JPH11143069A - Master plate for printed wiring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a master plate for printed wiring having a photopolymerizable layer, which has high sensitivity and high resolution for argon laser light or the like and has excellent physical properties of the film by forming a photopolymerizable layer containing a thermoplastic polymer binder, an ethylene-type unsatd. compd., a specified sensitizing dye and a radical polymn. initiator on a substrate provided with a conductive thin film on an electric insulating plate. SOLUTION: A photopolymerizable layer containing a thermoplastic polymer binder, an ethylene-type unsatd. compd., one kind of sensitizing dye selected from compds. expressed by the formula, and a radical polymn. initiator is formed on a substrate provided with a conductive thin film on an electric insulating plate. In the formula, R<1> to R<6> are each independently hydrogen atoms, halogen atoms, alkyl groups, substd. alkyl groups, aryl groups, substd. aryl groups or the like, X is O, S, NH or nitrogen atoms having substituents, G<1> , G<2> may be same or different and are hydrogen atoms, cyano groups alkoxycarbonyl groups, substd. alkoxycarbonyl groups or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate obtained when a photopolymerization layer is provided on a substrate having a conductive thin film provided on an electrically insulating plate in a manufacturing process of a printed wiring board (in the present invention, More specifically, it is referred to as an “original sheet for printed wiring”.) More specifically, it has a high sensitivity and a high resolution that can be drawn with visible light such as argon laser light, FD-YAG laser light, and helium-neon laser light, and is excellent. The present invention also relates to the above-mentioned original plate for printed wiring, which gives the film physical properties.

[0002]

2. Description of the Related Art In general, a printed wiring board is manufactured by providing a photopolymerization layer on a substrate formed by providing a conductive thin film on an electrically insulating plate, and performing image exposure, development, and etching on the substrate. Is formed. With the recent demand for higher density in the field of electronics industry, it is expected that the photopolymerized layer has a higher resolution. Also, high sensitivity is required to shorten the process time. Furthermore, by directly exposing digital data such as a circuit diagram of a printed wiring board designed by a personal computer to the photopolymerized layer using a laser, research has been carried out to omit the conventional film working process and improve the process efficiency. In. Conventionally, studies have been made on increasing the sensitivity of a photopolymerizable composition for forming a photopolymerizable layer, and many photopolymerization initiation systems have been proposed. For example, US Pat.
No. 8828, benzoin ethers described in U.S. Pat. No. 3,046,127, anthraquinones described in Japanese Patent Publication No. 49-11936, aminophenyl ketone and active methylene or amino compound, U.S. Pat. No. 3,682,641 Michler's ketone and benzophenone described in the specification, benzophenone and 4-N, N-diethylaminobenzophenone described in JP-B-48-38403, Michler's ketone and lophine dimer described in JP-B-48-38403, 56-351
No. 34, a ternary system of a photopolymerizable ethylenically unsaturated monomer and a 4-N, N-dialkylaminobenzophenone and an organic halogen compound described in JP-A-59-478339. And so on. Although these photopolymerization initiation systems show an improvement in sensitivity, they have a photosensitive wavelength of 450 nm or less and have little sensitivity to visible lasers such as argon, FD-YAG, and helium-neon lasers. It was impossible to create.

Further, the photopolymerized layer used for producing a printed wiring board is required to have a high film strength, and in particular, a resistance to an etching solution. When making a printed wiring board, the metal exposed from the photocured portion of the photopolymerized layer is dissolved with an etchant, and a circuit pattern is formed by leaving only the metal under the photocured portion. If the etching resistance is low, the metal is eluted by the etchant, and the underlying metal that should form a circuit disappears. In addition, when used in the form of a dry film resist, if the film strength is insufficient, the film breaks during the etching process and the phenomenon during the creation of through holes by the tenting method, resulting in conduction between the front and back surfaces of the printed wiring board. In some cases, the copper plating portion inside the through-hole is melted by the etchant to cause conduction failure. As described above, the conventional photopolymerizable layer is in a state where the sensitivity to visible light, the resolving power, and the film properties are not sufficient.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a light having high sensitivity to visible light such as argon, FD-YAG, helium-neon laser, etc., high resolving power and excellent film properties. An object of the present invention is to provide a printed wiring board having a polymerized layer.

[0005]

As a result of various studies, the present inventors have found that a photopolymerization layer containing a specific sensitizing dye has remarkably high sensitivity to visible light and excellent film properties. And found the present invention. That is, in order to achieve the above object, the original plate for printed wiring of the present invention comprises a thermoplastic polymer binder, an ethylenically unsaturated compound, A photopolymerization layer containing at least one sensitizing dye selected from the group and a radical polymerization initiator is provided. Group A: a compound represented by the following general formula (I)

[0006]

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(Wherein R ^{1 to} R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted amino group. the R ¹ to R ⁴ are ring may be the other to form .R ⁵ consisting of nonmetallic atoms together with the carbon atoms to which it is attached, R ⁶
Each independently represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaromatic group, an acyl group, a cyano group, an alkoxycarbonyl group, a carboxyl group, or a substituted alkenyl group. R ⁵ and R ⁶ may together form a ring composed of a nonmetallic atom. X represents O, S, NH, or a nitrogen atom having a substituent. G ¹ and G ² may be the same or different, and each represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, or an aryl group. Carbonyl group, substituted arylcarbonyl group, alkylthio group, arylthio group,
Represents an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G ¹ and G ² may form a ring composed of a non-metallic atom together with the carbon atom to which they are bonded. ) A compound represented by the following general formula (II)

[0008]

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(Wherein R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group, A represents an alkynyl group or a substituted alkynyl group, A represents a carbon atom substituted by an oxygen atom, a sulfur atom, an alkyl group or an aryl group, or a carbon atom substituted by two alkyl groups, and J represents a nitrogen-containing hetero 5 member. Y represents a phenyl group, a substituted phenyl group, an unsubstituted or substituted heteroaromatic ring, Z ¹ represents a hydrogen atom, an alkyl group, a substituted alkyl group, Represents an aryl group, a substituted aryl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group , Z ¹ and Y may combine with each other to form a ring.) A compound represented by the following general formula (III)

[0010]

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(Where R^Ten~ R¹³Are independent of each other
Unsubstituted or substituted alkoxy having 1 to 6 carbon atoms
Si group, unsubstituted or substituted alkenyloxy having 1 to 6 carbon atoms
Si group, unsubstituted or substituted alkylthio having 1 to 6 carbon atoms
A dialkyl group having 1 to 4 carbon atoms in each alkyl group
Mino group, hydroxyl group, acyloxy group, halogen atom, nitro
B represents a group or a plurality of ring groups. R^Ten~ R¹³Two or
3 pieces and the R⁹~ R¹³Ring structure to which the substituent of is attached
Each fused ring is a 5- or 6-membered ring;
Condensed rings or fused ring systems may be formed. R⁹Is hydrogen
An atom, an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms or
Is an unsubstituted or substituted aryl group having 6 to 12 carbon atoms,
Is R¹⁴Represents -CO-. Where R ¹⁴Is an alkoxy group,
Cycloalkoxy group, hydroxyl group, aryloxy group, al
Kenyloxy group, aralkyloxy group, alkoxycal
Bonylalkoxy group, alkylcarbonylalkoxy
Groups or substituents represented by the following (III-a) to (III-c)
Represents

[0012]

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R ^{15 to} R ¹⁸ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group,
Represents an alkoxyalkyl group or a cycloalkyl group, m is 1 to 5, and n is 0 to 10. Q ¹ is a cyano group,
A heterocyclic or -Z ² -R ^19,. Here, R ¹⁹ is an unsubstituted or substituted alkyl group, alkenyl group, or alkoxy group having 1 to 10 carbon atoms, an unsubstituted or substituted aryl group having 6 to 12 carbon atoms, an unsubstituted or substituted aryloxy group having 6 to 12 carbon atoms. An unsubstituted or substituted heterocyclic group having 5 to 15 carbon atoms and hetero atoms constituting the group or the ring,
Or a hydroxyl group or an acyl group. Z ² is a carbonyl group,
Represents a sulfonyl group, a sulfinyl group or an arylenedicarbonyl group,-(CH = CH) _k (k is 1 or 2). )

The reason why the photopolymerizable layer of the present invention exhibits high sensitivity to visible light and excellent film physical properties is that the photosensitization efficiency of the ethylenically unsaturated compound by the sensitizing dye shown in the above group A is high. It is presumed to be due to a significant increase.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a printed wiring board according to the present invention will be described in detail. The photopolymerizable composition for forming the photopolymerizable layer of the present invention comprises a sensitizing dye (A
Group).

The sensitizing dye used in the present invention is selected from the compounds represented by formula (I), formula (II) or formula (III). In the general formula (I), R ^{1 to} R
^As the alkyl group ⁴ , those having 1 to 20 carbon atoms, such as methyl, ethyl and t-butyl, can be used.
Further, as the aryl group, phenyl such as 1 to 10 carbon atoms may be used.
Up to one can be used. Further, R ^{1 to} R
^As the alkoxy group ( ⁴ ), those having 1 to 6 carbon atoms, such as methoxy, ethoxy and butoxy, can be used. In addition, as the substituted amino group for R ^{1 to} R ⁴ , an alkylamino group having 1 to 20 carbon atoms such as methylamino, dimethylamino, diethylamino, diphenylamino, piperidino, and morpholino, and an arylamino group can be used. These alkyl group, aryl group, alkoxy group, alkylamino group, and arylamino group may have a substituent. Examples of the substituent include a halogen atom such as fluorine, chlorine and bromine, an alkoxycarbonyl group such as an ethoxycarbonyl group, an alkoxy group such as methoxy and ethoxy, an aryl group such as phenyl, and a cyano group. When R ^{1 to} R ⁴ form a ring composed of a nonmetallic atom together with a carbon atom bonded thereto, examples of the structure containing a ring include those shown in the following (A), (B) and (C).

[0017]

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When R ⁵ and R ⁶ are acyl groups, alkyl groups having 1 to 10 carbon atoms such as acetyl and benzoyl;
Examples thereof include those having an aryl group and those having an alkyl group having 1 to 6 carbon atoms such as ethoxycarbonyl in the case of an alkoxycarbonyl group. Further, in the case of a substituted alkenyl group, those having 2 to 10 carbon atoms such as a styryl group can be used, and in the case of a heteroaromatic group, those shown in the following (D) to (F) can be used.

[0019]

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Further, both R ⁵ and R ⁶ may form a ring together with the carbon atom bonded thereto. Examples include the structure shown in (G) below.

[0021]

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When X is a nitrogen having a substituent, the same substituents as the alkyl groups and aryl groups described for R ^{1 to} R ⁶ can be used. G ¹ and G ² may be the same or different, and each represents a hydrogen atom, a cyano group,
An alkoxycarbonyl group having an alkyl group having 1 to 10 carbon atoms such as an ethoxycarbonyl group, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms such as a phenoxycarbonyl group, an acetyl group, a propionyl group having 1 to 1 carbon atoms. 7 to 7 carbon atoms such as acyl group and benzoyl group
C1-C6 arylthio groups such as 11-arylcarbonyl group, methylthio group, ethylthio group, etc. C1-C6 alkylthio group, C6-C10 arylthio group such as phenylthio group, and C6-C10 arylsulfonyl such as phenylsulfonyl group Represents an alkylsulfonyl group having 1 to 6 carbon atoms such as a group, a methylsulfonyl group, an ethylsulfonyl group, or a fluorosulfonyl group. These alkoxycarbonyl group, aryloxycarbonyl group, acyl group, arylcarbonyl group, alkylthio group, arylthio group, arylsulfonyl group, and alkylsulfonyl group may have a substituent, and the substituent may be a halogen such as chlorine. Examples include an atom, an alkoxycarbonyl group having an alkyl group having 1 to 6 carbon atoms, a carboxyl group, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group. In the case of an aryloxycarbonyl group, an arylcarbonyl group, an arylthio group, or an arylsulfonyl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group can be used in addition to the above substituents.

When G ¹ and G ² form a ring composed of a nonmetallic atom together with the carbon atom to which they are bonded, the ring is usually a merocyanine dye used as an acidic nucleus and includes the following. . (A) 1,3-dicarbonyl nucleus, for example, 1,3-indandione, 1,3-cyclohexanedione, 5,5-
Dimethyl-1,3-cyclohexanedione and 1,3-dioxane-4,6-dione. (B) pyrazolinone nucleus, for example 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-
Pyrazolin-5-one, 1- (2-benzothiazoyl)
-3-Methyl-2-pyrazolin-5-one. (C) isoxazolinone nucleus, for example 3-phenyl-
2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like. (D) oxindole nucleus, for example 1-alkyl-
2,3-dihydro-2-oxindole. (E) 2,4,6-triketohexahydropyrimidine nucleus, for example barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of such derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl; 1,3-dialkyl compounds such as 1,3-diethyl and 1,3-dibutyl;
3-diphenyl, 1,3-di (p-chlorophenyl),
Examples thereof include 1,3-diaryl compounds such as 1,3-di (p-ethoxycarbonylphenyl) and 1-alkyl-3-aryl compounds such as 1-ethyl-3-phenyl. (F) 2-thio-2,4-thiazolidinedione nuclei such as rhodanine and its derivatives. Such derivatives include 3-alkyl rhodanines such as 3-ethyl rhodanine and 3-allyl rhodanine, and 3-aryl rhodanines such as 3-phenyl rhodanine. (G) 2-thio-2,4-oxazolidinedione (2
-Thio-2,4- (3H, 5H) -oxazoledione) nucleus, for example 2-ethyl-2-thio-2,4-oxazolidinedione. (H) thianaphthenone nucleus, for example, 3 (2H) -thianaphthenone and 3 (2H) -thianaphthenone-1,1-
Dioxide. (I) 2-thio-2,5-thiazolidinedione nucleus, for example, 3-ethyl-2-thio-2,5-thiazolidinedione. (J) 2,4-thiazolidinedione nucleus, for example, 2,4
-Thiazolidinedione, 3-ethyl-2,4-thiazolidinedione and 3-phenyl-2,4-thiazolidinedione. (K) Thiazolidione nucleus, for example, 4-thiazolidinone, 3-ethyl-4-thiazolidinone. (L) 4-thiazozolinone nucleus, for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one. (M) 2-imino-2-oxozolin-4-one (coagulation hydantoin) nucleus. (N) 2,4-imidazolidinedione (hydantoin) nucleus, for example, 2,4-imidazolidinedione, 3-
Ethyl-2,4-imidazolidinedione. (O) 2-thio-2,4-imidazolidinedione (2
-Thiohydantoin) nuclei such as 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-
It is imidazolidinedione. (P) 2-imidazolin-5-one nucleus, for example 2-
n-propyl-mercapto-2-imidazolin-5-one. (Q) Furan-5-one.

The compound represented by formula (I) used in the present invention includes a compound represented by formula (Ia) or (Ib) and a compound represented by (Ic) Can be synthesized from

[0025]

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[0026] (L _1, L ₂ in the above formula is an alkyl group, Za ^-
Represents an anion) Specific examples of the compound represented by formula (I) used in the present invention are shown below.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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Next, the sensitizing dye represented by formula (II) will be described. In the formula (II), R ⁷ and R ⁸ are a hydrogen atom,
Alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkoxycarbonyl group, aryl group, substituted aryl group, alkynyl group, represents a substituted alkynyl group,
They may be the same or different. Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group,
Isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2
-Methylhexyl, cyclohexyl, cyclopentyl, and 2-norbornyl groups. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent for the substituted alkyl group, a monovalent nonmetallic atomic group other than hydrogen is used. Preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, Alkoxy, aryloxy, mercapto, alkylthio, allyl-thio, alkyldithio, aryldithio, amino, N-alkylamino, N, N-dialkylamino, N-arylamino, N, N- Diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N An arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group,
N'-alkylureido groups, N ', N'-dialkylureido groups, N'-arylureido groups, N', N'-diarylureido groups, N'-alkyl-N'-arylureido groups,

N-alkylureido, N-arylureido, N'-alkyl-N-alkylureido,
N'-alkyl-N-alkylureido groups, N ', N'
-Dialkyl-N-alkylureido group, N ', N'-
Dialkyl-N-arylureido, N'-aryl-N-alkylureido, N'-aryl-N-arylureido, N ', N'-diaryl-N-alkylureido, N', N'- Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-
N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-
N-alkoxycarbonylamino group, N-alkyl-N
-Aryloxycarbonylamino group, N-aryl-N
-Alkoxycarbonylamino group, N-aryl-N-
Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N
- arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfo group (-SO ₃ H) and its conjugate Base group (hereinafter,
Sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N
-Diarylsulfinamoyl group, N-alkyl-N-
Arylsulfinamoyl group,

Sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-
Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, referred to as phosphonate group) , dialkyl phosphono group ₍₂ -PO ₃ (alkyl)), diaryl phosphono group (-PO ₃ (aryl) _2), alkyl aryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono Group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter, arylphosphonate) Phonooxy group (-OPO ₃ H ₂ ) and its conjugated base group (hereinafter, referred to as “onato group”).
Phosphodiesterase referred to isocyanatomethyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), diaryl phosphonooxy group (-OPO ₃ (aryl) _2), alkylaryl phosphonooxy group (-OPO ₃ (alkyl ) (Aryl)), monoalkylphosphonooxy group (—OPO ₃ H
(Alkyl)) and its conjugate base group (hereinafter, referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter, arylphosphonatooxy group) ), A cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group and the like.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group,
Examples include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butynyl group, a cinnamyl group and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. As R in the acyl group (RCO-),
Examples include hydrogen, and the above-described alkyl and aryl groups. Of these substituents, an even more preferred one is a halogen atom (-F, -Br, -Cl,-
I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N-
Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group , N, N-dialkylcarbamoyl, N-arylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulfo, sulfonato, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl A group, an N-arylsulfamoyl group,
An N-alkyl-N-arylsulfamoyl group, a phosphono group, a phosphonate group, a dialkylphosphono group, a diarylphosphono group, a monoalkylphosphono group, an alkylphosphonato group, a monoarylphosphono group, an arylphosphonate group, Examples include a phosphonooxy group, a phosphonatoxy group, an aryl group, and an alkenyl group.

Specific examples include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, and tolylthiomethyl. Group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group,
N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonyl Methyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl Group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- ( Phosphono Enyl) sulfamoyl, octyl, phosphonobutyl, phosphonatohexyl, diethylphosphonobutyl, diphenylphosphonopropyl, methylphosphonobutyl, methylphosphonatobutyl, tolylphosphonohexyl, tolylphospho Onatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group,
Allyl group, 1-propenylmethyl group, 2-butenyl group,
2-methylallyl group, 2-methylpropenylmethyl group,
Examples thereof include a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include those in which one to three benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Examples of the substituent of the substituted aryl group include the substituents of the above-mentioned substituted alkyl group. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acetonaphthenyl group, and a fluorenyl group. Examples of the alkenyl group include linear, branched and cyclic alkenyl groups having 1 to 20 carbon atoms. Examples of the substituent of the substituted alkenyl group include the substituents described for the substituted alkyl group. Specific examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, and a 1-methyl-1 group. -Propenyl, styryl, 2-pentenyl, 2-cyclohexynyl and the like. Examples of the alkynyl group include a linear or branched alkynyl group having 1 to 20 carbon atoms.

The substituent of the substituted alkynyl group includes
The substituents described for the substituted alkyl group can be mentioned, and specific examples thereof include ethynyl, 2-phenylethynyl, 1-butynyl group and the like. Examples of the alkoxycarbonyl group include a residue in which a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxycarbonyl group. Specific examples thereof include a methoxycarbonyl group, Ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group,
Examples thereof include a sec-butoxycarbonyl group and a tert-butoxycarbonyl group. Although R ⁷ and R ⁸ have been described above, in the present invention, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group are preferred.

A in the general formula (II) represents an oxygen atom, a sulfur atom,
A carbon atom substituted by an alkyl or aryl group,
Or a carbon atom substituted by two alkyl groups. A
Examples of the aryl group and the alkyl group therein include those described for R ⁷ and R ⁸ . Examples of the nitrogen-containing five-membered ring completed by J in cooperation with A, C and N in the general formula (II) include the following.

[0045]

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The substituent E in the formulas (a-1) to (a-4)
Means that the Hammett ρ value is in the range of -0.9 to +0.5
There is something. Examples include hydrogen, methyl
Group, isopropyl group, tert-butyl group, phenyl
Group, trifluoromethyl group, acetyl group, ethoxycal
Bonyl group, carboxyl group, carboxylate group (-CO
O ^-), Amino group, methylamino group, dimethylamino
Group, ethylamino group, diethylamino group, acetylamino
No group, -PO_ThreeH group, methoxy group, ethoxy group, propo
Xy, isopropoxy, butoxy, benzyloxy
Groups, phenoxy groups, hydroxy groups, acetoxy groups,
Tylthio, ethylthio, isopropylthio, mel
Capto group, acetylthio group, thiocyano group (-SC
N), a methylsulfinyl group, an ethylsulfinyl group,
Methylsulfonyl group, ethylsulfonyl group, aminosulfon
Honyl group, dimethylsulfonyl group, (-S⁺(C
H_Three)_Two), A sulfonato group, (—SO_Two ^-), A fluorine atom,
Chlorine, bromine, iodine, iodyl, trimethyl
Lucyl group (-Si (CH_Three)_Three), Triethylsilyl
Group, trimethylstannyl group (-Sn (CH_Three)_Three)
be able to. Preferred among these substituents
Represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group,
Xyl group, dimethylamino group, diethylamino group, chlorine atom
Child, bromine atom.

Examples of Y in the general formula (II) are shown below. Examples of the substituent of the substituted phenyl group include the same as those described above for E. Examples of the polynuclear aromatic ring include a naphthyl group, an anthryl group, and a phenanthryl group, and these may be substituted with the substituent E described above. Examples of the heteroaromatic ring include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyrrolyl group, and a 3-pyrrolyl group, which are substituted by the substituent E described above. May be. An example of Z ¹ in the general formula (II) will be described below. Examples of the alkyl group, substituted alkyl group, aryl group and substituted aryl group include R ^{7 of the} general formula (II)
It includes the same as those as described as examples of R ^8. Examples of the alkylthio group and the arylthio group include a linear, branched, and cyclic alkyl group having 1 to 10 carbon atoms and a residue in which an aryl group having 1 to 20 carbon atoms is bonded to a thio group (sulfur atom). Can be mentioned,
Specific examples include methylthio, ethylthio, propylthio, butylthio, sec-butylthio, t
Examples thereof include an tert-butylthio group, a phenylthio group, and a naphthylthio group.

Examples of the alkoxyl group include a residue in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxy group (oxygen atom). Group, ethoxyl group,
Examples include a propoxyl group, a butoxyl group, a sec-butoxyl group, and a tert-butoxyl group. As the substituted amino group, a linear group having 1 to 10 carbon atoms,
An amino group substituted by a branched or cyclic alkyl group can be mentioned, and specific examples thereof include a dimethylamino group, a diethylamino group, and a dipropylamino group. Examples of the acyl group include a hydrogen atom, a residue in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, a phenyl group or a naphthyl group is bonded to carbonyl. Specific examples thereof include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a benzoyl group, and a naphthoyl group. Examples of the alkoxycarbonyl group include a residue in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxycarbonyl group. Specific examples thereof include a methoxycarbonyl group and an ethoxy group. Carbonyl group, propoxycarbonyl group, butoxycarbonyl group,
Examples thereof include a sec-butoxycarbonyl group and a tert-butoxycarbonyl group. Examples of a ring formed by combining Y and Z ¹ with each other are shown below.

[0049]

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[0050]

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The group of compounds represented by the general formula (II) is “Ru
ll. Soc. Chimie Belges, Vol. 57, 364-372
Page (1948) Abstract: Chemical Abstracts, No. 4
The compound can be synthesized according to the method described in Vol. 4, columns 60e to 61d (1950). Specific examples of the compound represented by the general formula (II) are shown below.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

[Table 1]

[0059]

[Table 2]

Next, in the general formula (III) used in the present invention,
The sensitizing dye represented will be described. Where R^Ten~ R¹³Are
Independently independently of a hydrogen atom, unsubstituted or substituted C 1 -C 6
Substituted alkoxy group, unsubstituted or substituted alkyl group having 1 to 6 carbon atoms
Kenyloxy group, unsubstituted or substituted alkyl having 1 to 6 carbon atoms
Dialkyl having a carbon number of 1 to 4;
Alkylamino group, hydroxyl group, acyloxy group, halogen source
, A nitro group, or a multiple ring group. R^Ten~ R¹³2
Or three and the R^Ten~ R¹³Is attached to
And the condensed ring is 5 or 6
A fused ring or fused ring system that is a membered ring may be formed. R
⁹Is a hydrogen atom, an unsubstituted or substituted alkyl having 1 to 4 carbon atoms.
Or an unsubstituted or substituted aryl having 6 to 12 carbon atoms
Group, or R¹⁴Represents -CO-. Where R ¹⁴Is Arco
Xy group, cycloalkoxy group, hydroxyl group, aryloxy
Group, alkenyloxy group, aralkyloxy group, alcohol
Xycarbonylalkoxy group, alkylcarbonylalkyl
Coxy group or substitution represented by (III-a) to (III-c)
Group (R ^Fifteen~ R¹⁸Represents a hydrogen atom, an alkyl group,
Alkyl group, hydroxyalkoxyalkyl group, alkoxy
Represents a silalkyl group or a cycloalkyl group. ). Q
¹Is -CN, heterocyclic, -Z^Two-R¹⁹And R¹⁹Is meth
, Ethyl, propyl, isopropyl, t-butyl, i
Sobutyl, butyl, amyl, hexyl, heptyl, octane
Tyl, nonyl, decyl and cyclopentyl, cyclohexyl
C1-C10 containing cycloalkyl such as xyl
Alkyl; substituted alkyl; aryl such as phenyl
Nitro, alkoxy, halogen, carboalkoxy
Si, alkyl, aryl, carboxy, hydroxy, a
Mino, dialkylamino or trialkylammonium
Aryl substituted with a substituted amino or the like;
Alkoxy, ethoxy, butoxy, etc .; phenoxy, etc.
Aryloxy having about 5 ring carbon atoms and about 5 hetero atoms
To 15 heterocyclic groups, e.g.

[0061]

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(Wherein R ⁴¹ is methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl,
alkyl having 1 to 4 carbon atoms including s-butyl and the like;
^- the FSO ₃ ^-, Br ₄ ^-, p-toluenesulfonate, halogen (e.g., Cl, Br, I) is an anion, and the like) of pyridinium; nicotinyl; Nikochiniumu; furyl; 2- benzofuranyl; 2-thiazolyl; 2-thienyl or the like; or a formula

[0063]

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(Wherein R ^{42 to} R ⁴⁶ are selected from the same groups as the above-mentioned substituents), and is an acyl group such as 3-substituted coumarinyl or acetyl, and Z ² is carbonyl, sulfonyl, sulfinyl or aryl. A bonding group selected from range carbonyl. As the aryl group for R ¹⁹ ,
Examples include a phenyl group, a naphthyl group and an indenyl group. Examples of the heterocyclic ring include those having the following structure.

[0065]

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Here, M is -CH or a nitrogen atom, and T is-
CH ₂ —, NH, and S are represented, and W represents a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear or dinuclear aromatic heterocyclic group. In particular,

[0067]

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And the like. Examples of the sensitizing dye of the formula (III) include the following. 3-benzoyl-5,7-dimethoxycoumarin 3-benzoyl-7-methoxycoumarin 3-benzoyl-6-methoxycoumarin 3-benzoyl-8-ethoxycoumarin 7-methoxy-3- (p-nitrobenzoyl) coumarin 3-benzoyl Coumarin 3- (p-nitrobenzoyl) coumarin 3-benzoylbenzo [f] coumarin 3,3'-carbonylbis (7-methoxycoumarin) 3-acetyl-7-methoxycoumarin 3-benzoyl-6-bromocoumarin 3,3 '-Carbonylbiscoumarin 3-benzoyl-7-dimethylaminocoumarin 3,3'-carbonylbis (7-diethylaminocoumarin) 3-carboxycoumarin 3-carboxy-7-methoxycoumarin 3-ethoxycarbonyl-6-methoxycoumarin3- Ethoxycal Nyl-7-methoxycoumarin 3-acetylbenzo [f] coumarin 3-acetyl-7-methoxycoumarin 3- (1-adamantoyl) -7-methoxycoumarin 3-benzoyl-7-hydroxycoumarin 3-benzoyl-6-nitro Coumarin 3-benzoyl-7-acetocoumarin 3-benzoyl-7-diethylaminocoumarin 7-dimethylamino-3- (4-iodobenzoyl) coumarin 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin 7-methoxy-3- (4-methoxybenzoyl) coumarin 3- (4-nitrobenzoyl) benzo [f] coumarin 3- (4-ethoxycinnamoyl) -7-methoxycoumarin 3- (4-dimethylaminocinnamoyl) coumarin 3- (4- Diphenylaminocinnamoyl) coumarin 3-[(3-methylbenzothiazole-2-ylidene)
Acetyl] coumarin 3-[(1-methylnaphtho [1,2-d] thiazole-
2-ylidene) acetyl] coumarin 3,3'-carbonylbis (6-methoxycoumarin) 3,3'-carbonylbis (7-acetoxycoumarin) 3,3'-carbonylbis (7-dimethylaminocoumarin) 3,3 '-Carbonylbis- (5,7-diisopropoxy) coumarin 3,3'-carbonylbis- (5,7-di-n-propoxy) coumarin 3,3'-carbonylbis- (5,7-di- n-butoxy) coumarin 3-cyano-6-methoxycoumarin 3-cyano-7-methoxycoumarin 7-methoxy-3-phenylsulfonylcoumarin 7-methoxy-3-phenylsulfinylcoumarin 1,4-bis (7-diethylamino-3 -Coumarylcarbonyl) benzene 7-diethylamino-5 ', 7'-dimethoxy-3,
3'-carbonylbiscoumarin 7-dimethylamino-3-thenoylcoumarin 7-diethylamino-3-furoylcoumarin 7-diethylamino-3-thenoylcoumarin 3-benzoyl-7- (1-pyrrolidinyl) coumarin 5,7, 6'-trimethoxy-3,3'-carbonylbiscoumarin 5,5,7'-trimethoxy-3,3'-carbonylbiscoumarin 7-diethylamino-6'-methoxy-3,3'-carbonylbiscoumarin 3-nicotinoyl -7-methoxycoumarin 3- (2-benzofuranylcarbonyl) -7-methoxycoumarin 3- (7-methoxy-3-coumarinoyl) -1-methylpyrimidium fluorosulfate 3- (5,7-diethoxy-3 -Coumarinoyl-1-methylpyrimidium fluoroborate N- (7-methoxy 3 Kumari hexanoyl methyl) pyridinium bromide 9- (7-diethylamino-3-Kumarinoiru) -1,
2,4,5-tetrahydro-3H, 6H, 10H [1]
Benzopyrano [a, 9a.l-gh] quinolazine-10
And compounds represented by the following chemical formulas (III-1) to (III-15).

[0069]

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[0070]

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The sensitizing dyes represented by formulas (I) to (III) may be used alone or in combination of two or more.
These sensitizing dyes are used in an amount of 0.05 to 30 parts by weight per 100 parts by weight of the compound having an ethylenically unsaturated double bond.
Parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight.

Next, the radical polymerization initiator used in the present invention will be described. The radical polymerization initiator is not particularly limited, but the compounds shown in the following (a) to (nu) are preferable. (A) Compound having a carbon-halogen bond (b) Ketone compound represented by the following general formula (IV)

[0073]

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(Where Ar is the following (VI-a) or (VI-a)
b) an aromatic group represented by ²⁰, R^{twenty one}Is hydrogen
Represents an atom or an alkyl group;²⁰, R^{twenty one}Are each other
It may be linked to represent an alkylene group.

[0075]

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In the above formula, R ^{22 to} R ²⁶ may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group,
Hydroxyl group, alkoxy group, -SR ²⁸ group, -SO-R
²⁸ groups represent a -SO ₂ -R ²⁸ group, at least one -S-R ²⁸ group of ^{R 22 ~R 26, -SO-R} 28 group, -SO ₂ -
A R ^{2 8} group, R ²⁸ represents an alkyl group, an alkenyl group. R ²⁷ represents a hydrogen atom, an alkyl group or an acyl group, and Y ¹ represents a hydrogen atom or

[0077]

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Represents the following. R ²⁹ has the same meaning as R ^20, and R ³⁰ has the same meaning as R ²¹ . (C) a ketoxime compound represented by (V) in the following general formula

[0079]

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(Wherein R ³¹ and R ³² may be the same or different and each represents a substituent or a hydrocarbon group or a heterocyclic group which may contain an unsaturated bond. R ³³ and R ³⁴ are the same. Or may be different, a substituent, a hydrocarbon group which may contain an unsaturated bond, a heterocyclic group, a hydroxy group,
Represents a substituted oxy group, a mercapto group, or a substituted thio group. R ³³ and R ³⁴ are bonded to each other to form a ring, and —O— and —N
R ³⁷ —, —O—CO—, —NH—CO—, —S— and / or —SO ₂ — represent an alkylene group having 2 to 8 carbon atoms which may be contained in the ring main chain. R ³⁷ represents a hydrogen atom, a substituent, a hydrocarbon group optionally having an unsaturated bond, or a substituted carbonyl group. R ³⁵ , R ³⁶
Represents a hydrogen atom, a substituent, a hydrocarbon group which may contain an unsaturated bond, or a substituted carbonyl group. (D) Organic peroxide (e) Thio compound represented by the following general formula (VI)

[0081]

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(Where R ³⁸ represents an alkyl group, an aryl group or a substituted aryl group, R ³⁹ represents a hydrogen atom or an alkyl group, and R ³⁸ and R ³⁹ are bonded to each other to form an oxygen, sulfur, or nitrogen atom Represents a group of nonmetallic atoms necessary for forming a 5- to 7-membered ring which may contain a heteroatom selected from the group consisting of: (f) hexaarylbiimidazole (g) aromatic onium salt (h) ketoxime Ester (li) N-phenylglycine (nu) titanocene compound

As the compound (A) having a carbon-halogen bond, compounds represented by the following formulas (VII) to (XIII) are preferable. General formula (VII)

[0084]

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(Wherein X represents a halogen atom; Y ²
Is ^{_{-CX 3, -NH 2, -NHR 47}} , -NR 47, -OR 47
Represents Here, R ⁴⁷ is an alkyl group, a substituted alkyl group,
Represents an aryl group or a substituted aryl group. R ⁴⁸ is -C
X _{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ). General formula (VIII)

[0086]

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(Where R ⁴⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxy group, a nitro group or a cyano group; Is a halogen atom, and n is an integer of 1 to 3.).

Formula (IX) R⁵⁰-Z^Three-CH_2-mX_m-R⁵¹ (IX) (However, R⁵⁰Is an aryl group or a substituted aryl group
R⁵¹Is -CO-NR ⁵²R⁵³Or

[0089]

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Or Z ³ is -CO-,-
CS- or -SO ₂ - and is, R ^52, R ⁵³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, R ⁵⁴ is R in the general formula (VII) Same as ⁴⁷ , m is 1 or 2. ). General formula (X)

[0091]

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Wherein R ⁵⁵ is an optionally substituted aryl group or a heterocyclic group, and R ⁵⁶ is
A trihaloalkyl or trihaloalkenyl group having three, and p is 1, 2 or 3. General formula (XI)

[0093]

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(Where L is a hydrogen atom or a compound of the formula: CO—
^{_{(R 57) n (CX 3}} ) substituents represented by _m (n is 0 to 2, m is 1 to 3) and, D is a substituted or unsubstituted alkylene group, Q ² Is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or an NR ⁵⁸ group;
+ Q ² together form a 3 or 4 heterocycle, R ⁵⁸ is an alkyl, aralkyl or alkoxyalkyl group, R ⁵⁷ is a carbocyclic or heterocyclic aromatic group, X
Is a chlorine, bromine or iodine atom, q = 0 and r = 1
Or q = 1 and r = 1 or 2. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group; General formula (XII)

[0095]

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(Where X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁵⁹ is a hydrogen atom or a CH _{3-t Xt} group, ⁶⁰ is an s-valent optionally substituted unsaturated organic group). Represented by
4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivatives. General formula (XIII)

[0097]

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(Where X is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ⁶¹ is a hydrogen atom or a CH _{3-v Xv} group, ⁶² is a u-valent unsaturated organic group which may be substituted). Represented by
2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivatives.

Compounds having such a carbon-halogen bond are described, for example, in Wakabayashi et al., Bull. Chem. Soc.
Japan, 42 , 2924 (1969).
-Phenyl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
Tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2-
(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6- Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (triclomethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis ( Trichloromethyl) -S-triazine and the like. In addition, British Patent No. 1388
No. 492, for example, 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-
Compounds described in JP-A-53-133428, such as triazine and 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine;
-(4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S -Triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
The compounds described in German Patent No. 3337024, for example, the following compounds can be mentioned.

[0100]

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[0101]

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Also, J. Org. Che by FC Schaefer et al.
m .; 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S
-Triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like. Further, there may be mentioned the compounds described in JP-A-62-58241, for example, the following compounds.

[0103]

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[0104]

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Further, there may be mentioned the compounds described in JP-A-5-281728, such as the following compounds.

[0106]

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Alternatively, MPHutt, EFElslager
And LMWerbel, Journal of Heterocyclic Chemist
The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis method described in ry Vol. 7 (No. 3), pp. 511 et seq. (1970) can be mentioned.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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Alternatively, compounds such as those described in DE-A-264 1100, for example 4-
(4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5
-Trimethoxy-styryl) -6-trichloromethyl-
2-pyrone or the compounds described in DE 33 33 450, for example,

[0118]

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Alternatively, a group of compounds described in German Patent No. 3021590,

[0120]

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Alternatively, a group of compounds described in German Patent No. 3021599, for example,

[0122]

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The following can be mentioned.

Next, the ketone compound represented by the general formula (IV) of (b) will be described. In the formula, R ²⁰ and R ²¹ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ²⁰ and R ²¹ may combine to represent an alkylene group. R ^{22 to} R in (IV-a) and (VI-b) which are Ar
²⁶ independently of one another are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group,- SR- ²⁸ group, -SO-R- ²⁸ group, -S
Represents an O ₂ —R ²⁸ group, wherein R ²⁷ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an acyl group having 2 to 13 carbon atoms. These alkyl group, aryl group, alkenyl group, and acyl group may be further substituted with a substituent having 1 to 6 carbon atoms. R ^{29 in} Y ¹ has the same meaning as R ^20, and R ³⁰ has the same meaning as R ²¹ . Specific examples thereof include the following compounds described in U.S. Pat. No. 4,318,791 and European Patent No. 0284561A.

[0125]

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[0126]

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Next, the ketoxime compound represented by the general formula (V) of (c) will be described. Wherein R ³¹ ,
R ³² is the same or different and represents a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group. R ³³ and R ³⁴ are the same or different and are a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted Represents a thio group. Also, R
³³ and R ³⁴ are bonded to each other to form a ring, -O-, -NR
^{37 -, - O-CO -} , - S-, and -SO ₂ - represents an alkylene group having from 2 carbon atoms which may contain a linking backbone of the ring 8. R ³⁷ represents a hydrogen atom, a substituent, a hydrocarbon group optionally having an unsaturated bond, or a substituted carbonyl group. R ³⁵ and R ³⁶ represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. As specific compounds,
The following can be mentioned, but not limited thereto.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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Examples of the organic peroxide (d) include compounds having an oxygen-oxygen bond in the molecule. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane,
2,2-bis (tertiarybutylperoxy) butane, tertiarybutylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-di Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide,
Dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide,

2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, dimethoxyisopropylperoxy Carbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxypivalate, tertiary butyl peroxypivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxyoctano Eat,
Tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy laurate, tertiary butyl peroxy benzoate,
Ditertiary butyl peroxyisophthalate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary butyl peroxide maleic acid, tertiary butyl peroxyisopropyl carbonate,
3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) 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, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Of these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) Benzophenone, 3,3 ', 4,4'
-Tetra- (t-xylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone,
Peroxide esters such as di-t-butyldiperoxyisophthalate are preferred.

The above (e) thio compound has the general formula (VI)
Indicated by The alkyl group of R ³⁸ and R ³⁹ in the general formula (VI) is preferably one having 1 to 4 carbon atoms. The aryl group of R ³⁸ is preferably a group having 6 to 10 carbon atoms such as phenyl and naphthyl. As the substituted aryl group, a halogen atom such as a chlorine atom and a methyl group And those substituted with an alkoxy group such as an alkyl group, a methoxy group or an ethoxy group.

Specific examples of the thio compound represented by the general formula (VI) include the compounds shown in the following table.

[0138]

[Table 3]

[0139]

[Table 4]

[0140]

[Table 5]

The hexaarylbiimidazole of the component (f) used in the present invention includes 2,2'-bis (o-
(Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Bis (o, p-dichlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and the like.
Examples of the ketoxime ester include 3-benzoyloximinobtan-2-one and 3-acetoxyiminobutan-
2-one, 3-propionyloxy iminobutan-2-
On, 2-acetoxyiminopentan-3-one, 2-
Acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropane-1
-One, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-
1-phenylpropan-1-one and the like.

The (g) aromatic onium salts include elements of Groups V, VI and VII of the Periodic Table, specifically N, P, As, Sb, Bi, O, S, Se, Te or I aromatic onium salts are included. Examples of such aromatic onium salts include JP-B-52-14277 and JP-B-52-1.
No. 4278 and JP-B No. 52-14279 can be mentioned, and specifically, the following compounds can be mentioned.

[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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Among these, preferred are BF ₄ salts,
Or a compound of a PF ₄ salt, more preferably a BF ₄ salt or a PF ₄ salt of an aromatic iodonium salt.

Examples of the above-mentioned (T) ketoxime esters include 3-benzoyloximinobtan-2-one,
Acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-
1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-
ON and the like.

The (nu) titanocene compound is a titanocene compound capable of generating an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye, and is, for example, disclosed in JP-A-59-152396 and JP-A-59-152396. Known compounds described in JP-A-61-151197 can be appropriately selected and used. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,
6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1
-Yl, di-cyclopentadienyl-Ti-bis-2,
4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis -2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl,
Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium and the like can be mentioned.

These radical polymerization initiators (a) to (nu) can be used alone or in combination of two or more. The use amount is suitably from 0.05 to 100 parts by weight, preferably from 1 to 80 parts by weight, more preferably from 3 to 50 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound. The content of these photopolymerization initiation systems in the photosensitive composition of the present invention is usually low. In addition, when the number is inappropriately large, undesired results such as blocking of the effective light beam occur. The amount of the photopolymerization initiation system in the present invention is from 0.01% by weight to 60% by weight based on the total amount of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular weight polymer added as required. It is preferable to use it in the range. More preferably, 1% to 30% by weight gives good results.

Further, the photopolymerizable composition of the present invention may contain an organic halogen compound and a leuco dye for the purpose of distinguishing the color of the exposed portion and the unexposed portion.
As the organic halide, the above-mentioned radical polymerization initiator (a) a compound having a carbon-halogen bond is generally used. The amount of the organic halogen compound used in the present invention as such a printing-out agent is in the range of 0.001% by weight to 5% by weight based on the solid content of the photopolymerizable composition. More preferably, it is 0.005% by weight to 1% by weight.

Representative leuco dyes that can be used in the present invention include the following. Tris (p-dimethylaminophenyl) methane, leuco crystal violet, tris (p-diethylaminophenyl) methane, tris (p-dimethylamino-o-methylphenyl) methane, tris (p-diethylamino-o-methylphenyl) methane, Bis (p-dibutylaminophenyl)-[p- (2-cyanoethyl) methylaminophenyl] methane, bis (p-dimethylaminophenyl) -2
Aminotriarylmethanes such as quinolylmethane and tris (p-dipropylaminophenyl) methane;
-Bis (diethylamino) -9-phenylxanthene,
3-amino-6-dimethylamino-2-methyl-9-
Aminoxanthenes such as (o-chlorophenyl) xanthene, 3,6-bis (diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene, 3,6-
Aminothioxanthenes such as bis (dimethylamino) thioxanthene, 3,6-bis (diethylamino) -9,
Amino-9,10-dihydroacridines such as 10-dihydro-9-phenylacridine, 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine, and 3,7-bis (diethylamino) phenoxy Aminophenoxazines such as sagin; aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine;
3,7-bis (diethylamino) -5-hexyl-5,
Aminodihydrophenazines such as 10-dihydrophenazine; aminophenylmethanes such as bis (p-dimethylaminophenyl) anilinomethane; 4-amino-4'-
Dimethylaminodiphenylamine, 4-amino-α, β
-Aminohydrocinnamic acids such as methyl-dicyanohydrocinnamate, hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine, 1,4-bis (ethylamino) -2,3-dihydroanthraquinone and the like Amino-
Phenethylanilines such as 2,3-dihydroanthraquinones and N, N-diethyl-p-phenethylaniline;
It has no oxidizable hydrogen such as an acyl derivative of a leuco dye containing a basic NH group such as 10-acetyl-3,7-bis (dimethylamino) phenothiazine and tris (4-diethylamino-o-tolyl) ethoxycarbonylmethane. , A leuco-like compound which can be oxidized to a color-forming compound, a leucoin digoid dye, which can be oxidized to a color-forming form as described in U.S. Pat. Nos. 3,042,515 and 3,042,517. Such organic amines. The following may be mentioned as typical compounds of this type. 4,4'-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4'-methylenediaminetriphenylamine, N-vinylcarbazole.
Of these, particularly preferred is leuco crystal violet. The amount of the leuco dye used in the present invention is in the range of 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the solid content of the photopolymerizable composition.

In the present invention, a dye can be used for the purpose of coloring the photopolymerizable composition or imparting storage stability. Examples of suitable dyes include brilliant green sulfate, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymol phthalein, methyl violet 2B, quinaldine red, rose bengal, methanyl-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange N, diphenylthiocarbazone, 2,7-
Dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl-red, nile blue A, phenacetaline, methyl violet, malachite green oxalate, parafuchsin,
Oil Blue # 603 [Orient Chemical Industry Co., Ltd.
Manufactured), rhodamine B, rhodamine 6G and the like. A particularly preferred dye is malachite green oxalate.

It is preferable to further add a thermal polymerization inhibitor to the photopolymerizable composition of the present invention. Specific examples of the thermal polymerization inhibitor include, for example, p-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone,
t-butylcatechol, pyrogallol, cuprous chloride, chloranil, naphthylamine, β-naphthol, 2,6
-Di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, organic copper, methyl salicylate and the like. These thermal polymerization inhibitors are used in an amount of 0.00
It is preferably contained in the range of 1 to 5% by weight.

In the present invention, a plasticizer may be added to control the physical properties of the film. Representative examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, Phthalates such as dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diaryl phthalate, dimethyl glycolose phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene Glycol esters such as glycol dicaprylate, and phosphate esters such as tricresyl phosphate and triphenyl phosphate. , Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, fatty acid dibasic acid esters such as dibutyl malate, benzenesulfonamide, p-toluenesulfonamide, N-n-butylacetamide and the like Examples include amides, triethyl citrate, glycerin triacetyl ester, and butyl laurate.

In the present invention, a known so-called adhesion promoter can be used to improve the adhesion. For example, Japanese Patent Publication No. 50-9177, Japanese Patent Publication No. 54-1979
No. 5,292, JP-B-55-22,481, JP-A-5
1-64,919, JP-A-51-64,920, JP-A-50-63,087, JP-A-52-2,724.
JP-A-53-702 and JP-A-53-12454.
No. 1, JP-A-53-124,594, JP-A-54-1
33,585, JP-A-54-133,586, JP-A-55-65,947, and JP-B-57-46,053.
No., JP-B-57-46,054, JP-A-56-11,
No. 904, JP-B-57-21,697, JP-A-56-
No. 75,642, JP-A-56-67844, JP-B-57-40,500, JP-A-56-99,202,
JP-A-56-100,803, JP-A-57-60,3
No. 27, JP-A-57-62,047, DAS 2, 44
No. 8,850, US Pat. No. 4,629,679, Japanese Patent Publication No. 57
-49,894, JP-A-57-148,392, JP-A-57-192,946, JP-A-58-100,8
No. 44, JP-A-59-113432, JP-A-59-113432
125,725, JP-A-59-125,726, JP-A-59-125,727, JP-A-59-125,727
No. 28, JP-A-59-152,439, JP-A-59-152439
154,440, JP-A-59-154,441, JP-A-59-165,051, JP-A-60-12,54.
No. 3, JP-A-60-12,544, JP-A-60-13
5,931, JP-A-60-138,540, JP-A-60-146,233, JP-A-61-4,038,
JP-A-61-6,644, JP-A-61-6,646
JP-A-61-166,541, JP-A-61-17
No. 2,139, JP-A-61-186,952, JP-A-61-190,330, JP-A-61-198,146.
JP-A-61-223,836 and JP-A-61-28
2,835, JP-A-61-360,237, JP-A-62-91,935, JP-A-62-96,939,
JP-A-62-180,354, JP-A-62-180,
355, JP-A-62-180,356, JP-A-62
-180,357, JP-A-62-181,303,
JP-A-62-208,042, JP-A-62-240,
No. 950, JP-A-62-277,405 and JP-A-62
-286,035, JP-A-62-290,702,
JP-B-63-13,526, JP-A-63-24,24
No. 3, JP-A-63-57,622 and JP-A-63-6
There are compounds described in JP-A Nos. 1,241 and each publication or specification. Specifically, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl-1-
Phenyl-triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole and the like There is. Particularly preferred compounds include 3-morpholinomethyl-1-phenyltriazole-2
-Thione.

The other main components of the thermoplastic polymer binder and the non-gaseous ethylenically unsaturated compound contained in the photopolymerizable composition of the present invention are not particularly limited, and examples thereof include the following. Each compound can be used. The thermoplastic polymer binder is a wide variety of synthetic,
Semi-synthetic or natural polymer substances satisfying the following conditions are used. That is, the compatibility with the ethylenically unsaturated compound, the photopolymerization initiator, the organic halogen compound, and the leuco dye causes demixing during the manufacturing process from preparation of the coating solution to coating and drying, and storage of the obtained coated product. Not so good, properties according to the use of the present invention, for example, when used in the form of a photoresist for tenting, the strength of the binder, stretchability, abrasion resistance, chemical resistance and the like are appropriate. In addition, the molecular weight, intermolecular force, hardness, softening temperature, crystallinity, elongation at break, etc. of the binder are appropriate. Specific examples of the binder include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, and poly (meth) acrylic acid alkyl esters such as polymethyl (meth) acrylate (where the alkyl group is a methyl group, an ethyl group, or a butyl group). ), (Meth) acrylic acid and (meth)
Copolymers with acrylic acid alkyl esters (alkyl groups are as described above), poly (meth) acrylic acid, (meth) acrylic acid alkyl esters (alkyl groups are as described above) and acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc. Copolymers with at least one of the monomers, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, copolymers of vinyl acetate and vinyl chloride, Polyacrylonitrile, a copolymer of acrylonitrile and styrene, a copolymer of acrylonitrile and butadiene and styrene, a copolymer of styrene and an unsaturated dibasic acid anhydride such as maleic anhydride, polyvinyl butyral, styrene butadiene rubber, Chloride rubber, cyclized rubber, acetyl cellulose Scan the like homopolymers or copolymers of such. In the case of a copolymer, the content ratio of the component monomers can take a wide range of values, but in general, it is preferable that the content of the other copolymer monomer is 5% or more in a molar ratio. Further, polymers other than these can be used as the binder of the present invention as long as they satisfy the above conditions.

Of the above-mentioned polymers, those particularly preferably used as the binder of the present invention include chlorinated polyethylene,
Chlorinated polypropylene, polymethyl methacrylate,
Methyl methacrylate-acrylonitrile copolymer (molar content of methyl methacrylate 20-80%), vinyl chloride-acrylonitrile copolymer (molar content of vinyl chloride 20-80%), vinylidene chloride-acrylonitrile copolymer (mol of vinylidene chloride) Content 20-80%),
Styrene-maleic anhydride copolymer, Japanese Patent Application No. 59-11
No. 4736 (the binder is a quaternary copolymer of methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / benzyl methacrylate), and JP-B-54-34.
No. 327 (the binder is, for example, a terpolymer of methyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid), and JP-B-55-38961 (the binder is, for example, styrene / mono-n-butyl maleate). JP-B-54-25957 (the binder is, for example, a quaternary copolymer of ethylene / methyl methacrylate / ethyl acrylate / methacrylic acid);
No. 99810 (the binder is, for example, benzyl methacrylate /
A methacrylic acid copolymer), and JP-B-58-1257.
No. 7 (the binder is, for example, a terpolymer of acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid) and JP-B-55-6210 (the binder is, for example, methyl methacrylate / ethyl acrylate / acrylic acid). And styrene / maleic anhydride copolymer partially esterified with isopropanol) and the binders described in each publication or in the specification.

These binders may be used alone as a binder, but demixing is carried out during the production process from preparation of two or more coating solutions to coating and drying and storage of the obtained coating material. Polymers compatible with each other to such an extent that they do not occur can be mixed at an appropriate ratio and used as a binder. The molecular weight of the high molecular substance used as the binder can take a wide range of values depending on the type of the polymer.
2,000 to 2,000,000, more preferably 50,
Those having a range of 000 to 1,000,000 are suitably used in the present invention. The amount of the binder is 5 to 95% by weight, preferably 40 to 80% by weight, based on the solid content of the photopolymerizable composition.

The ethylenically unsaturated compound suitable for use in the present invention is a compound having at least two terminal unsaturated groups and capable of being photopolymerized by irradiation with actinic rays (hereinafter referred to as a polyfunctional monomer). Abbreviated.) In particular,
JP-B-35-5,093, JP-B-35-14,7
No. 19, JP-B-44-28,727 and the like. First, as acrylates and methacrylates, there are polyacrylates and polymethacrylates of polyhydric alcohols (here, “poly” refers to diacrylate or higher).
Examples of the polyhydric alcohol include polyethylene glycol, polypropylene glycol, polybutylene glycol, polycyclohexene oxide, polystyrene oxide, polyoxetane, polytetrahydrofuran, cyclohexanediol, xylylene diol, di- (β
-Hydroxyethoxy) benzene, glycerin, diglycerin, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol,
Dipentaerythritol, sorbitan, sorbitol,
Butanediol, butanetriol, 2-butene-1,
4-diol, 2-n-butyl-2-ethyl-propanediol, 2-butene-1,4-diol, 3-chloro-1,2-propanediol, 1,4-cyclohexanedimethanol, 3-cyclohexene- 1,1-dimethanol, decalindiol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-dihydroxy-1,2,3 ,
4-tetrahydronaphthalene, 2,5-dimethyl-2,
5-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol, dodecanediol, mesoerythritol,
2-ethyl-1,3-hexanediol, 2-ethyl-
2- (hydroxymethyl) -1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, heptanediol, hexanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, hydroxy Ethyl resorcinol, 2-methyl-
1,4-butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol, pentanediol, 1-phenyl-1,2-ethanediol, propanediol, 2,2,4,4-tetra Methyl-1,3-cyclobutanediol, 2,3,5,6-tetramethyl-p-xylene-α, α'-diol, 1,
1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-
1,4-diol, 1,2,6-trihydroxyhexane, 1,1'-bi-2-naphthol, dihydroxynaphthalene, 1,1'-methylenedi-2-naphthol, 1,
2,4-benzenetriol, biphenol, 2,2 '
-Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, 3,4-dihydroxyhydrocinnamic acid, hydroquinone, hydroxy Benzyl alcohol, methylhydroquinone, methyl-2,
4,6-trihydroxybenzoate, phloroglucinol, pyrogallol, resorcinol, glucose, α
-(1-aminoethyl) -p-hydroxybenzyl alcohol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1, 2-propanediol, N-
(3-aminopropyl) -diethanolamine, N,
N'-bis- (2-hydroxyethyl) piperazine,
2,2-bis (hydroxymethyl) -2,2 ', 2 "-
Nitrilotriethanol, 2,2-bis (hydroxymethyl) propionic acid, 1,3-bis (hydroxymethyl) urea, 1,2-bis (4-pyridyl)-
1,2-ethanediol, Nn-butyldiethanolamine, diethanolamine, N-ethylenediethanolamine, 3-mercapto-1,2-propanediol, 3-piperidino-1,2-propanediol, 2-
(2-pyridyl) -1,3-propanediol, triethanolamine, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenyl sulfone, and the like. Of these acrylates and methacrylates, the most preferred are ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetrapropylene glycol diacrylate, dodecapropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, penta Erythritol tetraacrylate, Pentaery Lithol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate,
Dipentaerythritol pentaacrylate, glycerin triacrylate, diglycerin dimethacrylate,
1,3-propanediol diacrylate, 1,2,4
-Butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,5-pentanediol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate to which ethylene oxide is added, and the like.

On the other hand, acrylamides and methacrylamides include methylenebisacrylamide, methylenebismethacrylamide, ethylenediamine,
Diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene, bis (2-aminopropyl)
Amines, diethylenetriaminediamine, heptamethylenediamine, octamethylenediamine, polyamines interrupted by hetero atoms, ring-containing polyamines (for example, phenylenediamine, xylylenediamine, β-
(4-aminophenyl) ethylamine, diaminobenzoic acid, diaminotoluene, diaminoanthraxine, diaminofluorene, etc.) and polyacrylamide and polymethacrylamide.

As the allyl compound, for example, phthalic acid,
Diallyl esters of dicarboxylic acids such as terephthalic acid, sebacic acid, adipic acid, glutaric acid, malonic acid, oxalic acid, for example, anthraquinone disulfonic acid, benzenedisulfonic acid, 2,5-dihydroxy-p-benzenedisulfonic acid, dihydroxynaphthalenedisulfonic acid And diallyl esters of disulfonic acids such as naphthalenedisulfonic acid and diallylamide.

Examples of the vinyl ether compounds include polyvinyl ethers of the above-mentioned polyhydric alcohols, for example, ethylene glycol divinyl ether, 1,3,5-tri-β
-Vinyloxyethoxybenzene, 1,3-di-β-vinyloxyethoxybenzene, glycerol trivinyl ether and the like.

As vinyl esters, divinyl succinate, divinyl adipate, divinyl phthalate,
Divinyl terephthalate, divinylbenzene-1,3-
Disulfonate and divinylbutane-1,4-disulfonate.

Examples of the styrene compound include divinylbenzene, p-allylstyrene, p-isopropenestyrene and the like. Different addition polymerizable unsaturated bonds such as N-β-hydroxyethyl-β- (methacrylamido) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, allyl methacrylate, etc.
Compounds having more than one compound are also suitably used in the present invention.

Further, a reaction product obtained by reacting a polyol compound having at least two hydroxyl groups with a slightly excess polyisocyanate compound having at least two isocyanate groups is added to at least one hydroxyl group and at least one ethylenically unsaturated compound. A polyfunctional urethane compound having at least two ethylenically unsaturated groups obtained by reacting a compound having a group is also suitably used in the present invention. These polyfunctional monomers can be used alone or in combination of two or more.
It is used in the range of ~ 90wt%, preferably 15 ~ 60wt%.

The photopolymerizable composition of the present invention prepared as described above is provided on a substrate as a photoresist for producing a printed wiring board. At that time, a coating solution is prepared by dissolving or dispersing in a solvent, and is directly applied on a substrate using a spinner or a wheeler and dried to form a film, or the coating solution is applied to an appropriate support. It is generally applied by a suitable method, dried, and if necessary, a protective film is overlaid thereon, used as an image forming material (dry film resist), and adhered to a substrate. As the substrate, a metal, for example, a thin layer or foil of copper, aluminum, silver, or the like, an electrically insulating plate, for example, a substrate obtained by laminating an upper or lower surface of a plastic plate or a film, or a further electrically insulating plate Or a hole formed through a through hole, that is, an inner wall surface of a through-hole, or a thin metal film provided on an electrically insulating plate by vapor deposition or plating.

Examples of the solvent for forming the coating liquid include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and n-hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.
Ketones such as diisobutyl ketone, esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate, and ethyl benzoate; and aromatic carbons such as toluene, xylene, benzene, and ethylbenzene. Hydrogens, carbon tetrachloride, trichloroethylene, chloroform, halogenated hydrocarbons such as 1,1,1-trichloroethane, methylene chloride, monochlorobenzene, etc., tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1 Ethers such as -methoxy-2-propanol, dimethylformamide,
And dimethyl sulfoxide.

The material used as a support when used as an image forming material needs to have good light transmittance and a uniform surface. Specifically, polyethylene terephthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, alkyl poly (meth) acrylate, poly (meth) acrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene , Cellophane, polyvinylidene chloride copolymer, polyamide, polyimide,
Various plastic films such as a vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene can be used. Furthermore, a composite material composed of two or more of these can also be used. This support generally has a thickness of 5 to 150 μm, preferably 10 to 50 μm.
μm is used, but other ranges can be used. The thickness of the layer of the photopolymerizable composition provided on the support is provided so as to perform a desired function of an image finally formed, but is generally 5
１００100 μm, preferably 10-80 μm
m. Further, if necessary, a protective film can be provided on the photopolymerizable composition layer. Such a protective film can be appropriately selected from those used for the support and paper, for example, paper on which polyethylene, polypropylene or the like is laminated. The thickness is generally 5 to 100 μm and 10 to 50 μm.
m is more preferred. At this time, the adhesion A between the photopolymerizable composition and the support and the adhesion B between the photopolymerizable composition layer and the protective film B
Need to satisfy the relationship of A> B. Specific examples of the combination of the support and the protective film include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyamide (nylon 6) / polyethylene, polyvinyl chloride / cellophane, and polyimide / polypropylene.

In addition to the above-described method of selecting the support and the protective film from mutually different materials, at least one of the support and the protective film is subjected to a surface treatment so that the above-described relationship of the adhesive force is obtained. Can be satisfied.
The surface treatment of the support is generally performed in order to increase the adhesive force with the photopolymerizable composition layer, for example, coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, There are a high frequency irradiation treatment, a glow discharge irradiation treatment, an active plasma irradiation treatment, a laser beam irradiation treatment and the like. Further, the surface treatment of the protective film, contrary to the surface treatment of the support,
It is generally applied to reduce the adhesive strength with the photopolymerizable composition layer. For example, there is a method in which a polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or the like is provided as an undercoat layer. Drying after application is generally 3
It is preferable to carry out at 0 ° C to 150 ° C, particularly at 50 ° C to 120 ° C for 1 to 30 minutes. When the image forming material has a protective film, the protective film is peeled off to expose the surface of the photopolymerizable composition layer, and the photopolymerizable composition layer is laminated on the surface of a desired cleaned printed wiring board by pressing. The lamination of the photopolymerizable composition layer on the printed wiring board can be performed at room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.).
It is preferably performed at 0 ° C.

The printed wiring board can be prepared according to a known method. That is, after applying a photoresist or an image forming material containing the photopolymerizable composition of the present invention on a substrate as described above to form a photopolymerized layer, the photopolymerized layer is exposed to a circuit pattern through a mask, or A latent image of a circuit pattern is formed by scanning with a laser beam. The light source is an electromagnetic wave that is active with respect to the photopolymerization initiation system, and can further transmit through a transparent support when used as an image forming material. Specifically, a light source having a wavelength in the visible or ultraviolet to visible range, that is, a wavelength of 310 to
A light source that emits ultraviolet-visible light in the range of 700 nm, more preferably 350-500 nm, is used. For example, argon laser light, FD-YAG laser light, helium-
Although neon laser light is preferable because it can directly draw, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a fluorescent tube for copying, or the like can also be used. After imagewise exposure, the unexposed portions are eluted with a suitable developing solution, for example, an organic solvent, an alkaline aqueous solution containing an organic solvent, or an alkaline aqueous solution to obtain a photocured image on a printed wiring board.

After image formation, the exposed metal was etched using a known etching solution such as an aqueous solution of copper chloride or ferric chloride, or exposed using a known plating solution such as copper pyrophosphate or copper sulfate. Can be plated on metal. The photopolymerizable layer of the present invention not only has high sensitivity to visible light but also has excellent film properties, and particularly has high elasticity of the film, and therefore has high resistance to an acidic etching solution. Therefore, unlike the conventional case, the photo-cured portion is not eluted in the etching step and the metal circuit pattern thereunder is not lost, so that the circuit pattern can be accurately formed as designed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Incidentally, “parts” means “parts by weight” unless otherwise specified.

(Examples 1 to 20, Comparative Examples 1 to 5) The following materials were mixed to prepare a uniform solution (hereinafter referred to as a mother liquor). 42.9 parts of methyl methacrylate / methacrylic acid / 2-ethylhexyl 35% by weight solution of a methacrylate / benzyl methacrylate copolymer (molar ratio 55 / 28.8 / 11.7 / 4.5, weight average molecular weight 90,000) ( Solvent: methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (weight ratio) polypropylene glycol diacrylate (average molecular weight: 822) 6.5 parts tetraethylene glycol dimethacrylate 1.5 parts p-toluenesulfonamide 0.5 Part Malachite green oxalate (1% methanol solution) 1.625 parts 3-morpholinomethyl-1-phenyltriazole-2-thione 0.01 part Phenyltribromomethylsulfone 0.05 part Leuco crystal violet 0.20 part

The sensitizing dye and the radical polymerization initiator in the amounts shown in Examples 1 to 20 of Table A were added to the above mother liquor. After further stirring and dissolving, each coating solution was applied to a 23 μm polyethylene terephthalate temporary support, and
After drying at a temperature of 2 ° C. for 2 minutes, an image forming material having a photosensitive coating film having a thickness of about 30 μm was obtained. This image forming material was laminated on a cleaned copper-clad laminate (substrate) at 105 ° C., and the following pattern was drawn by laser scanning at various exposures with an argon laser. Pattern A: line width / space width (L / S) = 1 /
1. Line width = 30 μm to 100 μm (five lines of each width are present) Pattern B: L / S = 1/3, the same as pattern A. In order to further evaluate the sensitivity, the density step is 0.15. Was placed on the sample and exposed from above with a laser beam having a light intensity of 10 mJ / cm ² so as to form a solid image. 15 minutes after the exposure, spray development (spray pressure 2) with a 1% aqueous solution of sodium carbonate (30 ° C.) for 40 seconds
kg / cm ² ) and then washed with water at 20 ° C. for 40 seconds. The resist patterns A and B thus obtained were observed with an optical microscope. The evaluation was performed as follows.

<Highest resolution> First, 4 mJ / c for pattern A
observing the pattern obtained by exposing m ^2, and the peeled off five lines were thinnest line width which is not or remain developed no portions (resolution) recorded. Then 2
Exposure was performed while increasing the exposure amount at intervals of mJ / cm ² , and the resolution of each sample was recorded in the same manner. Generally, in a low exposure amount region, an image having a small line width cannot be obtained because the resist pattern is easily peeled. Conversely, in a high exposure area, clogging is likely to occur between lines, and the tendency is larger for a line having a smaller line width, and the resolution has a minimum value. Here, among the resolutions of the respective exposure amounts obtained by the above-described method, the smallest value is set as the highest resolution.

<Sensitivity> The number of clear steps in the step guide pattern obtained by the above exposure was defined as sensitivity. That is, the greater the number of stages, the higher the sensitivity.

<Tent film strength> After laminating a photosensitive coating film on both sides of a substrate having a through-hole (2000 holes) of 6 mmφ, the entire surface was exposed with a laser at the exposure amount obtained with the highest resolution, and the above-described method was performed. The film was developed under the conditions to form a tent film. To this was sprayed an aqueous solution of copper chloride (35 ° B
e, 45 ° C., 2.5 kg / cm ² , 4 minutes) and then sprayed with water (18 ° C., 2 kg / cm ² , 3 minutes). Repeat this operation for 2 more
After repeating the number of times, the percentage of torn tent membrane was recorded. The results are shown in Table A. As is clear from the above, it was confirmed that the photopolymerized layer of the present invention exhibited high sensitivity to argon laser light, and had excellent resolution and tent film strength.

[0182]

[Table 6]

[0183]

As described above, the photopolymerizable layer of the present invention has a high sensitivity to visible light, a high resolving power, and gives excellent film properties. Therefore, when producing a printed wiring board, the photo-cured portion is not eluted by the etchant as in the conventional case, and the metal circuit pattern thereunder does not disappear, and the circuit pattern is accurately formed as designed. Can be.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI H05K 3/06 H05K 3/06 H

Claims (1)

[Claims] 1. A base comprising a conductive thin film provided on an electrically insulating plate.
On the board, a thermoplastic polymer binder, ethylenically unsaturated compound
, At least one sensitizing dye selected from the following group A
And a photopolymerization layer containing a radical polymerization initiator.
And a printed wiring board. Group A: a compound represented by the following general formula (I):(However, R in the formula¹~ R^FourAre independently a hydrogen atom,
Halogen atom, alkyl group, substituted alkyl group, aryl
Group, substituted aryl group, hydroxyl group, alkoxy group, substituted
Represents a xy group, an amino group, or a substituted amino group. Also R¹~
R^FourIs a non-metallic atom together with the carbon atom to which it is attached.
May form a ring. R^Five, R⁶Are independent of each other
Hydrogen, halogen, alkyl, substituted alkyl
Group, aryl group, substituted aryl group, heteroaromatic group,
Sil group, cyano group, alkoxycarbonyl group, carboxy
Represents a sil group or a substituted alkenyl group. Also R^FiveAnd R⁶Is
May form a ring composed of a non-metallic atom. X is
O, S, NH, or a nitrogen atom having a substituent.
G¹, G^TwoMay be the same or different from each other.
Hydrogen atom, cyano group, alkoxycarbonyl group,
Alkoxycarbonyl group, aryloxycarbonyl group,
Substituted aryloxycarbonyl group, acyl group, substituted acyl
Group, arylcarbonyl group, substituted arylcarbonyl
Group, alkylthio group, arylthio group, alkylsulfo
Nil group, arylsulfonyl group, fluorosulfonyl group
Represents Where G¹And G^TwoIs the carbon atom to which it is attached
May form a ring composed of a non-metallic atom together. ) A compound represented by the following general formula (II):(However, R in the formula⁷, R⁸May be the same or different
Hydrogen, alkyl, substituted alkyl, alkenyl
Group, substituted alkenyl group, alkoxycarbonyl group,
Reel, substituted aryl, alkynyl or substituted
Represents a rukinyl group. A is an oxygen atom, a sulfur atom, an alkyl
A carbon atom substituted by a group or an aryl group, or
Represents a carbon atom substituted by two alkyl groups. J is nitrogen-containing
Non-metallic atoms necessary to form a 5-membered heterocyclic ring
You. Y is a phenyl group, a substituted phenyl group, unsubstituted or substituted
Represents a substituted heteroaromatic ring. Z¹Is a hydrogen atom, al
Kill group, substituted alkyl group, aryl group, substituted aryl
Group, alkoxy group, alkylthio group, arylthio group,
Substituted amino group, acyl group, or alkoxycarbonyl
Z represents a group¹And Y may combine with each other to form a ring
No. ) A compound represented by the following general formula (III):(However, R in the formula^Ten~ R¹³Are independently a hydrogen atom,
An unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, carbon number
1-6 unsubstituted or substituted alkenyloxy groups, carbon number
1-6 unsubstituted or substituted alkylthio groups, each alkyl
Dialkylamino group having 1 to 4 carbon atoms, hydroxyl
Group, acyloxy group, halogen atom, nitro group, or
Represents a multiple ring group. R^Ten~ R¹³Two or three of the above and R
^Ten~ R¹³And the ring-constituting carbon atom to which the substituent of
A fused ring wherein each fused ring is a 5- or 6-membered ring
May form a fused ring system. R⁹Is hydrogen atom, carbon number
1-4 unsubstituted or substituted alkyl groups or 6-carbon atoms
12 unsubstituted or substituted aryl groups, or R¹⁴-CO
Represents-. Where R ¹⁴Is an alkoxy group, cycloalkoxy
Xy, hydroxyl, aryloxy, alkenyloxy
Group, aralkyloxy group, alkoxycarbonyl alcohol
A xy group, an alkylcarbonylalkoxy group, or
Represents a substituent represented by any of the following (III-a) to (III-c). Embedded imageR^Fifteen~ R¹⁸Is a hydrogen atom, an alkyl group, a hydroxyalkyl
Group, hydroxyalkoxyalkyl group, alkoxyl
Represents an alkyl group or a cycloalkyl group, and m is 1 to 5.
And n is 0 to 10. Q¹Is a cyano group, a heterocyclic ring,
Or -Z^Two-R¹⁹Represents Where R¹⁹Has 1 to 10 carbon atoms
An unsubstituted or substituted alkyl group, alkenyl group, or
Alkoxy group, unsubstituted or substituted ant having 6 to 12 carbon atoms
Unsubstituted or substituted aryloxy having 6 to 12 carbon atoms
5 carbon atoms and hetero atoms constituting the xy group or the ring
Up to 15 unsubstituted or substituted heterocyclic groups, or hydroxyl
Represents an acyl group. Z^TwoIs carbonyl group, sulfonyl
Group, sulfinyl group or arylenedicarbonyl group,
-(CH = CH)_k(K is 1 or 2). )