JP2001228607A - Infrared curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an IR curable composition having high sensitivity to infrared laser light, excellent in durability and handleable under a white light. SOLUTION: In the IR curable composition containing (a) a compound containing an ethylenically unsaturated double bond, (B) an IR absorbent and (C) a polymerization initiator, (d) an epoxy compound is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having high sensitivity to infrared laser light and excellent heat resistance, and more particularly to a photo solder resist suitable for forming a solder mask on a printed wiring board.

[0002]

2. Description of the Related Art As a method for forming a solder mask, there are known two methods: 1) a printing method and 2) a photographic method. The printing method is to transfer a resist ink onto a printed circuit board by screen printing, which is advantageous in terms of cost, but is inferior in positional accuracy and resolving power, and is therefore mainly used for low-density printed circuit boards. In recent years, electronic devices have become smaller and thinner,
Although the specific gravity of production has shifted to high-density printed circuit boards due to the sophistication, photographic methods are used to form these solder masks. The photographic method is formed by applying a photosensitive heat-resistant resin described in Japanese Patent Publication No. 1-54390 or the like on the entire surface of the substrate, exposing the image through a negative film, and removing the uncured portion by a developing treatment. The photographic method is superior to the printing method in the positional accuracy and the resolution, but cannot sufficiently cope with an ultra-high-density substrate represented by a build-up substrate or the like. This is because, in a photographic method using a negative film, a decrease in positional accuracy and resolution due to film expansion and contraction, light scattering, and the like is inevitable. As a method for overcoming this problem, a direct drawing method of a solder mask using a laser beam without using a negative film is effective, and is disclosed in JP-A-10-115921.
Publications are technically known. These laser direct writing methods are performed by an ultraviolet light or visible light laser, and largely depend on a conventionally known photo solder resist having sensitivity from ultraviolet light to visible light. Direct drawing with an ultraviolet laser has a problem that sufficient productivity cannot be obtained due to low sensitivity of the photo solder resist and low output of the ultraviolet laser, and has not been put to practical use. On the other hand, in the case of direct drawing with a visible light laser, the photo solder resist is exposed to yellow light, which is a work in a dark room, and has problems in handling. In addition, since there is no high-power laser similarly to the ultraviolet laser, there is a problem in productivity. Further, both the ultraviolet and visible lasers have a short life and are expensive, so there is a problem in terms of cost. On the other hand, with the advent of long-wavelength lasers, infrared curable compositions containing an ethylenic compound, an infrared absorber and a polymerization initiator and having sensitivity to infrared light have been proposed. The application of is not known.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides an infrared curable composition which does not require work in a dark room, is excellent in productivity, is excellent in sensitivity, resolution and durability, and is useful as a solder resist. To provide.

[0004]

Means for Solving the Problems An infrared laser beam having a long life and high output has been obtained, and if a photo solder resist having high sensitivity and excellent durability to the infrared laser beam can be obtained, No need to work in a dark room, good productivity,
A solder mask forming method by a laser direct writing method can be realized. As a result of intensive studies, the present inventor has found that the infrared curable composition contains the epoxy compound (d), so that the composition is highly sensitive to infrared laser light, and has the resolution and durability required for a solder mask. The present invention was also found to have both properties and completed the present invention. That is, the gist of the present invention is an infrared curable composition containing (a) an ethylenically unsaturated double bond-containing compound, (b) an infrared absorber and (c) a polymerization initiator. The infrared ray curable composition is characterized in that the composition contains (d) an epoxy compound. Hereinafter, the present invention will be described in detail.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The (a) ethylenically unsaturated double bond-containing compound includes a compound in which an unsaturated double bond is polymerized by a radical, and from the viewpoint of polymerization activity, (meth)
It is a compound having an acryloyl group, and a so-called acrylic monomer can be mentioned as a preferable one. Here, the (meth) acryloyl group represents an acryloyl group and a methacryloyl group. As an acrylic monomer, an ester acrylate compound obtained by condensing an unsaturated carboxylic acid with an aliphatic alcohol or an aromatic hydroxy compound,
Epoxy acrylate compounds in which unsaturated carboxylic acids are added to aliphatic or aromatic epoxy compounds, urethane acrylate compounds in which unsaturated hydroxy compounds are added to isocyanate compounds, phosphate esters having a (meth) acryloyl group, and the like. It is possible, but not necessarily limited to these.

Examples of the ester acrylate compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin methacrylate (meth) acrylate, trimethylolpropane di (meth) acrylate Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane ethylene oxide added tri (meth) acrylate, glycerin propylene oxide added Tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth)
Examples include acrylate, sorbitol hexa (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.

[0007] Examples of the epoxy acrylate compound include compounds obtained by adding an α, β-unsaturated carboxylic acid to an epoxy compound having an epoxy ring such as a glycidyl group or an alicyclic epoxy group. As the epoxy compound, the base skeleton to which the epoxy ring is bonded is an aliphatic, aromatic, or heterocyclic ring, or various epoxy compounds having a structure in which these are mixed. Examples of the aromatic epoxy compound include halogenated compounds such as phenol novolak epoxy compound, (o, m, p) -cresol novolak epoxy compound, bisphenol-A epoxy compound, bisphenol-F epoxy compound, and brominated phenol novolak epoxy compound. Epoxy compounds and the like. These compounds may be low molecular weight compounds or oligomers or high polymers that become resins.

Examples of the aliphatic epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, (poly) glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl diglycidyl ether, hexanediol diglycidyl ether, and (poly) Examples include ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) tetramethylene glycol diglycidyl ether, (poly) pentamethylene glycol diglycidyl ether, and the like. Examples of the epoxy compound having a heterocyclic structure include triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

The alicyclic epoxy compounds include Celloxide 2021, 2080, 3000 manufactured by Daicel Chemical Industries, Ltd.
2000, EPOLIDE GT300, GT400 and the like. Α, β-
As the unsaturated carboxylic acid, for example, an epoxy acrylate compound to which (meth) acrylic acid or the like is added as a catalyst with a quaternary ammonium salt or the like can be preferably used, and further, an acid anhydride such as maleic anhydride or tetrahydrophthalic anhydride can be used. Modified epoxy acrylates further modified with

As urethane acrylate compounds, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate;
Aliphatic diisocyanate such as 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω ′
Alicyclic diisocyanate such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α,
aliphatic diisocyanate having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate
4-isocyanatomethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptanetriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate and other triisocyanates such as hydroxymethyl (meth) acrylate, hydroxyethyl Examples thereof include compounds obtained by reacting an acrylic compound having a hydroxyl group such as (meth) acrylate.

The phosphate ester has a structure in which a part of a hydroxyl group of phosphoric acid such as methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate, methacryloxyethylene glycol phosphate is esterified. A compound having a (meth) acryloyl group is exemplified. Among the acrylic monomers mentioned above, two or more, especially three or more (meth) in the molecule
Ester acrylate having an acryloyl group, or
It is particularly preferred to include urethane acrylate.

More specifically, the (b) infrared absorber used in the present invention is a near-infrared absorbing dye having an absorption band in a part or the whole of a wavelength range of 650 to 1300 nm, an organic or inorganic pigment, and a metal. And the like. Specifically, for example, carbon black; graphite; metals such as titanium and chromium; metal oxides such as titanium oxide, tin oxide, zinc oxide, vanadium oxide, and tungsten oxide; metal carbides such as titanium carbide; metal borides; Examples thereof include inorganic black pigments, azo black pigments, and black or green organic pigments such as "Lionol Green 2YS" and "Green Pigment 7" described in JP-A-4-322219. And, as the above-mentioned carbon black, "MA-7", "MA-100", "MA-220",
"# 5", "# 10", "# 40", and "Color Black FW2", "FW20", "Printex V", etc., which are products of Degussa Corporation.

[0013] Also, "special functional dyes" (edited by Ikemori and Hashiya, 1986, published by CMC Inc.), "chemistry of functional pigments" (edited by Higaki, 1981, issued by CMC Inc.), " Dye Handbook "(edited by Okawa, Hirashima, Matsuoka, Kitao, published by Kodansha)
Exciton Inc., a catalog published in 1995.
And dyes having absorption in the near infrared region described in Laser Dye Catalog issued in 1989.

As the infrared absorbing agent, an organic infrared absorbing dye which does not require a dispersion treatment is preferable.
Organic dyes having an absorption maximum in the range of 1200 nm are preferred. For example, phthalocyanine dye, porphyrin dye, pentacene dye, Ni thio complex dye, anthraquinone dye, phenanthroline dye, cyanine dye,
Merocyanine dye, carbocyanine dye, rhodamine dye, azomethine dye, azurenium dye, polymethine dye, indoline dye, thiazine dye, xanthene dye,
Acridine dyes, oxazine dyes, and the like. Of these, phthalocyanine dyes are preferred, and specific chemical structures are listed below. In the following structures, Me represents a methyl group and Ph represents a phenyl group.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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(C) The polymerization initiator is a radical generator which generates a radical directly by irradiation with actinic rays or by an interaction with a sensitizing dye.
No. 3-133428, British Patent No. 1388492, Wakabayashi et al. Bull.Chem. Soc. Japan; 42, 2924 (1969), F.
C. Schaefer et al .; J. Org. Chem .; 29, 1527 (1964); halogenated hydrocarbon derivatives described in JP-A-59-15239.
6, JP-A-61-151197, JP-A-63-41
No. 484, JP-A-2-249, JP-A-2-4705
And titanocene compounds described in JP-A-5-83588, hexaarylbiimidazole compounds described in JP-B-6-29285, etc., organic boron complexes, carbonyl compounds, and organic peroxides. No.

Here, specific examples of the halogenated hydrocarbon derivative include, for example, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-
Bis (trichloromethyl) -s-triazine, 2-n-
Propyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4 , 6-Bis (trichloromethyl) -s
-Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′,
4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (P-methoxyphenyl) -2,
4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6- Bis (trichloromethyl)-
s-triazine, 2- (p-methoxystyryl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(P-methoxystyryl) -4-amino-6-trichloromethyl-s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (4-ethoxynaphthyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- [4- (2-ethoxyethyl) naphthyl] -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(4,7-dimethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-acenaphthyl-
4,6-bis (trichloromethyl) -s-triazine,
2-phenylthio-4,6-bis (trichloromethyl)
-S-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2-methoxy-4-methyl-6-trichloromethyl-s-triazine, 2,4,6-tris (tribromo Methyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, 2-amino-
Examples include s-triazine compounds such as 4-methyl-6-tribromomethyl-s-triazine, among which bis (trichloromethyl) -s-triazine compound is preferable.

Examples of the titanocene compound include, for example, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,4-
Difluorophenyl), dicyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3 , 5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis (2,3,4,5,6
-Pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,4,6-trifluorophenyl), di (methyl Cyclopentadienyl) titanium bis (2,3,5
6-tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl titanium bis (2,6-difluoro-3- ( 1-pyrrolyl) phenyl) and the like.

As the hexaarylbiimidazole compound, specifically, for example, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chlorophenyl) biimidazole, , 2'-Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 , 5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5′-tetra (p-chloronaphthyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2′-bis (o, p-dichlorophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4 , 4 ', 5,5'-tetra (o-chloro-p
-Methoxyphenyl) biimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole and the like.

Examples of the organic boron complex include, for example, JP-A Nos. 8-21813, 9-106242, 9-188865, and 9-18868.
No. 6, JP-A-9-188710, and Kunz, Marti
n “Rad Tech'98.Proceeding April 19-22,1998, Chicag
o "and the like, and the organic boron ammonium complexes described in
JP-A-1576232, JP-A-6-175561, JP-A-6-175564, etc., organoboron sulfonium complexes or organoboron oxosulfonium complexes, JP-A-6-175553, JP-A-6-1755
No. 54, the organic boron iodonium complex described in JP-A No. 9-188710, the organic boron phosphonium complex described in JP-A No. 9-188710, JP-A No. 6-348011, JP-A No. 7-1
28785, JP-A-7-140589, JP-A-7-140
No. 292014, JP-A-7-306527, and the like. Specific examples include an organic boron complex having a basic structure represented by the following formula (I).

[0025]

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R ^{1 to} R ⁴ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkaryl group which may have a substituent, or a substituent. alkenyl group which may be, an optionally substituted alkynyl group, a heterocyclic group which may have a even better alicyclic substituted hydrocarbon ring group and a substituted group, R ¹ To R ⁴ may combine to form a ring, and X ⁺ represents a cationic group.

From the viewpoints of stability and high polymerization activity, R ¹ to
An aryl group in which three of R ⁴ may have a substituent and a triarylalkyl borate complex in which one is alkyl are preferred. Aryl group is preferably a phenyl group, an alkyl group preferably an alkyl group of C ₁ -C _10. In particular, the aryl group is preferably a phenyl group substituted with an electron-withdrawing group such as an F atom.

Further, X ⁺ which is a cation residue is disclosed in
Those having absorption in the visible light region, such as the cationic dyes described in 2-143044 and JP-A-62-150242, are not preferred from the viewpoint of stability, and those having as little absorption as possible in the visible light region are preferred. . Examples thereof include onium cation groups such as ammonium, phosphonium, arsonium, stibonium, oxonium, sulfonium, selenonium, stannonium, and iodonium, and transition metal coordination cation complexes. Particularly preferred is quaternary ammonium, and more preferred is tetraalkylammonium. In particular, an alkyl group having 1 to 10 carbon atoms is particularly preferred.

If the specific chemical structure of a particularly preferred organic boron complex is listed, for example, the following may be mentioned. In the following, Et is an ethyl group, Bu
Represents a butyl group.

[0030]

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[0031]

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[0032]

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Specific examples of the carbonyl compound include, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michler's ketone Derivatives such as benzophenone derivatives, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl)
Ketone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl-
(P-butylphenyl) ketone, α-hydroxy-2-
Acetophenone derivatives such as methylphenylpropanone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, thioxanthone,
Thioxanthone derivatives such as ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, ethyl p-dimethylaminobenzoate, p-diethylamino Benzoic acid ester derivatives such as ethyl benzoate are exemplified.

As the organic peroxide, specifically,
For example, methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,
Ketone peroxides such as 3,5-trimethylcyclohexanone peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl Diacyl peroxides such as peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -bis (T-
Butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, etc. Dialkyl peroxides,
1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,3
Peroxy ketals such as 5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t
-Butyl peroxy acetate, t-butyl peroxy octoate, t-butyl peroxy pivalate, t-
Alkyl peresters such as butyl peroxy neodecanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, di-2- Ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxide Peroxycarbonates such as oxyisopropyl carbonate, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′,
4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t
-Octylperoxycarbonyl) benzophenone,
3,3 ′, 4,4′-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ -Tetra (aminoperoxycarbonyl) benzophenone, carbonylbis (t-butylperoxy dihydrogen 2-phthalate), carbonyl bis (t-hexylperoxy dihydrogen 2-phthalate) and the like.

Of the above-mentioned polymerization initiators, organic boron complexes are the most preferable. Among them, an organic boron ammonium complex can be mentioned as a particularly preferred polymerization initiator. In the case of an organic boron complex, a complex of a cationic infrared absorbing dye and an organic boron anion may be used, and (b) an infrared absorbing agent and (c) a polymerization initiator may be combined as one component.

The epoxy compound (d) may be any compound having an epoxy group in its structure, but preferably has two or more epoxy groups in the molecule, and has a glycidyl group or a cyclohexene oxide group. Compounds having two or more in the molecule are preferably used, and examples thereof include Epicron N-770 (manufactured by Dainippon Ink and Chemicals, Inc.) and D.C. E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
Phenol novolak type epoxy resins such as RE-306 (manufactured by Nippon Kayaku Co., Ltd.); Epicron N-695
(Manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102
Cresol novolak type epoxy resin such as S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.);
TACTICX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (Yukaka Epoxy Co., Ltd.)
Dicyclopentadiene phenol type epoxy resin such as Epicron EXA-7200 (manufactured by Dainippon Ink and Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Company); Epicoat 828 , Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.I. E. FIG. Bisphenol A type epoxy resin such as R-331 (manufactured by Dow Chemical Company); UVR-6
Bisphenol F type epoxy resin such as 490 (manufactured by Union Carbide); Bixylenol type epoxy resin such as YX-4000 (manufactured by Yuka Shell Epoxy); YL-
Bicron type epoxy resin such as 6121 (manufactured by Yuka Shell Epoxy); Epicron N-880 (manufactured by Dainippon Ink and Chemicals, Inc.); Epicoat E157S75
Bisphenol A such as (manufactured by Yuka Shell Epoxy)
Novolak type epoxy resin; Naphthalene skeleton-containing epoxy resin such as EXA-4750 (manufactured by Dainippon Ink and Chemicals, Inc.); alicyclic epoxy resin such as EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.); TEPIC, TE
PIC-L, TEPIC-H (manufactured by Nissan Chemical Industries, Ltd.)
And the like. These may be used alone or in combination of two or more. The epoxy compound may be any of a monomer, an oligomer, and a polymer. The molecular weight is not particularly limited, but is usually about 30,000 or less.

The preferred compounding ratio of the composition of the present invention described above is as follows: (a) Ethylenically unsaturated double bond-containing compound 10
Based on 0 parts by weight, (b) 1 to 20 parts by weight of the infrared absorber, (c) 1 to 30 parts by weight of the polymerization initiator, and (d) 10 to 200 parts by weight of the epoxy compound. When the amount is out of the above range, problems such as insufficient sensitivity and insufficient durability such as heat resistance and chemical resistance are likely to occur.

The composition of the present invention may contain, in addition to the above essential components, an alkali-soluble resin, an epoxy curing agent, a filler, a leveling agent, an antifoaming agent, a pigment, a stabilizer and the like. In particular, it is preferable to add an alkali-soluble resin from the viewpoint of imparting alkali developability and improving coating properties, and an epoxy curing agent from the viewpoint of improving durability. Examples of the alkali-soluble resin include a resin obtained by modifying a vinyl resin having a carboxyl group or an epoxy acrylate resin with an acid anhydride.

Examples of the vinyl resin having a carboxyl group include vinyl monomers having a carboxyl group such as (meth) acrylic acid, maleic anhydride, crotonic acid, and styrene.
α-methylstyrene, vinylphenol, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate,
Dodecyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylonitrile, vinyl acetate, acrylamide , N-methylolacrylamide, glycidyl (meth) acrylate and the like are preferably used.

As the vinyl resin having a carboxyl group, a (meth) acrylic resin containing (meth) acrylic acid as an essential component is particularly preferable.
Resin acid value is 30 to 250 KOH.
The weight average molecular weight (Mw) in terms of polystyrene as determined by gel permeation chromatography (GPC) is from 1,000 to 300,000, and more preferably from 1500 to 200,000.

The above vinyl resin is disclosed in JP-A-4-345.
609, JP-A-6-138659, JP-A-5-586
As described in JP 19467 and JP-A-6-11831, an epoxy compound containing an ethylenically unsaturated double bond such as glycidyl methacrylate or 3,4-epoxycyclohexylmethyl acrylate is added to a carboxyl group to form a resin. Unsaturated groups may be introduced into the chain. By introducing unsaturated groups into the resin side chains, heat resistance, chemical resistance,
Such a resin is preferable because printing durability, sensitivity, adhesion, and the like can be improved. In particular,
An ethylenic alicyclic epoxy compound represented by 4-epoxycyclohexylmethyl acrylate is preferable because of its large effect.

Examples of the resin obtained by modifying the epoxy acrylate resin with an acid anhydride include bisphenol A epoxy resin,
Bisphenol-S epoxy resin, cresol novolak epoxy resin, phenol novolak epoxy resin,
Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, phthalic anhydride, an epoxy acrylate resin obtained by adding an acrylic monomer having a carboxyl group such as acrylic acid or methacrylic acid to an epoxy group of an epoxy resin such as a trisphenol epoxy resin. Dibasic acid anhydrides such as tetrahydrophthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride; Aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride; and other accompanying compounds such as 5- (2,5-dioxotetrahydrofuryl) -3-
A resin to which a polyvalent carboxylic anhydride derivative such as methyl-3-cyclohexene-1,2-dicarboxylic anhydride is added and modified is exemplified.

The resin obtained by modifying the epoxy acrylate resin with an acid anhydride is preferably a resin obtained by modifying a novolak epoxy acrylate resin with tetrahydrophthalic anhydride or hexahydrophthalic anhydride.
Those having a resin acid value of 20 to 150 (KOH.mg/g) and a weight average molecular weight of 1,000 to 20,000 are particularly preferred.

When the above-mentioned alkali-soluble resin is contained, the content is preferably in the range of 50 to 500 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound (a).

Epoxy curing agents used for improving durability include C11Z, 2PHZ, 2MZ-AZINE,
2E4MZ-AZINE, 2E4MZ-CN, 2MA-
Imidazole and its derivatives such as OK (all manufactured by Shikoku Chemicals Co., Ltd.); hexa (N-methyl) melamine;
Tertiary amines such as 2,4,6-tris (dimethylamino) phenol; benzoguanamine, acetoguanamine,
Triazine compounds such as melamine and vinyl triazine;
5- (2,5-dioxotetrahydro-3-furanyl)
Acid anhydrides such as -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; polyamines such as dicyandiamide; and organic phosphines such as triphenylphosphine. Particularly preferred as epoxy curing agents are triazines, and the preferred amount is in the range of 0.1 to 3 parts by weight based on 10 parts by weight of the epoxy compound.

The infrared curable composition of the present invention can be used as a film-like laminate such as a photosensitive liquid or a dry film in which the above-mentioned components are dissolved in a diluent. From the viewpoint of adhesion to the substrate, etc.,
It is preferably used as a photosensitive solution dissolved in a diluent.
The viscosity of the photosensitive liquid can be adjusted according to the coating method, and includes a liquid having a high viscosity such as ink.

The diluent is not particularly limited as long as it has sufficient solubility in the components used and gives good coating properties. Methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, cellosolve solvents such as ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
Propylene glycol monobutyl ether acetate,
Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, 3 Ester solvents such as methyl methoxypropionate, heptanol, hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, cyclohexanone,
Ketone solvents such as methyl amyl ketone, polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, non-polar solvents such as hexane, Solvesso # 150, petroleum ether, or mixed solvents thereof, and aromatic solvents. Those to which hydrocarbons are added are exemplified.

The substrates to which the photosensitive liquid is applied include a paper-based phenolic resin substrate, a paper-based polyester resin substrate, a paper-based epoxy resin substrate, a glass-based epoxy resin substrate, a glass-based polyimide resin substrate, and a glass-based substrate. BT resin substrate, polyimide flexible substrate, polyester flexible substrate, composite substrate, ceramic substrate,
A so-called printed wiring board in which a wiring layer such as copper is formed on one or both surfaces of a substrate such as a heat-resistant thermoplastic resin substrate is preferable. As the coating method, a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, screen printing, or the like can be used.

The thickness of the photosensitive layer provided on the support is from 1 to
A range of 70 μm is preferred, preferably 5 to 60 μm,
More preferably, it is in the range of 10 to 50 μm. If the film thickness is out of the above range, it is not desirable in terms of durability and cost. Known means such as a convection oven and a hot plate are used for drying, and the drying temperature is 50 to 120 ° C.
The drying may be performed under the conditions of 30 seconds to 60 minutes.

The light source for imagewise exposing the infrared curable composition of the present invention includes a laser light source such as a HeNe laser, an argon ion laser, a YAG laser, a semiconductor laser, and a ruby laser.
m, even light sources that emit near-infrared laser
Light having a wavelength of 50 to 1200 nm is preferable, and examples thereof include solid lasers such as a ruby laser, a YAG laser, and a semiconductor laser. Particularly, a small-sized and long-life semiconductor laser and a YAG laser are preferable. Usually, after scanning and exposure with these light sources, an image is formed by developing with a developer.

Examples of the developer used for developing the photosensitive layer subjected to image exposure include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, and the like.
Potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tertiary sodium phosphate, dibasic ammonium phosphate, tertiary ammonium phosphate, sodium borate, boric acid Inorganic alkali salts such as potassium and ammonium borate, or monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine And an alkali developer comprising an aqueous solution of about 0.1 to 10% by weight of an organic amine compound such as diisopropanolamine.
Incidentally, a nonionic, anionic, cationic or amphoteric surfactant or an organic solvent such as alcohol may be added to the developer as required. In addition, development is carried out by immersion development, spray development, brush development, ultrasonic development, etc.
Usually, it is preferably about 10 to 60 ° C, more preferably 1 to 60 ° C.
It is performed at a temperature of about 5 to 45 ° C.

After image formation, post-baking is preferably performed to impart durability to the resist film. Post baking may be performed at 100 to 200 ° C., preferably 120 to 180 ° C., for 30 seconds to 60 minutes. Known post-baking equipment such as a convection oven, a hot plate, and an infrared furnace can be used for the post-baking.

[0053]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention. Example-1 Composition of photosensitive solution Alkali-soluble resin (resin having a repeating unit of the following formula I) 70 parts by weight Dipentaerythritol hexaacrylate 30 parts by weight Infrared absorbing dye (the above R-1) 5 parts by weight Polymerization initiator (the above B-1) 10 parts by weight Epoxy compound Epicoat 1004 (trade name, manufactured by Yuka Shell Co., bisphenol epoxy) 20 parts by weight Epoxy curing agent 5 parts by weight acetoguanamine Solvent 300 parts by weight cyclohexanone

[0054]

Embedded image

In the above, the numbers after () indicate the copolymer molar ratio. The above-mentioned photosensitive solution was applied to a double-sided copper-clad laminate having a thickness of 0.2 mm in a thickness of 20 μm. The application was performed with a wire bar, and the drying was performed in a convection oven at 70 ° C. for 5 minutes. An exposure apparatus equipped with a semiconductor laser of 830 nm (trend setter)
3244 (manufactured by Creo Corporation)
Developed with a 30% aqueous solution of sodium carbonate at 30 ° C for 1 minute.
After development, the sample is placed in a convection oven for 150
Post-baking was performed at 30 ° C. for 30 minutes. The following items were evaluated for the sample.

Evaluation item 1) Sensitivity The sensitivity was defined as the minimum exposure energy amount at which an image was formed with almost no film loss during development. 2) Developability In the visual observation, those where the non-image area was completely removed and there was no background stain were evaluated as good, and those which were not were evaluated as poor. 3) Resolution Observed with a microscope at a magnification of 100 times, a sample having a sharp line and space of 20 μm was defined as good, and a sample with a line and space other than 20 μm was defined as poor. 4) Safelight property The sample was left in a room illuminated with a white fluorescent lamp for 1 hour before exposure and development before exposure and development. sensitivity,
Those having good developability and resolution were defined as good safelight properties. 5) Durability The samples subjected to post-baking were immersed in isopropyl alcohol, 5% hydrochloric acid, and 5% sodium hydroxide aqueous solution at room temperature for 30 minutes, and the state of the film was observed. Those with no change such as peeling or swelling from the substrate were evaluated as having good durability, and those with no change were evaluated as being poor. The evaluation results are summarized in Table 1 including Examples 2 to 6 below.

Example 2 Evaluation was performed in the same manner as in Example 1 except that the epoxy compound in the photosensitive solution composition of Example 1 was changed to Epicoat 180 (trade name, manufactured by Yuka Shell Co., alicyclic epoxy compound). . Example 3 The epoxy compound in the photosensitive solution composition of Example 1 was used as EX
Evaluation was performed in the same manner as in Example 1 except that the product was changed to -411 (trade name, manufactured by Nagase Kasei Co., aliphatic epoxy compound). Example-4 The epoxy compound in the photosensitive solution composition of Example-1 was replaced with EX.
The evaluation was performed in the same manner as in Example 1 except that -512 (trade name, manufactured by Nagase Kasei Co., aliphatic epoxy compound) was used. Example-5 The epoxy compound in the photosensitive solution composition of Example-1 was replaced with N-
Evaluation was performed in the same manner as in Example 1 except that 680 (trade name of Dainippon Ink and Novolak epoxy compounds) was used. Example-6 The epoxy compound in the photosensitive solution composition of Example-1 was replaced with N-
Evaluation was performed in the same manner as in Example 1 except that the sample was changed to 695 (trade name, a novolak epoxy compound manufactured by Dainippon Ink and Chemicals, Inc.).

[0058]

[Table 1]

[0059]

According to the present invention, it is possible to obtain an infrared curable composition which is extremely sensitive to infrared laser light, has excellent durability, and can be handled under a white lamp. For this reason,
Sufficiently high productivity can be obtained by scanning exposure with a laser beam, and since it has excellent durability, it can fulfill a sufficient function as a solder resist.

Continued on front page F-term (reference) 2H025 AA01 AA02 AA07 AA08 AA10 AB15 AB20 AC08 AD01 BC13 BC42 BC81 CA39 CC12 CC17 FA10 4J011 QA12 QA13 QA17 QA18 QA22 QA23 QA24 QA33 QA34 QA39 QA42 QB19 QB20 SA22 RA22 SA24 SA26 SA27 SA29 SA61 SA64 SA76 SA78 SA86 SA87 SA88 TA08 TA10 UA02 VA01 WA01

Claims (6)

[Claims] An infrared curable composition comprising (a) an ethylenically unsaturated double bond-containing compound, (b) an infrared absorber and (c) a polymerization initiator, wherein the composition is (D) an infrared curable composition comprising an epoxy compound. (B) the infrared absorber is 750-1200 nm;
The infrared curable composition according to claim 1, which is an organic dye having an absorption maximum in the range of. 3. The infrared curable composition according to claim 1, wherein (c) the epoxy compound is a compound having two or more epoxy groups in a molecule. 4. The infrared curable composition according to claim 1, wherein (b) the infrared absorbing agent is a phthalocyanine infrared absorbing dye. 5. The infrared curable composition according to claim 1, wherein (c) the polymerization initiator is an organic boron complex. 6. A photo solder resist.
The infrared light curable composition according to any one of items 1 to 5,