WO2007049579A1

WO2007049579A1 - Squarylium compound and photopolymerizable composition for short-wavelength light source using same

Info

Publication number: WO2007049579A1
Application number: PCT/JP2006/321098
Authority: WO
Inventors: Yutaka Osedo; Junzo Yamano
Original assignee: Kyowa Hakko Chemical Co., Ltd.
Priority date: 2005-10-24
Filing date: 2006-10-24
Publication date: 2007-05-03
Also published as: JPWO2007049579A1; TW200720842A

Abstract

Disclosed is a photopolymerizable composition containing a squarylium compound represented by the general formula (I) below, a radical initiator and a compound having an ethylenically unsaturated double bond. (I) [In the formula, R1 and R2 independently represent a hydrogen atom, an optionally substituted alkyl group or the like; and X represents a group expressed as the formula (A) below (wherein R3 represents an optionally substituted phenyl group or the like; R4 represents a methyl group or an ethyl group; and R5, R6, R7 and R8 independently represent a hydrogen atom, an optionally substituted alkyl group or the like) or the like.]

Description

Specification

SQUARYLIUM COMPOUND AND PHOTOPOLYMERIZABLE COMPOSITION FOR SHORT WAVE LIGHT SOURCE

[0001] The present invention relates to a photopolymerizable composition using a squarylium compound as a sensitizer for a short wavelength light source.

Conventional technology

[0002] With the development of short-wavelength light source technology, research and development in the lithography field and printing field that use this as an exposure light source are being actively conducted. In addition, due to a decrease in the price of short wavelength light sources, its use in direct imaging (DI) using this is being studied. Along with this, research and development of photopolymerizable compositions for short-wavelength light sources has been conducted, and application research not only for DI materials but also for wiring pattern materials, solder resist materials and resist ink materials has become active. Has been done.

However, since the output of a short wavelength light source is generally smaller than that of a conventional light source in the visible region, the output to a photopolymerizable composition in the wavelength region of a short wavelength light source (350ηπ! To 450 nm) is increased. Sensitization is required. As sensitizers corresponding to light of 350 nm to 450 nm, benzophenone compounds and coumarin compounds are known (for example, see Patent Document 1). Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004-086122

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to provide a photopolymerizable composition having excellent sensitivity to light in the wavelength region of a short wavelength light source.

Means for solving the problem

[0005] The present invention provides the following [1] to [6].

[1] General formula (I)

[0006] [Chemical 1]

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. Each represents an aralkyl group that may have, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, or R ¹ and R ² are each It may be substituted with an adjacent nitrogen atom to form a heterocyclic group.

X is the following formula (A)

[0008] [Chemical 2]

(Wherein R ³ has a substituent! /, May represent a benzyl group or a phenyl group which may have a substituent, and

R ⁴ represents a methyl group or an ethyl group,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and have a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. Represents an aralkyl group, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, or R ⁵ and R ⁷ and / or R ⁶ and R ⁸ may each form an aromatic ring together with adjacent C—C), or the following formula (B)

[0010] [Chemical 3]

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above, respectively)

R ⁹ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. A compound having a squarylium compound, a radical initiator, and an ethylenically unsaturated double bond represented by V), an aryl group, or a substituent, which may represent a heterocyclic group. A photopolymerizable composition containing the product.

[2] The squarylium compound has the general formula (IA)

[0012] [Chemical 4]

[0013] (where

R ⁷ and R ⁸ are as defined above, respectively.) The photopolymerizable composition according to [1].

[3] The squarylium compound has the general formula (IB)

[0014] [Chemical 5]

[0015] The photopolymerizable composition according to the above [1], wherein RR ² , RR ⁶ , RR ⁸ and R ⁹ are as defined above.

[4] The squarylium compound is 350ηπ! The photopolymerizable composition according to any one of the above [1] to [3], which has a maximum absorption wavelength in a wavelength region of 450 nm.

[5] General formula (la)

[0016] [Chemical 6]

(Wherein R ^LA is the same or different and has a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. A force representing an optionally substituted aralkyl group or an optionally substituted heterocyclic group, or R ^LA and R ^2A each have a substituent together with the adjacent nitrogen atom. May form a heterocyclic group

R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are the same as R ³ ,

R ⁷ and are synonymous with each other).

[6] General formula (lb)

[0018] [Chemical 7]

(Wherein R ^lb , R ^2b , R ^5b , R ^6b , R ^7b and R ^8b have the same ^{meanings as} R ¹ R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ , respectively) ,

R ^9b may have an alkyl group that may have a substituent, an aralkyl group that may have a substituent, an aryl group that may have a substituent, or may have a substituent. Represents a heterocyclic group).

The invention's effect

[0020] According to the present invention, a photopolymerizable composition having excellent sensitivity to light in a wavelength region of a short wavelength light source can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0021] Hereinafter, the compound represented by the general formula (I) is referred to as a compound (I). The same applies to compounds with other formula numbers.

In the definition of each group in the general formula, the alkyl moiety in the alkyl group and the alkoxyl group includes, for example, a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 2-methylbutyl group, tert —Pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

[0022] Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group. Examples of aryl groups include a phenyl group, a naphthyl group, an anthryl group, and the like.

[0023] Examples of the heterocyclic group include an aromatic heterocyclic group and an alicyclic heterocyclic group.

Examples of the aromatic heterocyclic group include a 5-membered or 6-membered monocyclic aromatic heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom, and sulfur nuclear power, and a condensed 3- to 8-membered ring. A bicyclic or tricyclic nitrogen atom, an oxygen atom and a sulfur atom, and a condensed aromatic heterocyclic group containing at least one atom, and more specifically, a pyridyl group, a pyradyl group, Pyrimidyl group, pyridazyl group, quinolyl group, isoquinolyl group

, Phthaladyl group, quinazolyl group, quinoxalinyl group, naphthyridyl group, cinnolinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, benzyl group, furyl group, thiazolyl group, oxazolyl group, indolyl Group, isoindolyl group, indazolyl group, benzimidazolyl group, benzotriazolyl group, benzothiazolyl group, benzoxazolyl group, purinyl group, carbazolyl group and the like.

As the alicyclic heterocyclic group, for example, a 5-membered or 6-membered monocyclic alicyclic heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and sulfur nuclear power, 3 to 8 Bicyclic or tricyclic fused member ring, nitrogen atom, oxygen atom, and sulfur nuclear power, and at least one atom selected from condensed cycloaliphatic heterocyclic group, and more specifically, Pyrrolidyl group, piperidyl group, piperazil group, morpholinyl group, thiomorpholinyl group

, Homopiperidyl group, homopiperazyl group, tetrahydropyridyl group, tetrahydroquinolyl group, tetrahydroisoquinolyl group, tetrahydrofuryl group, tetrahydrobiral group, dihydrobenzofural group, tetrahydrocarbazolyl group, etc. It is done.

[0025] The aromatic ring formed by combining R ⁵ and R ⁷ and / or R ⁶ and R ⁸ together with C—C of the adjacent benzene ring includes, for example, bicyclic or tricyclic condensed ring Specific examples include aromatic rings, and specific examples include naphthalene rings and anthracene rings.

Examples of the heterocyclic group formed by combining R ¹ and R ² with the adjacent nitrogen atom and the heterocyclic group formed by combining R ^la and R ^2a with the adjacent nitrogen atom include at least 1 5- or 6-membered monocyclic heterocyclic group containing one nitrogen atom (the monocyclic heterocyclic group may contain other nitrogen atom, oxygen atom or sulfur atom), 3 to 8 member The rings of Bicyclic or tricyclic condensed ring heterocyclic group containing at least one nitrogen atom (the condensed heterocyclic group may contain other nitrogen atom, oxygen atom or sulfur atom), etc. Specific examples thereof include pyrrolidinyl group, piperidino group, piperazinyl group, morpholino group, thiomorpholino group, homopiperidino group, homopiperazinyl group, tetrahydropyridyl group, tetrahydroquinolyl group, tetrahydroisoquinolyl group, pyrrolyl group, Examples include an imidazolyl group, a pyrazolyl group, an indolyl group, an indolyl group, and an isoindolyl group.

[0026] Examples of the substituent of the alkyl group and the alkoxyl group include the same or different 1 to 3 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxyl group, an alkoxyalkoxyl group and the like. Can be given. Here, the alkyl part in the alkoxyl group has the same meaning as described above. The alkyl part of the alkoxyalkoxyl group has the same meaning as described above, and the alkylene part has the same meaning as that obtained by removing one hydrogen atom from the lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0027] Aralkyl group, aryl group, heterocyclic group, heterocyclic group formed by combining R ¹ and R ² together with adjacent nitrogen atom, R ^la and R ^2a together with adjacent nitrogen atom Examples of the substituent of the formed heterocyclic group, benzyl group, and phenyl group include the same or different 1 to 5 substituents, specifically, a hydroxyl group, a carboxyl group, a halogen atom, and an alkyl group. An alkoxyl group, a nitro group, an alkyl-substituted or unsubstituted amino group, a benzoyl group, and the like. Here, the alkyl moiety in the halogen atom, alkyl group and alkoxyl group has the same meaning as described above. The alkyl part of the alkyl-substituted amino group has the same meaning as the alkyl group. When the alkyl-substituted amino group is an amino group substituted with two alkyl groups, the two alkyl groups may be the same or different! /

[0028] Compound (I) can be produced according to a known method (WO01Z44233 or the like).

For example, the compounds (la) and (lb) can be produced as follows. Reaction formula 1

[0029] [Chemical 8]

[0030] Reaction Formula 2

[0031] [Chemical 9]

Compound (IV)

[0032] Reaction Formula 3

[0033] [Chemical 10]

R 1 a

Compound (V) + HN Compound (la)

R ^2a

(Via)

[0034] Reaction Formula 4

[0035] [Chemical 11]

[0036] Reaction formula 5

[0037] [Chemical 12] Compound (珊)

(DO

[0038] Reaction formula 6

[0039] [Chemical 13]

R 1 b

Compound (K) + HN Compound (lb)

_R 2b

圆

[0040] [wherein R ^la , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a , and R ^lb , R ^2b , R ^5b , R ^6b , R ⁷

R ^8b and R ^9b are as defined above, and W represents a chlorine atom or a bromine atom.]

Reaction formula 1

Compound (IV) is obtained by reacting Compound (IV) with 1 to 2 moles of Compound (III) in the presence of 0 to 2 moles of base in a solvent at 0 to 40 ° C for 1 to 20 hours. Can be obtained.

[0041] Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane, ethers such as jetyl ether and tert-butyl methyl ether, and aromatics such as toluene and benzene. Examples thereof include hydrocarbons, alcohols such as methanol, ethanol and propanol, tetrahydrofuran, ethyl acetate, dimethylformamide, dimethylsulfoxide (DMSO) and the like.

[0042] Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide, and sodium hydroxide. .

Compound (ΠΙ) is available as a commercial product.

Reaction formula 2

Compound (V) was prepared by mixing Compound (IV) in a 50 to 90 vol% acetic acid aqueous solution at 90 to 120 ° C. For 1 to 7 hours, or in a 50 to 99% by weight aqueous trifluoroacetic acid solution at 45 to 50 ° C for 0.1 to 3 hours.

Reaction formula 3

Compound (la) can be obtained by reacting compound (V) with 1 to 5 moles of compound (Via) in a solvent at a temperature of 80 to 150 ° C. for 1 to 15 hours.

[0043] As the solvent, for example, an alcohol solvent such as ethanol, propanol, 2-propanol, butanol, octanol, or a mixed solvent of the alcohol solvent (50% by volume or more) and benzene, toluene or xylene is used. It is done.

After the reaction, if necessary, the target compound may be purified by a method usually used in synthetic organic chemistry (column chromatography method or recrystallization method).

[0044] Compound (VI) is commercially available.

Reaction formula 4

Compound (VIII) is obtained by mixing Compound (IV) with 1 to 2 moles of Compound (VII) in the presence of 1 to 2 moles of an acidic catalyst in a solvent at 0 to 40 ° C for 1 to 20 hours. It is obtained by reacting.

[0045] Examples of the solvent include halogenated hydrocarbons such as chloroform, formaldehyde, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, nitromethane, nitroethane, and nitrogen pan. Aliphatic nitrated hydrocarbons.

Examples of the acidic catalyst include halogenated aluminum such as sodium chloride aluminum and aluminum bromide, ferric halide such as ferric fluoride, ferric chloride and ferric bromide, ferric oxide and the like. And iron oxides, diantimony fluorides, halogenated diantimones such as salt and ferric antimony, zinc chloride, ferric sulfate, trifluoromethanesulfonic acid, and fluorosulfonic acid.

[0046] Compound (VII) is commercially available.

Reaction formula 5

Compound (IX) is obtained by mixing Compound (VIII) in 50 to 90 vol% aqueous acetic acid solution at 90 to 120 ° C for 0.1 to 7 hours, or in 50 to 99 wt% trifluoroacetic acid aqueous solution, 45 to 50 ° C. It can be obtained by treating with C for 0.1 to 3 hours.

Reaction formula 6 Compound (lb) is obtained from compound (IX) and compound (VIb) by a method similar to the synthesis method of compound (la).

Hereinafter, preferred examples of the compounds (la) and (lb) will be exemplified.

[Chemical 14]

The squarylium compound of the present invention can be used as a photopolymerizable composition, a sensitizer for a short wavelength light source, a two-photon absorption dye as a three-dimensional recording material, a filter dye, or a recording material for a short wavelength light source. Can be used as

The photopolymerizable composition for short wavelength light sources is 350ηπ! The inclusion of a sensitizer having a maximum absorption wavelength in a wavelength region of ˜450 nm is also preferable from the viewpoint of operability under a yellow lamp. 350 nn! A squarylium compound having a maximum absorption wavelength in a wavelength region of ˜450 nm is suitable as a sensitizer for a short wavelength light source because the absorption wavelength region matches the wavelength region of a short wavelength light source.

[0049] Next, the photopolymerizable composition of the present invention will be described.

The photopolymerizable composition of the present invention can be obtained by mixing the compound (1), a radical initiator, and a compound having an ethylenically unsaturated double bond. If necessary, it may be prepared by mixing a binder or usual additives (for example, a polymerization accelerator, a thermal polymerization inhibitor, a plasticizer, etc.). Depending on the application, such as for solder resists and resist inks, an additive such as an inorganic filler may be added to improve the film formability by mixing a thermosetting compound with the photopolymerizable composition. You can mix them.

[0050] Radical initiators include s-triazine compounds substituted with at least one trihalomethyl group [2,4,6 tris (trichloromethyl) s-triazine, 2- (4-methoxyphenol) -4,6 -Bis (trichloromethyl) -S-triazine, 2— [2 (furyl-2-yl) bule]-4,6, bis (trichloromethyl) -S-triazine, 2-(4 methoxy 1 naphthalene) 4 , 6-bis (trichloromethyl) s triazine, etc.], organic peroxides [3,3 ', 4,4'-tetrakis (tert-butyldioxycarbol) benzophenone, etc.], N-phenol- Luglycines (N-phenylglycine, p-chlorodiethyl N-phenylglycine, m-methyl N-phenylglycine, etc.), aromatic sulfonyl halide compounds (benzenesulfonyl chloride, p-toluenesulfochloride, etc.), Imidazole dimers [2,2'-bis (o Black port Hue - Le) -4,4 ', 5,5' Tetorafue - biimidazole, etc.), metal - arene complexes [(7 ⁶ -? benzene) (r ⁵ cyclopentadienyl Jefferies -? Le) Iron (II) hexafluorophosphate, fluoroaryl lutitanocene, etc.), diarylhodonium salt (8-linonanaphthalene 1-sulfonic acid diphenol-rhodonium salt, etc.), triarylsulfo-um salt, min Branched polyethyleneimines, alkyl or aryl borates (tetrabutylammonium tributyl butylate, etc.), aromatic ketones (thioxanthone, etc.), alkylphenones (2-benzylthio 2 (dimethylamino) 4 ' Morpholinotylophenone, etc., or benzoin ether, benzyl dimethyl ketal, etc.), diketones, acyloxime esters, sulfur compounds (thiol, diss Fuido etc.), phosphine O sulfoxide and the like can be mentioned. radical An initiator is used individually or in mixture of 2 or more types.

[0051] The compound having an ethylenically unsaturated double bond may be any compound that undergoes addition polymerization by radicals generated when the photopolymerizable composition is exposed to light and cures the photopolymerizable composition. Any type, for example, a monomer having at least one ethylenically unsaturated double bond, an oligomer, or a polymer having an ethylenically unsaturated double bond in the main chain or side chain may be used alone or in combination. Are used as a mixture.

[0052] Examples of the monomer having at least one ethylenically unsaturated double bond include unsaturated carboxylic acid, ester of unsaturated carboxylic acid and monohydroxy compound, unsaturated carboxylic acid and aliphatic polyhydroxyl. Examples thereof include esters with compounds, esters of unsaturated carboxylic acids with aromatic polyhydroxy compounds, esters obtained by ester reactions of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds, and the like.

[0053] Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like.

Examples of the ester of an unsaturated carboxylic acid and a monohydroxy compound include methyl acrylate, butyl acrylate, 2-phenoxychetyl acrylate, p-chlorophenol acrylate, 2- (1 naphthyloxy) ethyl acrylate. Rate, o biphenyl acrylate, pentachlorophenol acrylate, 2,4,6 tribromophenol acrylate, 2 naphthyl acrylate, 2— (2-naphthyloxy) ethyl acrylate, trifluoroethyl acrylate Acrylate, tetrafluoropropyl acrylate, dibromopropyl acrylate, ethyl 2-chloro acrylate, tetrahydrofurfuryl acrylate, etc., compounds obtained by replacing these acrylates with methacrylic acid, These derivatives are exemplified.

[0054] Examples of the ester of an unsaturated carboxylic acid and an aliphatic polyhydroxy compound include, for example, ethylene glycol ditalylate, triethylene glycol ditalylate, tetraethylene glycol ditalylate, and propylene glycol ditalylate. , Neopentyl glycol diatalylate, 1,3 butanediol diatalylate, 1,4-cyclohexanediol diatalylate, hexanediol diatalylate, trimethylolpropane triallate, trimethylol ethane tritalate, trimethylol Methylolpropane tris (ataryl oxypropyl) ether, pentaerythritol ditalylate, pentaerythritol triac Relate, Pentaerythritol Tetratalylate, Dipentaerythritol Diatalylate, Dipentaerythritol Triatalylate, Dipentaerythritol Tetratalylate, Dipentaerythritol Pentatalylate, Dipentaerythritol Hexaatalylate, Glycerol Atarylate, Acrylic acid esters such as sorbitol tritalylate, sorbitol tetratalylate, sorbitol pentaatarylate, sorbitol hexatalylate, compounds in which these acrylic acid moieties are replaced with methacrylic acid, and other aliphatic polyhydroxyl compounds Itaconic acid ester, crotonic acid ester, maleic acid ester and the like.

[0055] Examples of the ester of an unsaturated carboxylic acid and an aromatic polyhydroxy compound include, for example, a nodule quinone diatalylate, a hydride quinone dimetatalylate, a resorcin diatalate, a resorcin dimetatalylate. In addition to pyrogallol triatalylate, etc., EO-modified bisphenol A diatalylate, tris (j8-ataryllooxychetyl) s cyanurate, etc., esters of unsaturated carboxylic acids and aromatic polyhydroxyl compound derivatives, etc. can give.

[0056] Examples of the ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound include condensates of acrylic acid, phthalic acid and ethylene glycol, and acrylic acid and maleic acid. Condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol, and glycerin, condensates of acrylic acid, trimetic acid, and diethylene glycol. It is done.

[0057] Other monomers or oligomers having at least one ethylenically unsaturated double bond used in the present invention include, for example, acrylic amides such as ethylene bisacrylamide, aryl esters such as diacrylic phthalate, and prepolymers thereof. And bure group-containing compounds such as dibutyphthalate, urethane acrylates such as a condensate of glycerin dimetatalylate and hexamethylene diisocyanate, N-bulucarbazole, and N-bulpyrrolidone.

[0058] Examples of the polymer having an ethylenically unsaturated double bond in the main chain include polyesters obtained by polycondensation reaction of unsaturated divalent carboxylic acids and dihydroxy compounds, and unsaturated divalent carboxylic acids. Examples thereof include polyamides obtained by polycondensation reaction with diamine. Examples of the polymer having an ethylenically unsaturated double bond in the side chain include, for example, an unsaturated polymer in the side chain. Examples thereof include polycondensates of divalent carboxylic acids having a sum bond, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid and the like with dihydroxy or diamine compounds. In addition, a polymer having a functional group such as hydroxy group, halogenated methyl group or epoxy group in the side chain

For example, polybutanol, poly (2-hydroxyethyl methacrylate), epoxy resin, phenoxy resin polychlorohydrin, etc. and unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, etc. A polymer obtained by a polymer reaction can also be used.

[0059] Examples of the binder include polymethacrylic acid ester or a partial hydrolyzate thereof, polyacrylic acid ester or a partial hydrolyzate thereof, polyacetic acid bull or a partial hydrolyzate thereof, and a copolymer of butyl acetate and ethylene. Or a partially hydrolyzed product thereof, polystyrene, polybul formal, polybulbutyral, polychloroprene, polysalt vinyl, chlorinated polyethylene, chlorinated polypropylene, phenol novolac or cresol monovolac resin, polybutanol Copolymers of burfenol and methacrylic acid esters, polyethylene oxide, polymethyl isopropanol ketone, copolymers of methacrylic acid ester and phenol isopropyl ketone, polyurethane, polyamide, polycarbonate, polyethylene Terephthalate, polybutylene terephthalate, acetylenic resin, acetyl cellulose, nitrocellulose, polybulur rubazole or its derivatives, copolymer of belcarbazole and styrene, copolymer of burcarbazole and methacrylic acid ester Copolymer of berylcarbazole and acrylate ester, polyvinylpyrrolidone or its derivative, copolymer of bulupyrrolidone and styrene, copolymer of bulupyrrolidone and methacrylic ester, bulupyrrolidone and acrylate ester Copolymers of styrene and maleic acid (monoester), others, acrylic acid ester, acrylic acid, methacrylic acid ester, methacrylic acid, (anhydrous) maleic acid, acrylonitrile, acrylamide, styrene , Vinyl acetate, vinyl chloride, bi - Ride down, butadiene, isoprene, copolymers and the like produced by two or more selection from copolymerizable monomers, such as black hole Puren.

[0060] Examples of the polymerization accelerator include 2-mercaptobenzothiazole.

Examples of the thermal polymerization inhibitor include p-tert-butylcatechol, hydroquinone, chloral and the like. Examples of the plasticizer include jetyl hexyl phthalate, diisobutyl phthalate, tricresyl phosphate, jetyl hexyl sebacate, jetyl hexyl adipate, and the like.

[0061] Examples of the thermosetting compound include, for example, a metatalylate monomer or acrylate monomer having at least one epoxy group, a styrene monomer having at least one epoxy group, and a polyglycidyl ester having no other reactive group. Polymers having two or more epoxy groups such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol _F type epoxy resin , Urethane-modified epoxy resin, epoxy group-containing copolymer and the like.

[0062] Examples of the inorganic filler include calcium carbonate, barium sulfate, silicon oxide, and acid medium.

The amount of the radical initiator used in the photopolymerizable composition of the present invention is 0.1 to: LOO parts, preferably 1 to 50 parts, relative to 1 part by weight of the compound (I) (hereinafter referred to as parts by weight). It is.

[0063] The amount of the compound having an ethylenically unsaturated double bond to be used is 2 to: L 000 parts, preferably 20 to 200 parts, relative to 1 part of the compound (I).

The amount of Noinda is 10 to L000 parts, preferably 60 to 200 parts, per 100 parts of the compound having an ethylenically unsaturated double bond.

The amount of the thermal polymerization inhibitor used is 0.01 to 10 parts with respect to 100 parts of the compound having an ethylenically unsaturated double bond, or 0.01 to 10 parts with respect to the thermosetting compound.

[0064] The thermosetting compound and the inorganic filler are used in an amount of 0.1 to L00, preferably 1 to 20 and 0.1 to 80, respectively, with respect to 100 parts of the total composition. Is 1-10. The photopolymerizable composition of the present invention is 350 ηπ! It has excellent sensitivity in a wavelength region of ˜450 nm and is useful as a photosensitive material for a short wavelength light source.

[0065] The photopolymerizable composition of the present invention includes DI materials, wiring pattern materials, solder resist materials, resist ink materials, photon mode CTP plate materials, dry film resists, digital proofs, holograms, and short wavelength light sources. It can be used as a recording material for printing, and as a photosensitive material such as an adhesive. When the photopolymerizable composition of the present invention is used for applications such as DI materials, a substrate (aluminum plate, printed wiring board) coated with a solution containing the photopolymerizable composition of the present invention by a spin coat method or the like. , Copper-clad laminates, etc.) are irradiated with short-wavelength light, followed by development using aqueous solution of tetramethylammonium hydroxide as a developer, washing with water, and drying to make DI materials, etc. Can be obtained.

[0066] Hereinafter, the present invention will be described more specifically with reference to Examples and Test Examples.

Example 1

[0067] (Production of Compound 1)

The starting material, 4- (N-phenol-N-methylaminophenol) 3-hydroxycyclobutene 1,2-dione, was synthesized according to the method described in WO01Z44233.

4 (N phenyl N methylaminophenyl) 3 hydroxycyclobutene 1,2-dione 400 mg and aline 135 mg were added to a mixed solvent of butanol 1.5 ml and toluene 1.5 ml and reacted at 120 ° C. for 6 hours. Thereafter, the solvent was distilled off, the residue was recrystallized from methanol, and the precipitated yellow solid was collected by filtration to obtain Compound 1 (332 mg).

'H-NMR S (DMSO-d) ppm: 3.37 (3H, s), 6.89 (2H, d, J = 8.3Hz), 7.2

6

2- 7.47 (10H, m), 7.88 (2H, br), 10. 60 (1H, br).

Maximum absorption wavelength (CHC1): 409.0nm

Three

Molar extinction coefficient (CHC1): 42800 (molZl) — ¹ 'cm— ¹

Three

Example 2

[0068] (Production of Compound 2)

4 (N phenyl N methylaminophenyl) 3 hydroxycyclobutene 1,2-dione 400 mg and n-octylamine 185 mg were added to a mixed solvent of butanol 1.5 ml and toluene 1.5 ml, and reacted at 120 ° C. for 6 hours. Thereafter, the solvent was distilled off, the residue was recrystallized from methanol, and the precipitated yellow solid was collected by filtration to obtain Compound 2 (230 mg).

'H-NMR S (DMSO-d) ppm: 0.85 (3H, t, J = 6.8Hz), 1. 25— 1.61 (12H , m), 3.67 (2H, t, J = 6.8Hz), 6.90 (2H, d, J = 9.0Hz), 7.22 (3H, m), 7.43 (2H, m), 7.86 (2H, d, J = 9.0Hz), 8.81 (1H, s).

Maximum absorption wavelength (CHC1): 401.0nm

Three

Molar extinction coefficient (CHC1): 44000 (molZl) — ¹ 'cm— ¹

Three

Example 3

[0069] (Production of Compound 3)

The starting material, 4- (N benzyl-N-ethylaminophenol) 3-hydroxycyclobutene 1,2-dione, was synthesized according to the method described in WOO 1Z44233.

4 (N phenyl N methylaminophenyl) 3 hydroxycyclobutene 1,2-dione 400 mg and n-octylamine 168 mg were added to a mixed solvent of butanol 2.0 ml and toluene 2.0 ml and reacted at 120 ° C. for 6 hours. Thereafter, the solvent was distilled off, the residue was recrystallized from methanol, and the precipitated yellow solid was collected by filtration to obtain Compound 3 (549 mg).

'H-NMRS (DMSO-d) ppm: 0.84 (3H, t, J = 7.1Hz), 1.17 (3H, t, J = 6.8

6

Hz), 1.24-1.62 (12H, m), 3.52— 3.68 (2H, m), 3.73 (2H, t, J = 7.1Hz), 6.77 (1H, d, J = 3.4Hz), 6.79 (1H , d, J = 3.4Hz), 7.20-7.26 (3H, m), 7.31 -7.35 (2H, m), 7.82 (1H, d, J = 9.0Hz), 7.86 (1H, d, J = 9.0Hz) , 7.86 (2H, d, J = 9.0Hz), 10.92 (1H, s).

Maximum absorption wavelength (CHC1): 404.0nm

Three

Molar extinction coefficient (CHC1): 40300 (molZl) — ¹ 'cm— ¹

Three

Example 4

[0070] (Production of Compound 4)

Under a nitrogen atmosphere, 3.00 g of 3,4 dichloro-3 cyclobutene 1,2 dione and 1.83 g of toluene were dissolved in 5 ml of dichloromethane. To this solution, 3.98 g of aluminum chloride was added little by little and stirred at 35 ° C for 5 hours. Thereafter, water and dichloromethane were added to the reaction mixture, and the organic layer was washed with water and dried. The solvent was distilled off, 15 ml of acetic acid and 15 ml of water were added to the resulting yellow solid, and the mixture was stirred at 70 ° C. for 1 hour. The reaction mixture was extracted with dichloromethane, the organic layer was washed with water, dried and concentrated, and the resulting crystals were washed with water, dried and washed with 4-tolyl 3-hydroxycyclobute. 1.38 g dione, 2 dione was obtained.

[0071] 4 Tolyl 1-3 hydroxycyclobutene 1,2 dione 200 mg and n-octylamine 1 37 mg were placed in a mixed solvent of butanol 1.5 ml and toluene 1.5 ml, and reacted at 120 ° C for 5 hours. Thereafter, the precipitated white solid was collected by filtration to obtain Compound 4 (169 mg).

'H-NMRS (DMSO-d) ppm: 0.84 (3H, t, J = 6.8Hz), 1.25— 1.29 (10H,

6

m), 1.66 (2H, m), 2.35 (3H, s), 3.81 (2H, t, J = 6.8Hz), 7.31 (2H, d, J = 8 • 3Hz), 7.92 (1H, d, J = 8.3Hz), 11.71 (1H, br).

Maximum absorption wavelength (CHC1): 379.5nm

Three

Molar extinction coefficient (CHC1): 44900 (molZl) — ¹ 'cm— ¹

Three

Example 5

[0072] (Production of Compound 5)

The starting material, 4-tolyl-3 hydroxycyclobutene-1,2 dione, was obtained in the same manner as in Example 4.

4-Tolyl 3 hydroxycyclobutene 1,2 dione 50111 ₈ and 47 mg of 2,6-diisopropylphenol were added to a mixed solvent of 0.75 ml of butanol and 0.75 ml of toluene, and reacted at 120 ° C. for 5 hours. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 5 (54 mg).

'H-NMRS (DMSO-d) ppm: 1.14 (12H, s), 2.34 (3H, s), 2.98 (2H, q,

6

J = 6.8Hz), 7.28 (2H, d, J = 7.6Hz), 7.34 (2H, d, J = 8.3Hz), 7.41 (1H, t, J = 7.6Hz), 7.97 (2H, d, J = 8.1Hz).

Maximum absorption wavelength (CHC1): 389.5nm

Three

Molar extinction coefficient (CHC1): 41900 (molZl) ^_1 'cm ^_1

Three

Example 6

[0073] (Production of Compound 6)

Under a nitrogen atmosphere, 4.00 g of 3,4 dichloro-3 cyclobutene-1,2 dione and 2.87 g of 1,3,5 trimethylbenzene were dissolved in 5 ml of dichloromethane. To this solution, 3.53 g of aluminum chloride was added little by little and stirred at 35 ° C for 3 hours. Then add water and dichloromethane to the reaction mixture Methane was added and the organic layer was washed with water and dried. The solvent was distilled off, 20 ml of acetic acid and 20 ml of water were added to the resulting yellow solid, and the mixture was stirred at 70 ° C. for 1 hour. The reaction mixture was extracted with dichloromethane, the organic layer was washed with water, dried and concentrated, and the resulting crystals were washed with water and dried to give 4.37 g of 4- (1,3,5 trimethylphenyl) 3 hydroxycyclobutene 1,2 dione. Obtained.

[0074] 4— (1,3,5 Trimethylphenol) 3 Hydroxycyclobutene 1,2 Dione 1 OOmg and n-octylamine 60 mg were added to a mixed solvent of butanol l.Oml and toluene l.Oml, and 120 The reaction was performed at ° C for 6 hours. Thereafter, the solvent was distilled off, and the residue was separated and purified with a PLC preparative plate (developing solvent, chloroform: methanol = 5: 1) to obtain Compound 6 (16 mg).

— NMR S (DMSO-d) ppm: 0.85 (12H, s), 2.34 (3H, s), 2.98 (2H, q, J

6

= 6.8Hz), 7.28 (2H, d, J = 7.6Hz), 7.34 (2H, d, J = 8.3Hz), 7.41 (1H, t, J

= 7.6Hz), 7.97 (2H, d, J = 8.1Hz).

Maximum absorption wavelength (CHC1): 338.0nm and 390.0nm

Three

Molar extinction coefficient (CHC1): 21900

3 (πιοΐΖΐΓ ¹ · cm— ¹

Example 7

[0075] (Production of Compound 7)

Under a nitrogen atmosphere, 3.00 g of 3,4 dichloro-3 cyclobutene 1,2 dione and 1.55 g of benzene were dissolved in 5 ml of dichloromethane. To this solution, 3.98 g of aluminum chloride was added little by little and stirred at 35 ° C for 5 hours. Thereafter, water and dichloromethane were added to the reaction mixture, and the organic layer was washed with water and dried. The solvent was distilled off, 20 ml of acetic acid and 20 ml of water were added to the obtained yellow solid, and the mixture was stirred at 70 ° C for 3 hours. The reaction mixture was extracted with dichloromethane, the organic layer was washed with water, dried and concentrated, and the resulting crystals were washed with water and dried to give 1.92 g of 4-fluoro-3-hydroxycyclobutene 1,2 dione.

[0076] 4-Phenyl 3-hydroxycyclobutene 1,2 dione 1 OO mg and 74 mg of n-octylamine were added to a mixed solvent of 0.75 ml of butanol and 0.75 ml of toluene, and reacted at 120 ° C for 6 hours. Thereafter, the solvent was distilled off, the residue was recrystallized from methanol, and the precipitated white pink solid was collected by filtration to obtain Compound 7 (16 mg).

'H-NMR S (DMSO-d) ppm: 0.84 (3H, t, J = 6.8Hz), 1.25— 1.66 (12H, m), 3.83 (2H, t, J = 6.8Hz), 7.44— 7.51 (3H, m), 8.00— 8.03 (2H, m). Maximum absorption wavelength (CHC1): 372.5 nm

Three

Molar extinction coefficient (CHC1): 34200 (molZl) — ¹ 'cm— ¹

Three

Example 8

[0077] (Production of Compound 8)

The starting material, 4-phenol 3 hydroxycyclobutene 1,2 dione, was obtained in the same manner as in Example 7.

4 Phenolinole 3 Hydroxycyclobutene 1,2 Dione 1 OOmg and monoreforin 5 lmg were added to a mixed solvent of 0.75 ml of butanol and 0.75 ml of toluene and reacted at 120 ° C for 6 hours. Thereafter, the precipitated yellowish white solid was collected by filtration to obtain Compound 8 (118 mg). 'H-NMRS (DMSO-d) ppm: 3.91 (4H, t, J = 4.6Hz), 4.13 (4H, t, J = 4.4

6

Hz), 7.45-7.51 (3H, m), 8.00—8.01 (2H, m).

Maximum absorption wavelength (CHC1): 385.0nm

Three

Molar extinction coefficient (CHC1): 40800 (molZl) — ¹ 'cm— ¹

Three

Example 9

[0078] (Production of Compound 9)

Under a nitrogen atmosphere, 3.00 g of 3,4 dichloro-1 3 cyclobutene 1,2 dione and 2.55 g of naphthalene were dissolved in 5 ml of dichloromethane. To this solution, 3.98 g of aluminum chloride was added little by little and stirred at 35 ° C for 5 hours. Thereafter, water and dichloromethane were added to the reaction mixture, and the organic layer was washed with water and dried. The solvent was distilled off, and 15 ml of acetic acid and 15 ml of water were added to the obtained yellow solid, followed by stirring at 70 ° C. for 1 hour. The reaction mixture was extracted with dichloromethane, the organic layer was washed with water, dried and concentrated, and the resulting crystals were washed with water and dried to obtain 0.70 g of 4 (1 naphthyl) 3 hydroxycyclobutene 1,2-dione.

[0079] 4- (1 naphthyl) 3 hydroxycyclobutene 1,2 dione (50 mg) and n-octylamine (29 mg) were added to a mixed solvent of butanol (0.75 ml) and toluene (0.75 ml) and reacted at 120 ° C for 5 hours. Thereafter, the precipitated yellow solid was collected by filtration to obtain Compound 5 (9 mg).

'H-NMRS (DMSO-d) ppm: 0.84 (3H, t, J = 6.8Hz), 1.26— 1.32 (10H, m), 1.71 (2H, t, J = 6.8Hz), 3.91 (2H, t, J = 7.1Hz), 7.58—7.94 (3H, m), 7.96 (1H, d, J = 7.6Hz), 8.02 ( 1H, d, J = 8.1Hz), 8.62 (1H, d, J = 7.6Hz), 9.24 (1H, d, J = 8.1Hz).

Maximum absorption wavelength (CHC1): 420.5nm

Three

Molar extinction coefficient (CHC1): 41900 (molZl) ^_1 'cm ^_1

Three

Example 10

[0080] (Production of Compound 10)

4 (N-phenyl N-methylaminophenyl) 3 Hydroxycyclobutene 1,2-dione lOOmg and 2-aminobenzophenone 108 mg are added to a mixed solvent of butanol 1.5 ml and toluene 1.5 ml 1, and reacted at 120 ° C for 6 hours. It was. Thereafter, the precipitated reddish brown solid was collected by filtration to obtain Compound 10 (108 mg).

'H-NMRS (DMSO-d) ppm: 3.35 (3H, s), 6.84 (2H, d, J = 9.0Hz), 7.2

6

4-7.69 (16H, m), 10.76 (1H, br).

Maximum absorption wavelength (CHC1): 428.0nm

Three

Molar extinction coefficient (CHC1): 43100 (molZl) ^_1 'cm ^_1

Three

Example 11

[0081] Pentaerythritol triatalylate (manufactured by Shin-Nakamura Co., Ltd., NK ESTER-TMM-3) 100 parts, polyvinylpyrrolidone (Tokyo Chemical Industry Co., Ltd., K-90, weight average molecular weight 360000) 100 Part, 2 benzyl-2 (dimethylamino) -4'-morpholinob tyrophenone (Sigma Aldrich Japan Co., Ltd .; radical initiator) 8 parts, 1 part of squarylium compound of compounds 1-5 dissolved in 1900 parts of ethyl acetate sorb Polymerizable compositions 1 to 5 were obtained. Each of these photopolymerizable compositions was formed on a polyethylene terephthalate film by a spin coating method and dried in warm air to prepare a photopolymerizable composition film.

[Comparative Example 1]

Coumarinl53 (Sigma-Aldrich) instead of the sensitizer squarylium compound A film was prepared by the method described in Example 11 using a maximum absorption wavelength of 419 nm (in acetonitrile solution) manufactured by Japan Corporation. Further, in the method described in Example 11, a squarylium compound as a sensitizer was not added (other conditions were the same as in Example 11), and a dye-free film was produced.

[Test Example 1]

The sensitivity of the film of the photopolymerizable composition obtained in Example 11 and Comparative Example 1 was evaluated in accordance with “Basics and Applications of Photopolymer” (Supervised by Ao Yamaoka Co., Ltd. 1997).

[0082] Under nitrogen flow, light from an ultra-high pressure mercury lamp is Y-50 sharp-cut filter (Asahi Techno Glass), L-39 Sharp cut filter (Asahi Techno Glass), ND-25 Decrease filter (Asahi Techno Glass) And the film was exposed through a step tablet. Next, development is performed with water, and the transmittance of the step tablet corresponding to the remaining number of steps of the film, the UV integrated illuminance meter UVPF-AI (made by Eye Graphics Co., Ltd.) and the receiver PD405 (made by Eye Graphics Co., Ltd.) The minimum amount of energy required for curing was determined from the obtained irradiation light amount, and this was used as the film sensitivity of the photopolymerizable composition.

[0083] The sensitivity of the film when using the photopolymerizable composition 1 to 5 and the sensitivity of the film when prepared without a dye, the sensitivity of the film when using Coumarinl53 as 1, and the relative ratio ( The relative sensitivity is shown in Table 1.

[0084] [Table 1] Table 1. Relative sensitivity of photopolymerizable composition

Example 12 [0085] Pentaerythritol triatalylate (manufactured by Shin-Nakamura Co., Ltd., NK ESTER—TMM-3) 100 parts, polyvinylpyrrolidone (Tokyo Chemical Industry Co., Ltd., K-90, weight average molecular weight 360000) Part, 2- [2- (furan 2-yl) bur]-4,6-bis (triclo mouth methyl)-1,3,5-triazine (manufactured by Wako Pure Chemical Industries, Ltd .; radical initiator) 8 parts Then, 1 part of a squarylium compound of Compound 2, Compound 3 or Compound 5 was dissolved in 1900 parts of an ethyl acetate sorb to obtain photopolymerizable compositions 6-8. Each of these photopolymerizable compositions was formed on a polyethylene terephthalate film by a spin coating method and dried with warm air to prepare a photopolymerizable composition film.

[Comparative Example 2]

A film was prepared by the method described in Example 12 using Coumarinl53 (manufactured by Sigma-Aldrich Japan Co., Ltd., maximum absorption wavelength 419 nm (in acetonitrile solution)) instead of the squarilium compound as a sensitizer. Also, a dye-free film was produced by the method described in Example 12 under the same conditions except that the squarylium compound as a sensitizer could not be added.

[Test Example 2]

The film sensitivity of the photopolymerizable composition obtained in Example 12 and Comparative Example 2 was evaluated by the method described in Test Example 1.

[0086] The sensitivity of the film when the photopolymerizable composition 6 to 8 is used and the sensitivity of the film when prepared as a pigment-free composition, the sensitivity of the film when using Coumarinl53 is 1, and the relative ratio

(Relative sensitivity) is shown in Table 2.

[0087] [Table 2] Table 2. Relative sensitivity of photopolymerizable composition

Relative sensitivity [1]

Photopolymerizable composition ⁶ 1.0 0

Photopolymerizable composition ⁷ 0.6 6 0

Photopolymerizable composition ⁸ 1.0 0

Element to 4. 3 0 [0088] From the results in Table 1 or Table 2, the minimum energy required for curing is shorter and the short wavelength is shorter when the photopolymerizable composition of the present invention is used than when Coumarinl 53 is used and when no dye is used. It can be seen that it has excellent sensitivity to the light source.

Industrial applicability

[0089] According to the present invention, a photopolymerizable composition having excellent sensitivity to light in the wavelength region of a short wavelength light source can be provided.

Claims

The scope of the claims

Formula (I)

[Chemical 15]

[Wherein, R ¹ and R ² are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. which may be § La alkyl group which may have a substituent Ariru group or represents a heterocyclic group which may have a substituent, or R ¹ and R ^2, the nitrogen to which each adjacent It may have a substituent together with an atom, or it may form a heterocyclic group.

X is the following formula (Α)

[Chemical 16]

(Wherein R ³ represents an optionally substituted benzyl group or an optionally substituted phenyl group;

R ⁴ represents a methyl group or an ethyl group,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and have a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. May be Represents an aralkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, or R ⁵ and R ⁷ and / or R ⁶ and R ⁸ are May be combined with adjacent C—C to form an aromatic ring), or the following formula (B)

[Chemical 17]

Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above,

The squarylium compound has the general formula (IA)

[Chemical 18]

(Where

^{2. The} photopolymerizable composition according to claim 1, wherein R ² , R ³ , R ⁴ , R ⁵ , R °, R ⁷ and R ⁸ are as defined above.

The squarylium compound has the general formula (IB)

^{^{(Wherein, R \ R 2, R 5}} , R 6, RR 8 and R ⁹ are the same meanings as defined above, respectively) photopolymerizable composition of claim 1, wherein represented by.

The squarylium compound is 350ηπ! The photopolymerizable composition according to any one of claims 1 to 3, which has a maximum absorption wavelength in a wavelength region of ~ 450 nm.

Formula (la)

[Chemical 20]

(Wherein R ^LA is the same or different and is a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. A force representing a good aralkyl group or a heterocyclic group which may have a substituent, or R ^LA and R ^2A may each have a substituent together with an adjacent nitrogen atom. May form a good heterocyclic group

R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are the same as R ³ ,

R ⁷ and are synonymous with each other).

[6] General formula (lb) [Chemical 21]

(In the formula, R ^lb , R ^2b , R ^5b , R ^6b , R ^7b and R ^8b have the same ^{meanings as} R ¹ R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ , respectively.