot plate heated at 135 ℃ for 5 minutes, and then irradiated with UV-L ED to a transfer apparatus at an exposure of 400mJ/cm in the same manner as in example 6²～1,500mJ/cm²The reaction rate of acryloyl group was measured while varying within the range of (2). The reaction rate was determined in the same manner as in example 5.

Comparative example 3

The reactivity of acryloyl group was measured in the same manner as in example 9, except that composition 12 was used instead of composition 11. The results are shown in table 5.

[ Table 5]

TABLE 5

As is clear from the evaluation results, the cured film obtained by curing the composition containing the (meth) acrylate compound having a urea bond of the present invention has higher reactivity than the (meth) acrylate compound having a urethane bond. In particular at 1,000 (mJ/cm)²) In the following small exposure amount, the (meth) acrylate compound having a urea bond shows significantly higher reactivity than the (meth) acrylate compound having a urethane bond.

From the results, it can be said that the reactivity is affected by the bonding mode of the main chain of the compound having a urea bond.

< preparation of composition 13 >

Composition 13 of the present invention was obtained by mixing 0.540g of the aromatic compound C synthesized in synthesis example 3, 0.081g of IC379EG 0.081 as a hardener, 3.150g of MEK as a solvent, and 1.050g of NMP.

< preparation of composition 14 >

Composition 14 of the present invention was obtained in the same manner as in composition 13 except that the aromatic compound D synthesized in synthesis example 4 was used instead of the aromatic compound C.

< preparation of composition 15 >

Composition 15 of the present invention was obtained in the same manner as in composition 13 except that the aromatic compound G synthesized in synthesis example 5 was used instead of the aromatic compound C.

[ example 10]

The composition 13 was applied to a glass substrate cut to 10cm × 10cm, spin-coated at a rotation speed of 300rpm, dried on a hot plate heated at 80 ℃ for 5 minutes, further dried on a hot plate heated at 135 ℃ for 5 minutes, and then irradiated with UV-L ED using a UV-L ED irradiation conveyer at 1,000mJ/cm in the same manner as in example 6²And (3) photo-curing under the conditions to obtain a cured coating. The obtained hardened coating was a non-sticky, colorless and transparent coating.

[ example 11]

A colorless and transparent cured film was obtained in the same manner as in example 10, except that the composition 14 was used instead of the composition 13.

[ example 12]

A cured film was obtained in the same manner as in example 10, except that the composition 15 was used instead of the composition 13.

< evaluation of hardened coating >

Less than 5-20% weight minus temperature

The measurement was carried out at 40 ℃ to 550 ℃ using a differential thermal weight simultaneous measurement apparatus in the same manner as in example 3. In order to eliminate errors caused by moisture absorption of the film, the weight at 100 ℃ is set as 100%, and the temperatures at which the weight is reduced by 5% to 20% are set as 5%, 10%, and 20% weight reduction temperatures, respectively. The results are shown in table 6.

[ Table 6]

TABLE 6

	Example 10	Example 11	Example 12
				5% weight loss temperature (. degree.C.)	172	185	167
10% weight loss temperature (. degree.C.)	190	207	183
				20% weight loss temperature (. degree.C.)	227	278	203

As is clear from the evaluation results, the composition containing the urea-linked tetrafunctional acrylic-modified aromatic compound of the present invention was found to exhibit excellent heat resistance. In addition, a composition containing a compound having four aromatic rings in the main chain can obtain a cured film having excellent heat resistance by curing the composition, as compared with a composition containing a compound having two aromatic rings in the main chain.

From the above results, it can be said that the number of aromatic rings bonded to the main chain in the (meth) acrylate compound having a urea bond affects the heat resistance. It is found that, in a urea bond type (meth) acrylate compound having an aromatic ring in the main chain, the heat resistance of a cured film formed from a composition containing the urea bond type (meth) acrylate compound and a photopolymerization initiator is improved by setting the number of aromatic rings to four.

[ Synthesis example 6]

< Synthesis example of silanol-containing siloxane Compound having three-dimensional crosslinked Structure >

A three-necked flask having an internal volume of 200 ml and equipped with a dropping funnel, a reflux condenser and a thermometer was charged with 31.8g of phenyltrimethoxysilane, 33.5g of tetraethoxysilane, 4.9g of dimethyldimethoxysilane and 34.3g of diethylene glycol ethyl methyl ether, and the flask was sealed with dry nitrogen gas. After stirring the mixture at room temperature for 30 minutes while stirring the mixture with a magnetic stirrer, a mixture of 14.4g of ion-exchanged water and 22.4g of formic acid was added dropwise over 20 minutes. After 1 hour of reaction at room temperature, the reaction mixture was heated at 90 ℃ for 1.5 hours, 100 ℃ for 1 hour and 140 ℃ for 2.5 hours in an oil bath, and the reaction was terminated after confirming that the removal of the generated methanol and ethanol by distillation was stopped. The mixture was allowed to stand and cooled to room temperature, and 100g of ethyl acetate was mixed, followed by washing with water using a separatory funnel until the pH became neutral. Thereafter, the mixture was concentrated at room temperature using an evaporator until the weight of the solution became 50g, to prepare a silanol-containing siloxane compound solution having a three-dimensional crosslinked structure (matrix a) having a solid content of 44 wt%.

The IR spectrum of the substrate A was measured using a Fourier transform infrared spectrophotometer in the same manner as in example 5, and the IR spectrum was measured at 920cm based on silanol^-1Was confirmed to contain silanol (920 cm) in the silicone compound having a three-dimensional crosslinked structure^-1). Further, the substrate A was analyzed by Gel Permeation Chromatography (GPC)The weight-average molecular weight (Mw) was found to be 41,300, and the molecular weight distribution (Mw/Mn) was found to be 5.2. GPC analysis was performed under the conditions shown below.

＜GPC＞

Device L C-2000Plus series (detector: differential refractometer) made by Japanese Spectroscopy (Strand)

Solvent: tetrahydrofuran (THF)/N, N-Dimethylformamide (DMF) ═ 1/1(v/v)

Flow rate: 0.5ml/min

Temperature of the pipe column: 40 deg.C

Using a pipe column: showa Denko K.K., Asahipak (Asahipak) GF-1G 7B (guard bar) + Asahipak (Asahipak) GF-7M HQ, and a rejection limit molecular weight (PEG) of 10,000,000

Calibration curve standard: PSt

< preparation of composition 16 >

The silicon compound a synthesized in synthesis example 1 (0.18 g), the matrix a 3.673g (1.620 g as a siloxane compound having a three-dimensional cross-linked structure), ic1270.027g, and NMP 2.147g as a solvent were mixed to obtain the composition 16 of the present invention.

[ example 13]

Composition 16 was applied to a glass substrate cut to 4cm × 4cm, spin-coated at a rotation speed of 300rpm, dried on a hot plate heated at 80 ℃ for 5 minutes, further dried on a hot plate heated at 135 ℃ for 5 minutes to prepare two uncured films, and the two uncured films were formed by a high-pressure mercury irradiation apparatus at 1,000mJ/cm in the same manner as in example 1²Only one of the uncured coating films is photo-cured under the conditions (2) to form a cured coating film, and the remaining one is an uncured coating film. The exposure amount was measured by using an illuminometer in the same manner as in example 1. The solvent resistance of the uncured coating film and the cured coating film thus produced was evaluated under the following conditions.

< evaluation of solvent resistance >

The uncured coating film and the cured coating film obtained in example 13 were immersed in NMP at room temperature for 15 minutes 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 calculation formula, and as a result, the residual film ratio of the uncured coating film was 4% and the residual film ratio of the cured coating film was 83%.

Residual film rate (W1-W2)/W1

(W1: weight of film before immersion, W2: weight of film after immersion)

The results show that the cured coating obtained by reacting acryloyl groups exhibited solvent resistance, although the cured coating contained only 10 wt% of silicon compound a. The results showed that the silicon compound a formed a hydrogen bond with the siloxane compound having a three-dimensional cross-linked structure contained in the matrix a.

[ examples 14 to 16]

Compositions 17 to 19 were prepared according to the formulation shown in table 7, and a cured coating was produced by the same method as in example 8.

< evaluation of Heat-resistant adhesion >

In the respective cured films produced using compositions 17 to 19, adhesiveness before and after a heat test at 200 ℃ for 30 minutes was evaluated by a checkerboard peel test (cross cut test), and the adhesive tape for evaluation was No.610 manufactured by 3M, wherein no peel was observed was "○", and 1 to 100 peeled ones were "×", and as a result, as shown in table 7, good adhesiveness was exhibited before and after the heat test in all cured films, and no crack was generated in the cured films after the heat test, and therefore, the photocurable resin composition of the present invention can be preferably used as an insulating film for a semiconductor requiring a heating step.

[ Table 7]

TABLE 7

(unit: g)

SR-23 (manufactured by Xiaoxi chemical industry): silicone compound having three-dimensional crosslinking structure

DMDMS (tokyo chemical synthesis (stock) manufacturing): dimethyldimethoxysilane

TA-30 (manufactured by Matsumoto Fine Chemical Co., Ltd.): oriental Tess (ORGATIX) TA-30

Industrial applicability

The compound of the present invention has excellent reactivity even in L ED light source, and can be used as a protective film for optical device materials in which deterioration due to ultraviolet rays is a problem.

Claims

1. A urea-bonded tetrafunctional (meth) acrylate compound represented by the following formula (1);

[ solution 1]

(in the formula (1), A is a divalent organic group, Y is a C1-18 linear alkylene or branched alkylene, in the alkylene carbon number is more than 2 cases, can be arbitrary C-C bond insertion oxygen atom (-O-), can also be in the terminal C-N bond insertion-CO-, m is 0 or 1, X is the following formula (2) expressed by the group);

[ solution 2]

(in the formula (2), R₁And R₂Independently hydrogen or methyl).

2. The urea-linked tetrafunctional (meth) acrylate compound according to claim 1, wherein a in formula (1) is a divalent organic group having three or more aromatic rings.

3. The urea-linked tetrafunctional (meth) acrylate compound according to claim 1, wherein a in formula (1) is a divalent organic group of a structure represented by formula (3);

[ solution 3]

4. The urea-linked tetrafunctional (meth) acrylate compound according to claim 1,2 or 3, wherein m in formula (1) is 0.

5. The urea-linked tetrafunctional (meth) acrylate compound according to claim 3 or 4, wherein R in formula (3)₃、R₄、R₅、R₆、R₇And R₈Is methyl and Z is propylene.

6. A composition comprising the urea-linked tetrafunctional (meth) acrylate compound according to any one of claims 1 to 5.

7. A composition comprising the urea-linked tetrafunctional (meth) acrylate compound according to claim 3, and a siloxane compound having a three-dimensional crosslinking structure.

8. The composition according to claim 7, wherein the siloxane compound having a three-dimensional crosslinking structure is contained in an amount of 1 to 20 parts by weight relative to 1 part by weight of the urea-bonded type tetrafunctional (meth) acrylate compound.

9. A hardened coating film obtained from the urea-bonded tetrafunctional (meth) acrylate compound according to any one of claims 1 to 5 or the composition according to any one of claims 6 to 8.

10. An electronic component having the cured coating film according to claim 9.