JPH08314138A - Negative photosensitive composition - Google Patents

Abstract

PURPOSE: To provide a photosensitive compsn. having a high curing rate and suitable for use in direct pattern forming with a laser light source by using a specified (oxo)sulfonium-organoboron complex and a specified (thia)pyrylium deriv. CONSTITUTION: A photopolymn. initiator system is composed of a (oxo) sulfonium-organoboron complex represented by formula I and a (thia)pyrylium deriv. represented by formula II. In formula I, R<1> is benzyl, substd. benzyl, phenacyl, substd. phenacyl, etc., each of R<2> and R<3> means R<1> or alkyl, substd. alkyl, etc., R<4> is O or a lone electron-pair and each of R<5> -R<8> is alkyl, substd. alkyl, aryl, etc. In formula II, each of R<9> -R<13> is H, halogen, alkyl which may have a substituent, etc., Y is O or S and X is halogen, BF4 , BF6 , etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel negative-working photosensitive composition exhibiting high sensitivity characteristics in a wavelength range from ultraviolet to near infrared light.
The present invention relates to a negative photosensitive composition which is preferably used for producing a circuit for a printed circuit board by exposure through a mask film on which a pattern is recorded or direct drawing with a laser light source.

[0002]

2. Description of the Related Art In recent years, a photoresist method using a photosensitive resin has been used for manufacturing a printed wiring board and a relief board. In this photoresist method, for example, a photosensitive resin layer is first formed on a support such as a transparent film, and then the photosensitive resin layer is laminated so as to be in contact with the substrate surface on which a desired image is to be provided. Then, the photosensitive resin layer is exposed to active light through the original image to be exposed, and then the unexposed portion is removed by a developing treatment with a solvent or an aqueous alkaline solution to form an image corresponding to the original image. Is usually taken.

As the photopolymerization initiator used in the photosensitive resin composition used in such applications, conventionally, benzoins, ketones, quinones, diketones, alkyl oxime esters and the like, or a combination thereof is used. For example, benzophenone / Michler's ketone, thioxanthone / aromatic amine, 2,4,5-triarylimidazole dimer / Michler's ketone, etc. are known. However, in these photopolymerization initiators, the curing speed is generally not sufficient, and the irradiation time becomes long in the exposure of a large substrate, the work efficiency is lowered, or the photosensitivity in the visible light region is extremely low, so that the visible light laser However, there is a defect that it is not suitable as a photoresist for direct writing using.

In order to overcome such technical problems, a polymerizable composition characterized by using a sulfonium organic boron complex as a radical generator is disclosed in Japanese Patent Laid-Open No. 5-2.
55421 and JP-A-6-157623. According to the known technique, it is possible to construct a photopolymerization initiator system having extremely excellent sensitivity characteristics from the ultraviolet region to the near infrared region by combining various sensitizers with a sulfonium organic boron complex. However, in providing a composition in a specific application field such as a photoresist material, which is the main object of the present invention, there are still insufficient points in terms of characteristics or composition of components.

[0005]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned drawbacks, has an extremely high curing speed, and can be suitably used for direct writing by a laser light source, and is particularly preferably used for a photoresist material. It was made for the purpose of providing a negative photosensitive composition.

[0006]

The inventors of the present invention have achieved the present invention as a result of extensive studies in view of the above points in order to achieve the above object. That is, the present invention relates to a photosensitive composition comprising a solvent-developable polymer (A), a compound (B) having a radical-polymerizable ethylenically unsaturated bond, and a photopolymerization initiator system (C), The photopolymerization initiator system (C) has the general formula (1)

[0007]

Embedded image [In the formula, R ¹ represents a benzyl group, a substituted benzyl group,
Represents a group selected from a phenacyl group, a substituted phenacyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group and a substituted alkenyl group, and R ² and R ³ each independently constitute R ¹ . The same groups as those capable of forming an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, an alicyclic group, or a substituted group. Alicyclic group, alkoxy group, substituted alkoxy group, alkylthio group, substituted alkylthio group, amino group, substituted amino group, or R
² represents a cyclic structure in which R ³ is bonded to each other, R ⁴ represents an oxygen atom or a lone electron pair, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or a substituted alkyl group. A group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, and a substituted alkenyl group (provided that all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are aryl groups. Or a substituted aryl group, which does not become a substituted aryl group)] and an (oxo) sulfonium organoboron complex represented by the following general formula (2)

[0008]

[Chemical 4] [In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a haloalkyl which may have a substituent. Group, an ethylenyl group which may have a substituent, a styryl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a nitro group, a substituent A group selected from an amino group which may have a group, a hydroxy group and a heterocyclic group which may have a substituent is shown. R ⁹ and R ¹⁰ , R ¹⁰
And R ¹¹ , R ¹¹ and R ¹² , and R ¹² and R ¹³ may be integrated with each other to form an aromatic ring or a heterocycle. Also, Y
Represents an oxygen atom or a sulfur atom, X represents a halogen,
BF ₄ , PF ₆ , AsF ₆ , ClO ₄ , SbF ₆ , CF ₃ SO
₃ , CH ₃ SO ₃ or CH ₃ C ₆ H ₄ SO ₃ is shown. ] It is a negative photosensitive composition which consists of (thia) pyrylium derivative (b) represented by these.

The present invention will be described in detail below.
The basic constitution of the negative photosensitive composition of the present invention is as follows: (A) solvent developable high molecular weight polymer (B) radically polymerizable ethylenically unsaturated bond-containing compound (C) photopolymerization initiator system However, due to the use of the photoinitiator system (C) consisting of (oxo) sulfonium organoboron complex (a) and (thia) pyrylium derivative (b), which is particularly used in the present invention, a high curing rate and a laser It becomes possible to realize photosensitivity to the light source.

First, the solvent developable high molecular weight polymer (A) in the present invention is a solvent-soluble thermoplastic resin,
For example, epoxy resin, phenoxy resin, phenol resin, silicone resin, amide resin, synthetic rubber resin,
Urethane resin, diallyl phthalate resin, vinyl acetate resin, vinyl chloride resin, etc. can be mentioned,
In particular, a high molecular polymer having an α, β-unsaturated ethylene monomer unit is preferably used. Examples of the monomer constituting the α, β-unsaturated ethylenic monomer unit include, for example, styrene, o-methylstyrene, m-methylstyrene, p
-Methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-butylstyrene, p-tert-butylstyrene, p-hexylstyrene, p-octylstyrene, p-methoxystyrene,
Styrenes such as p-phenylstyrene and 3,4-dichlorostyrene, vinylnaphthalenes, ethylene and propylene, butylene, C _{3 to} C ₁₀ and higher α-olefins, vinyl chloride, vinyl bromide, vinyl fluoride. Such as vinyl halides, vinyl acetate, vinyl propionate, vinyl acetate and other vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, phenyl (meth) acrylate, α-chloroacryl Methyl acid, dimethylaminoethyl methacrylate, (meth) acrylamide (Meth) acrylic acid esters, vinyl ethers such as (meth) acrylonitrile, vinyl methyl ether, vinyl ethyl ether, vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone, N-vinylpyrrole, N-vinylpyrrolidone,
Examples include N-vinyl compounds such as N-vinylcarbazole and N-vinylindole. These monomers may be used alone or in combination of two or more. In particular, in the present invention, in order to make the solvent-developable polymer into a water- or alkali-developable polymer, a monomer containing a carboxyl group, for example, (meth) acrylic acid, fumaric acid, A monomer selected from cinnamic acid, crotonic acid, itaconic acid, maleic acid, maleic acid half ester and the like is used in combination.

Next, as the compound having a radical-polymerizable ethylenically unsaturated bond, at least one selected from monomers, polymers and prepolymers having at least one unsaturated double bond in the molecule is applied. Examples of such compounds include unsaturated acid compounds such as (meth) acrylic acid, itaconic acid, maleic acid, and methyl (meth).
(Meth) acrylic acid alkyl ester compounds such as acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, dimethyl Aminoethyl (meth) acrylate,
Morpholinoethyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, 2-
Vinyl monomers such as hydroxyethyl (meth) acrylate and N-vinylcarbazole, and aliphatic polyhydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol. , Tetrapropylene glycol, neopentyl glycol, 1,3-
Propanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,1
Di- or poly (meth) acrylic esters such as 0-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, sorbitol, mannitol, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate , A fluorine atom-containing (meth) acrylate compound such as hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate,
Tribromophenol triethylene oxide (meth) acrylate, p-bromophenoxyethyl (meth) acrylate, tetrabromobisphenol A ethyl (propi)
Bromine atom-containing (meth) acrylate compounds such as lenoxide-modified di (meth) acrylate, phenyl (meth)
Acrylate, 4-methoxycarbonylphenyl (meth) acrylate, 4-ethoxycarbonylphenyl (meth) acrylate, 4-butoxycarbonylphenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, benzyl (meth) acrylate, 4 -Phenoxyethyl (meth) acrylate, 4-
Phenylethyl (meth) acrylate, 4-phenoxydiethylene glycol (meth) acrylate, 4-phenoxytetraethylene glycol (meth) acrylate, 4-phenoxyhexaethylene glycol (meth)
(Meth) acrylate compounds containing an aromatic ring such as acrylate, 4-biphenylyl (meth) acrylate, epichlorohydrin phthalate-modified di (meth) acrylate, aromatic polyhydroxy compounds such as hydroquinone, resorcinol, catechol, and pyrogallol. Alternatively, poly (meth) acrylate compounds, isocyanuric acid eth (propylene) oxide-modified (meth) acrylate, bisphenol A eth (propylene) oxide modified di (meth) acrylate, (meth) acrylated epoxy resin, ferrocenylmethyl (meth) ) Heavy metal atom-containing (meth) acrylate compounds such as acrylate, ferrocenylethyl (meth) acrylate, and zinc di (meth) acrylate. You may use these compounds in combination of 2 or more types as needed.

Next, among the photopolymerization initiator systems (C) in the present invention, the following general formula (1)

[0013]

Embedded image [In the formula, R ¹ represents a benzyl group, a substituted benzyl group,
Represents a group selected from a phenacyl group, a substituted phenacyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group and a substituted alkenyl group, and R ² and R ³ each independently constitute R ¹ . The same groups as those capable of forming an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, an alicyclic group, or a substituted group. Alicyclic group, alkoxy group, substituted alkoxy group, arylthio group, substituted arylthio group, amino group, substituted amino group, or R
² represents a cyclic structure in which R ³ is bonded to each other, R ⁴ represents an oxygen atom or a lone electron pair, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or a substituted alkyl group. Represents a group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, or a substituted alkenyl group (provided that all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are aryl groups. Or, it does not become a substituted aryl group.)]], And the (oxo) sulfonium organoboron complex (a) will be described.

In the substituents R ¹ , R ² and R ³ on the sulfonium or oxosulfonium cation in the general formula (1), a benzyl group or a substituted benzyl group is a p-cyanobenzyl group or a p-nitrobenzyl group. , P-chlorobenzyl group, p-hydroxybenzyl group, p-methylbenzyl group, p-methoxybenzyl group,
A phenacyl group or a substituted phenacyl group such as a p-dimethylaminobenzyl group or a 1- (or 2-) naphthylmethylene group is a p-cyanophenacyl group, p
-Nitrophenacyl group, p-chlorophenacyl group, p-
Hydroxyphenacyl group, phenacyl group, p-methylphenacyl group, p-dimethylaminophenacyl group, etc.
Examples of the aryloxy group or the substituted aryloxy group include p-cyanophenoxy group, p-nitrophenoxy group, p-chlorophenoxy group, phenoxy group, p-tolyloxy group, p-methoxyphenoxy group, p-dimethylaminophenoxy group. Groups, etc., as an alkenyl group or a substituted alkenyl group, vinyl group, 1-propenyl group, 1-butenyl group, 3,3-dicyano-1-propenyl group, etc., as an alkyl group or a substituted alkyl group Is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group,
tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, allyl group, salicyl group, acetonyl group, cyanomethyl group, chloromethyl group, bromomethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group A group, a menthyl group, a pinanyl group, etc., an aryl group or a substituted aryl group, a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, a p-methoxyphenyl group, a biphenylyl group, a naphthyl group, Anthryl group, phenanthryl group, p-cyanophenyl group, p-nitrophenyl group,
2,4-bis (trifluoromethyl) phenyl group, p-
Fluorophenyl group, p-chlorophenyl group, p-dimethylaminophenyl group, p-phenylthiophenyl group and the like are alicyclic groups or substituted alicyclic groups, cyclopentyl group, cyclohexyl group, norbornyl group, bornyl group, A 1-cyclohexenyl group or the like is a methoxy group as an alkoxy group or a substituted alkoxy group,
Ethoxy group, n- (or iso-) propoxy group, n
-(Or sec-, tert-) butoxy group, benzyloxy group, p-cyanobenzyloxy group, p-chlorobenzyloxy group, p-nitrobenzyloxy group, p
-Methylbenzyloxy group, p-methoxybenzyloxy group, etc. are alkylthio groups or substituted alkylthio groups such as methylthio group, ethylthio group, butylthio group, etc., and amino groups or substituted amino groups are amino groups, methyl group Amino groups, dimethylamino groups, diethylamino groups, cyclohexylamino groups, anilino groups, piperidino groups, morpholino groups and the like, and arylthio groups or substituted alkylthio groups, phenylthio groups, p-tolylthio groups, p-cyanophenylthio groups. And R ² and R ³ may have a bonded cyclic structure, for example, a tetramethylene group,
Examples include cyclic structures such as an alkylene group which may have a substituent such as a pentamethylene group and a 1,4-dichlorotetramethylene group, an ethylenedioxy group, a diethylenedioxy group, an adipoyl group and an ethylenedithio group.

In the substituents R ⁵ , R ⁶ , R ⁷ and R ⁸ on the organic boron anion in the general formula (1), the alkyl group or the substituted alkyl group is a methyl group, an ethyl group or a propyl group. , Isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, allyl group, benzyl group are aryl groups or substituted Examples of the aryl group include a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, a p-methoxyphenyl group, a naphthyl group, a 2,4-bis (trifluoromethyl) phenyl group,
p-fluorophenyl group, p-chlorophenyl group, p-
Examples of the alkenyl group or a substituted alkenyl group such as a bromophenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, and the like. As an alkynyl group which may have a substituent, an ethenyl group, 2 Examples thereof include -tert-butylethenyl group and 2-phenylethenyl group.

Examples of such (oxo) sulfonium organic boron complex include the compounds described in JP-A-5-213861 and JP-A-5-255347, and specific examples thereof include dimethyl-tert. -Butylsulfonium-tert-butyltriethylborate,
Dimethylbenzylsulfonium phenyltriethylborate, dimethyl (p-chlorobenzyl) sulfoniummethyltriphenylborate, dibutyl (p-bromobenzyl) sulfonium isopropyltriphenylborate, dimethyl (p-cyanobenzyl) sulfoniumbutyltriphenylborate, dimethylphenacylsulfonium Butyltriphenylborate, dimethylphenacylsulfonium-sec-butyltriphenylborate,
Di-tert-butylphenacylsulfonium-sec
-Butyltriphenylborate, dimethyl (p-chlorophenacyl) sulfonium-tert-butyltriphenylborate, dimethyl (p-bromophenacyl) sulfoniumbenzyltriphenylborate, dimethyl (2
-Phenyl-3,3-dicyanoprop-2-enyl) sulfonium butyl tri (p-methoxyphenyl) borate, dibutylethoxysulfonium butyl tri (p-fluorophenyl) borate, dimethylphenoxysulfonium butyltri (p-chlorophenyl) borate, methyl (Dimethylamino) (p-tolyl) sulfoniumbutyltri (p-bromophenyl) borate, dimethyl (methylthio) sulfoniumbutyl tris [3,5-bis (trifluoromethyl) phenyl] borate, dimethylphenylthiosulfonium-sec-butyltri (P
-Methoxyphenyl) borate, methylphenyl (p-
(Cyanobenzyl) sulfonium-sec-butyltri (p-fluorophenyl) borate, methylphenylphenacylsulfonium, methylphenyl (2-phenyl-3,3-dicyanoprop-2-enyl) sulfonium-tert-butyltri (p-bromophenyl) Borate, methylphenylethoxysulfonium butyltriphenylborate, butylphenylphenoxysulfonium butyltriphenylborate, dimethylaminobis (p-tolyl) sulfonium-sec-butyltri (p
-Bromophenyl) borate, tetramethylenephenacylsulfonium-sec-butyltriphenylborate, dimethylallylsulfoniumbutyltriphenylborate, dimethylcyanomethylsulfoniumbutyltriphenylborate, dimethylacetonylsulfoniumbutyltriphenylborate, dimethylethoxycarbonylmethylsulfonium -Tert-butyltri (p-chlorophenyl) borate, dimethyl (methylthiomethyl) sulfonium butyltriphenylborate, tetramethylene-p-cyanobenzylsulfonium-sec-
Butyltri-p-fluorophenylborate, dimethylbenzyloxosulfonium butyltriphenylborate, dimethylphenacyloxosulfonium-sec-
Butyltri (p-chlorophenyl) borate, methylphenylbenzyloxosulfonium-tert-butyltri (p-methoxyphenyl) borate, methylphenylphenacyloxosulfonium-tert-butyltri (p-fluorophenyl) borate, diphenylbenzylsulfoniumbutyltriphenylborate , Diphenyl (p-chlorobenzyl) sulfonium butyl tris (p-methoxyphenyl) borate, diphenyl (p-
Bromobenzyl) sulfonium butyl tris (p-fluorophenyl) borate, diphenyl (p-cyanobenzyl) sulfonium butyl triphenyl borate, bis (p-tert-butylphenyl) benzyl sulfonium butyl tris (p-bromophenyl) borate, bis ( p-chlorophenyl) (p-cyanobenzyl) sulfonium butyltriphenylborate, diphenyl (p-
Cyanobenzyl) sulfoniumphenyl tributylborate, diphenyl (p-cyanobenzyl) sulfonium dibutyldiphenylborate, diphenyl (p-cyanobenzyl) sulfonium vinyltriphenylborate,
Diphenyl (p-cyanobenzyl) sulfonium-se
c-Butyltriphenylborate, diphenyl (p-cyanobenzyl) sulfonium cyclohexyltriphenylborate, diphenylphenacylsulfonium butyltriphenylborate, diphenyl (p-chlorophenacyl) sulfonium butyltriphenylborate, diphenyl (p-bromophenacyl) sulfonium Butyltriphenylborate, diphenyl (p-methoxyphenacyl) sulfonium butyltriphenylborate, diphenyl (p-cyanophenacyl) sulfonium cyclohexyl tris (p-methoxyphenyl) borate, bis (p-tert-butylphenyl) phenacylsulfonium-sec -Butyl tris (p-fluorophenyl)
Borate, bis (p-methoxyphenyl) (p-chlorophenacyl) sulfonium dibutyldiphenylborate, bis (p-chlorophenyl) (p-bromophenacyl) sulfonium benzyltriphenylborate, bis (p-methylphenyl) (p-methoxyphena) Sil) sulfonium-tert-butyltriphenylborate,
Bis (p-tert-butylphenyl) (p-cyanophenacyl) sulfonium benzyl tributylborate,
Diphenyl allyl sulfonium butyl triphenyl borate, diphenyl (2-methyl-3,3-dicyano-2
-Propenyl) sulfonium-2-phenylethynyltriphenylborate, diphenyl (2-phenyl-3,
3-dicyano-2-propenyl) sulfonium butyl triphenyl borate, diphenyl [2-phenyl-3,
3-bis (methoxycarbonyl) -2-propenyl] sulfonium-sec-butyltriphenylborate, bis (p-chlorophenyl) allylsulfoniumphenyltriethylborate, bis (p-tert-butylphenyl) (2-methyl-3,3 -Dicyano-2-propenyl) sulfonium di (sec-butyl) diphenylborate, bis (p-methylphenyl) (2-phenyl-
3,3-dicyano-2-propenyl) sulfonium butyl triphenyl borate, diphenyl acetonyl sulfonium butyl triphenyl borate, diphenyl cyanomethyl sulfonium butyl triphenyl borate, diphenyl methoxy carbonyl methyl sulfonium butyl triphenyl borate, diphenyl sulfomethyl sulfonium methyl tris (P-fluorophenyl) borate,
Diphenyl-p-toluenesulfonylmethylsulfonium dicyclohexyldiphenylborate, diphenyl (trimethylammoniumylmethyl) sulfonium bis (butyltriphenylborate), diphenyl (triphenylphenacylphosphoniumylmethyl) sulfonium bis (butyltriphenylborate), diphenyl ( Phenyliodonium ethynyl) sulfonium bis (butyltriphenylborate), diphenylbenzyloxosulfonium butyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfoniumbutyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfonium-sec- Butyltriphenylborate, diphenyl (p-cyanobenzyl) oxosulfonium cyclohexyl Rutorisu (p- fluorophenyl) borate, diphenyl phenacyl oxosulfonium butyl triphenyl borate, diphenyl (p- chlorophenacyl) oxosulfonium -sec- Buchirutorisu (p- fluorophenyl) borate, bis (p-t
ert-butylphenyl) phenacyloxosulfonium octyltris (p-fluorophenyl) borate,
Diphenylallyloxosulfonium butyltriphenylborate, diphenyl (2-phenyl-3,3-dicyano-2-propenyl) oxosulfonium-tert
-Butyltriphenylborate, diphenylmethoxycarbonylmethyloxosulfonium butyltriphenylborate, diphenyl (trimethylammoniumylmethyl) oxosulfonium bis (butyltriphenylborate), diphenyl (triphenylphenacyloxophosphoniumiumyl) oxosulfonium bis ( Butyl triphenyl borate) and the like. SB (A) to SB (L) are shown below as typical compounds.

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

Embedded image

Next, the following general formula (2), which is the other constituent compound of the photopolymerization initiator system (C):

[0021]

[Chemical 9] [In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a haloalkyl which may have a substituent. Group, an ethylenyl group which may have a substituent, a styryl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a nitro group, a substituent A group selected from an amino group which may have a group, a hydroxy group and a heterocyclic group which may have a substituent is shown. R ⁹ and R ¹⁰ , R ¹⁰
And R ¹¹ , R ¹¹ and R ¹² , and R ¹² and R ¹³ may be integrated with each other to form an aromatic ring or a heterocycle. Also, Y
Represents an oxygen atom or a sulfur atom, X represents a halogen,
BF ₄ , PF ₆ , AsF ₆ , ClO ₄ , SbF ₆ , CF ₃ SO
₃ , CH ₃ SO ₃ or CH ₃ C ₆ H ₄ SO ₃ is shown. ] The (thia) pyrylium derivative (II) represented by These (thia) pyrylium derivatives (b) represented by the general formula (2) can obtain a compound that can be exposed to a wide wavelength range from the ultraviolet region to the near infrared region by changing the substituents. When it is combined with the (oxo) sulfonium organoboron complex (a), it functions as a suitable spectral sensitizer in constructing a photopolymer initiator system having a high radical generating ability in the wavelength range. .

Specific compounds include 2,4,6-triphenylpyrylium, 2,4,6-tris (4-methoxyphenyl) pyrylium, 2,4,6-trimethylphenylpyrylium and 2,6. -Diphenyl-4- (4-methoxyphenyl) pyrylium, 2,6-diphenyl-4
-(4-Butoxyphenyl) pyrylium, 2,6-diphenyl-4- (4-dimethylaminophenyl) pyrylium, 2,6-diphenyl-4- (4-diethylaminophenyl) pyrylium, 2,6-bis (4- Methoxyphenyl) -4-phenylpyrylium, 2,6-bis (4-
Methoxyphenyl) -4- (4-butoxyphenyl) pyrylium, 2,6-bis (4-methoxyphenyl) -4
-Methylpyrylium, 2,6-bis (4-butoxyphenyl) -4-phenylpyrylium, 2,6-bis (4-
Butoxyphenyl) -4- (4-methoxyphenyl) pyrylium, 2,6-bis (4-butoxyphenyl) -4
-Butylpyrylium, 2,6-diphenyl-4- (2,
4-dichlorophenyl) pyrylium, 2,6-diphenyl-4- (4-ethylphenyl) pyrylium, 2- (4
-Butoxyphenyl) -4,6-diphenylpyrylium, 2- (4-ethoxyphenyl) -4,6-diphenylpyrylium, 2- (4-dimethylamino-β-ethylstyryl) -4,6-diphenylpyryl Rium, 2-
(Β, β-bis (4-dimethylaminophenyl) vinylene) -4,6-diphenylpyrylium, 2- (3,4-
Diethoxystyryl) -4,6-diphenylpyrylium, 4- (4-methoxyphenyl) -2-nitro-6-
Phenylpyrylium, 4,6-bis (4-dimethylaminostyryl) -2-nitropyrylium, 4,6-bis (4-butoxystyryl) -2-aminopyrylium,
4,6-bis (4-butylphenyl) -2- (4-nitrophenyl) pyrylium, 4,6-bis (4-dimethylaminophenyl-β-methoxystyryl) -2-hydroxypyrylium, 2-methoxy- 4-naphthyl-6-styrylpyrylium, 2,4,6-triphenylthiapyrylium, 2,4,6-tris (4-methoxyphenyl)
Thiapyrylium, 2,4,6-trimethylphenylthiapyrylium, 2,6-diphenyl-4- (4-methoxyphenyl) thiapyrylium, 2,6-diphenyl-4-
(4-Butoxyphenyl) thiapyrylium, 2,6-diphenyl-4- (4-dimethylaminophenyl) thiapyrylium, 2,6-diphenyl-4- (4-diethylaminophenyl) thiapyrylium, 2,6-bis (4-methoxy) Phenyl) -4-phenylthiapyrylium, 2,
6-bis (4-methoxyphenyl) -4- (4-butoxyphenyl) thiapyrylium, 2,6-bis (4-methoxyphenyl) -4-methylthiapyrylium, 2,6-
Bis (4-butoxyphenyl) -4-phenylthiapyrylium, 2,6-bis (4-butoxyphenyl) -4-
(4-Methoxyphenyl) thiapyrylium, 2,6-bis (4-butoxyphenyl) -4-butylthiapyrylium, 2,6-diphenyl-4- (2,4-dichlorophenyl) thiapyrylium, 2,6-diphenyl- 4- (4
-Ethylphenyl) thiapyrylium, 2- (4-butoxyphenyl) -4,6-diphenylthiapyrylium, 2
-(4-Ethoxyphenyl) -4,6-diphenylthiapyrylium, 2- (4-dimethylamino-β-ethylstyryl) -4,6-diphenylthiapyrylium, 2-
(Β, β-bis (4-dimethylaminophenyl) vinylene) -4,6-diphenylthiapyrylium, 2- (3
4-diethoxystyryl) -4,6-diphenylthiapyrylium, 4- (4-methoxyphenyl) -2-nitro-6-phenylthiapyrylium, 4,6-bis (4-dimethylaminostyryl) -2 -Nitrothiapyrylium,
4,6-bis (4-butoxystyryl) -2-aminothiapyrylium, 4,6-bis (4-butylphenyl)-
2- (4-nitrophenyl) thiapyrylium, 4,6-
Chlorine derivatives, bromine derivatives, iodine derivatives of pyrylium or thiapyrylium such as bis (4-dimethylaminophenyl-β-methoxystyryl) -2-hydroxythiapyrylium and 2-methoxy-4-naphthyl-6-styrylthiapyrylium, In addition to fluoroborate derivatives, perchlorate derivatives, fluoroantimonate derivatives, fluorophosphonate derivatives, fluoroarsenate derivatives, "Chemish Berichte (Chem. Ber)",
Pp. 2309-2320 (1959), or "Journal of Organic Chemistry," Vol. 36, 600-.
The compounds described on page 602 (1971) can be exemplified. PY-1 to PY-3 as typical compounds
And TPY-1 to TPY-3 are shown below.

[0023]

[Chemical 10]

[0024]

[Chemical 11]

In addition, in the negative photosensitive composition of the present invention, if necessary, a photopolymerization accelerator, a thermal polymerization inhibitor, a plasticizer, an ordinary dye or pigment and its dispersant, or a photocured portion and an uncured portion. A coloring substance such as a coloring dye or a fading dye that develops a color upon irradiation with light to distinguish it from a portion can be used in combination. For example, as the thermal polymerization inhibitor, hydroquinone, p-methoxyphenol, t-butylcatechol, pyrogallolnaphthylamine, cuprous chloride,
2,6-di-t-butyl-p-cresol, 2,2'-
Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (2-ethyl-6-t-)
Butylphenol), aryl phosphite, phenothiazine and the like can be used, and a chain transfer agent for the purpose of controlling the degree of polymerization, for example, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 4,4-
Thiobisbentiol, p-bromobenzenethiol,
Thiocyans, thiols such as 1,4-bis (mercaptomethyl) benzene and p-trienethiol can be used in combination. Examples of the plasticizer include phthalate compounds such as diethyl phthalate and diphenyl phthalate, polyether compounds such as polyethylene glycol, polyethylene glycol diacetate and polyethylene glycol dimethyl ether, and sulfonamide compounds such as N, N-dimethylsulfonamide. Is used.

The content of the developable high molecular weight polymer (A) used in the negative photosensitive composition of the present invention is from 5 to 5.
90% by weight is suitable, more preferably selected in the range of 30 to 70% by weight, and the content of the compound (B) having a radically polymerizable ethylenically unsaturated bond is usually 5 to 90% by weight. , Preferably in the range of 20 to 70% by weight. Further, the photopolymerization initiator system (C) is appropriately 0.1% by weight to 30% by weight in the composition, and more preferably 1% by weight to 15% by weight. It is desirable to optimize it in consideration of the balance with the sensitivity characteristics. Further, the addition amount of the (thia) pyrylium derivative (b) in the photopolymerization initiator system (C) is adjusted to an arbitrary thickness on the support. When the photosensitive layer is formed, it is preferably used within a range in which the absorbance at the irradiation wavelength used for exposure does not exceed 2.0.

The negative type photosensitive composition of the present invention is suitably used as a photoresist for producing a printed circuit board as described above, but is not particularly limited as long as it is an application field to which the photosensitive composition can be applied. For example, it can be suitably used for various printing plates such as PS plates for offset printing, relief printing for flexographic printing, and printing screens for silk screen.

Next, one example of using the present invention as a photoresist will be described. First, the composition is coated on a support such as a transparent film to form a photosensitive layer. The photosensitive layer is laminated by thermocompression bonding to the surface of the substrate on which a desired image is to be provided. The temperature range at this time is 40 to 150 ° C. Next, the photosensitive layer is irradiated with light through a mask film for image formation exposure, and then the support is peeled off, and development treatment is performed using, for example, an alkaline aqueous solution to remove the unexposed portion. Then, after a metal image pattern is formed by a known method by etching or plating on the metal surface by this development treatment, the cured resist image is more strongly alkaline than the alkaline aqueous solution used in the development treatment. A desired printed circuit board can be obtained by peeling with the aqueous solution of.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, “part” means “part by weight”.

Example 1 A MEK solution (solid content: 25% by weight) of a photosensitive composition having the following composition was prepared, and a polyethylene terephthalate (PET) film having a thickness of 25 μm was uniformly used as a support using a bar coater. After coating, it was dried in a dryer at 70 ° C. for 10 minutes to form a photosensitive layer having a thickness of 10 μm.
Next, a PET film having a thickness of 50 μm was laminated as a protective film on the surface of the photosensitive layer to prepare a laminated film. Peeling off the protective film of the laminated film,
The photosensitive layer was laminated on a copper-clad laminated substrate by a hot roll laminator at 80 ° C. This laminate was exposed through a negative film at 3 mJ / cm ² with an ultra-high pressure mercury lamp, then the support was peeled off, and a 1 wt% sodium carbonate aqueous solution was sprayed for about 60 seconds to dissolve and remove the unexposed portion. A different resist image (line / space: 30 μm) was obtained. Next, when etching was performed with a cupric chloride etching solution (50 ° C.), a sharp copper line that did not penetrate with the etching solution could be formed.

(A) MMA (70 mol%) / n-BA (8 mol%) / MAA (22 mol%) terpolymer (weight average molecular weight: 120,000) 10.0 parts (B) Tri Methylolpropane triacrylate 5.0 parts EO-added bisphenol A diacrylate 2.0 parts (Kyoeisha Yushi Co., Ltd. A-BPE4) (C) SB (A) 0.5 part PY-1 0.1 part

Example 2 In the photosensitive composition of Example 1, PY-1 was replaced with TPY-1.
Using the same photosensitive composition except that the above was changed to, a laminated film similar to that in Example 1 was produced. Image exposure of the laminated film is performed by a laser scanning exposure machine (LK3001 laser scanning kit: manufactured by General Scanning, Lexe).
195Ar ion laser: manufactured by Rexell, Inc., 48
1.0 mJ / cm ² with 8 nm light and 30 μm spot diameter
Direct drawing was performed with the irradiation energy of. Then, when the image was developed by the method of Example 1, a good resist image having a line width of 30 μm was obtained. Also, a sharp copper line could be formed in the etching treatment with a cupric chloride etching solution (50 ° C.).

Next, an example of using the present invention as a PS plate for offset printing will be shown.

Example 3 A photosensitive composition having exactly the same composition as in the photosensitive composition of Example 2 except that the amount of TPY-1 used was 0.5 parts was spin-coated on an anodized aluminum plate. Using 2
After being coated to a thickness of μm and dried in a dryer at 60 ° C. for 10 minutes, a polyvinyl alcohol (PVA) aqueous solution of 5% by weight is further coated on the photosensitive layer with a spin coater and dried to obtain a PS plate. It was created. The PS plate was used in Example 2
Direct drawing exposure (exposure energy: 0.1 mJ / cm ² , spot diameter: 30 μm) was performed using the same laser scanning exposure machine as described in 1. above, and then the PVA film was immersed in a 1 wt% sodium carbonate aqueous solution for about 60 seconds. When the unexposed portion was removed by dissolution, a good printing plate having a line image with a line width of 30 μm could be obtained.

[0035]

EFFECT OF THE INVENTION The use of the negative photosensitive composition of the present invention makes it possible to provide a photoresist and a PS plate which are highly sensitive and can be scanned and exposed by a laser beam.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location H05K 3/00 H05K 3/00 F

Claims (2)

[Claims] 1. A high-molecular polymer (A) capable of solvent development,
In a photosensitive composition comprising a compound (B) having a radically polymerizable ethylenically unsaturated bond and a photopolymerization initiator system (C), the photopolymerization initiator system (C) is represented by the following general formula (1). A negative photosensitive composition comprising the (oxo) sulfonium organoboron complex (a) represented by the formula (2) and the (thia) pyrylium derivative (b) represented by the following general formula (2). Embedded image [In the formula, R ¹ represents a benzyl group, a substituted benzyl group,
Represents a group selected from a phenacyl group, a substituted phenacyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group and a substituted alkenyl group, and R ² and R ³ each independently constitute R ¹ . The same groups as those capable of forming an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkynyl group, a substituted alkynyl group, an alicyclic group, or a substituted group. Alicyclic group, alkoxy group, substituted alkoxy group, alkylthio group, substituted alkylthio group, amino group, substituted amino group, or R
² represents a cyclic structure in which R ³ is bonded to each other, R ⁴ represents an oxygen atom or a lone electron pair, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or a substituted alkyl group. A group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkenyl group, and a substituted alkenyl group (provided that all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are aryl groups. Alternatively, it does not become a substituted aryl group.)] [In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a haloalkyl which may have a substituent. Group, an ethylenyl group which may have a substituent, a styryl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a nitro group, a substituent A group selected from an amino group which may have a group, a hydroxy group and a heterocyclic group which may have a substituent is shown. R ⁹ and R ¹⁰ , R ¹⁰
And R ¹¹ , R ¹¹ and R ¹² , and R ¹² and R ¹³ may be integrated with each other to form an aromatic ring or a heterocycle. Also, Y
Represents an oxygen atom or a sulfur atom, X represents a halogen,
BF ₄ , PF ₆ , AsF ₆ , ClO ₄ , SbF ₆ , CF ₃ SO
₃ , CH ₃ SO ₃ or CH ₃ C ₆ H ₄ SO ₃ is shown. ] 2. A solvent-developable polymer (A) comprises:
The negative photosensitive composition according to claim 1, which is a compound developable with water or an aqueous alkaline solution.