JP2003140334A - Photopolymerizable image forming material and image forming method - Google Patents

Abstract

(57) [Abstract] [Purpose] In addition to suppressing the effect of polymerization inhibition by oxygen in the photopolymerizable composition layer, it has excellent resolution and excellent safelight properties, and can be handled in a bright room. A novel photopolymerizable image forming material and an image forming method are provided. The present invention relates to a photopolymerizable image-forming material having a photopolymerizable composition layer on a substrate, and the exposure energy [S ₁ required for a residual film ratio of an exposed portion to become 50% when subjected to image exposure and development processing. (MJ / cm ² )], forming a 0.5 to 2 μm-thick polyvinyl alcohol layer on the photopolymerizable composition layer, exposing the image under the same conditions, removing the polyvinyl alcohol layer, and developing. A photopolymerizable image forming material having a ratio [S ₁ / S ₂ ] of exposure energy [S ₂ (mJ / cm ² )] required for the residual film ratio of the exposed portion to become 50% in the range of 1 to 5 And an image forming method comprising subjecting the photopolymerizable composition layer of the photopolymerizable image forming material to scanning exposure with near-infrared laser light having a wavelength range of 750 to 1200 nm, followed by development processing with an alkali developing solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable image forming material which suppresses the influence of polymerization inhibition by oxygen in a photopolymerizable composition layer, and an image forming method, a printed wiring board, a liquid crystal display device, and a plasma display. , A color filter, organic electroluminescence, useful for forming a conductor circuit or an electrode substrate in a thin transistor, etc., in particular, a photopolymerizable image forming material suitable for direct drawing by near-infrared laser light using a semiconductor laser or the like, And an image forming method.

[0002]

2. Description of the Related Art Conventionally, for example, in the formation of a conductor circuit in a printed wiring board or the like, a liquid resist material or a dry film resist material has been used as a resist material composed of a photosensitive composition. On the substrate such as the stretched surface,
A copper clad laminate having a photosensitive resist material layer formed by applying a liquid resist material and drying it, or peeling and laminating a dry film resist material covering film sandwiched between a supporting film and a covering film. Is exposed through a mask film on which a circuit pattern is drawn, the mask film is peeled off, and a developing process is performed to form a resist image corresponding to the circuit pattern. A method of forming a circuit pattern drawn on a mask film on a substrate by removing the resist material after removing the copper-clad portion that is not present.

Among the above resist materials, the dry film resist material is easy to form a layer on the substrate, but it is imagewise exposed through the supporting film, and the resist material layer has a thickness of 20 to 70 μm. The liquid resist material is attracting attention because it can obtain high resolution, while it has a drawback that it is difficult to obtain high resolution because it is thick. However, in the case of a liquid resist material, if the photosensitive composition constituting the resist material layer is a photopolymerizable composition,
When the film thickness of the resist material layer is made thin, there is a drawback that the sensitivity is remarkably affected by polymerization inhibition by oxygen and the sensitivity is reduced to several tens to several hundreds. Although a method of substituting a gas or an inert gas such as argon gas and a method of providing an oxygen blocking layer on the resist material layer are known, both methods are economical in view of an increase in the number of devices or steps. In addition, it was inevitable to work disadvantages.

On the other hand, due to the recent trend of improving the functions of electronic equipment and making lighter, thinner, shorter, smaller, etc., higher circuit density is required,
In response to this, it is required to improve the resolution of the resist material, but by using laser light, a method of drawing directly based on digital information of a computer without using a mask film is a high-resolution circuit. It is attracting attention as a method that can be formed. However, under the present circumstances, the sensitivity and resolution of the photosensitive composition as a resist material have not yet been satisfied in the exposure with a laser beam.

On the other hand, for example, Japanese Patent Laid-Open No. 2000-1
47767 discloses a carboxyl group-containing unsaturated resin obtained by reacting a polymer of an epoxy group-containing ethylenically unsaturated monomer with a specific amount of an ethylenically unsaturated monocarboxylic acid, an ethylenically unsaturated compound, and photopolymerization initiation. It is disclosed that by using a photopolymerizable composition containing an agent, high sensitivity can be obtained without providing an oxygen barrier layer, and direct writing with a laser beam is possible, but high sensitivity is pursued. Therefore, it exhibits reactivity to light in a wavelength region other than the exposure wavelength, and has a drawback that it can be handled only in a working environment such as a dark room.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art. Therefore, the present invention suppresses the influence of oxygen-induced polymerization inhibition in the photopolymerizable composition layer. It is an object of the present invention to provide a photopolymerizable image forming material which is excellent in resolution and safelight and can be handled in a bright room, and an image forming method.

[0007]

The present invention is a photopolymerizable image forming material having a layer of a photopolymerizable composition on a substrate,
Exposure energy [S ₁ (mJ / cm ² )] required for the residual film ratio of the exposed portion to be 50% when imagewise exposed and developed
And a polyvinyl alcohol layer having a film thickness of 0.5 to 2 μm is formed on the photopolymerizable composition layer, imagewise exposed under the same conditions, the polyvinyl alcohol layer is removed, and a development treatment is carried out. The ratio [S ₁ / S ₂ ] of the exposure energy [S ₂ (mJ / cm ² )] required for the ratio to reach 50% is 1 to 5
The photopolymerizable image forming material in the range of, and the photopolymerizable composition layer of the photopolymerizable image forming material is subjected to scanning exposure with a near-infrared laser beam in the wavelength range of 750 to 1200 nm, and then with an alkali developing solution. The gist is an image forming method of developing.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable image forming material of the present invention comprises
Photopolymerizable imaging having a layer of photopolymerizable composition on a substrate
Material, the residual film in the exposed area when imagewise exposed and developed
Exposure energy [S₁(MJ
/ Cm²)] And a film thickness of 0.5 on the photopolymerizable composition layer.
~ 2μ polyvinyl alcohol layer is formed under the same conditions
Imagewise exposure to remove the polyvinyl alcohol layer and develop
Dew required to reach a residual film ratio of 50% in the exposed area when processed
Light energy [S₂(MJ / cm²)] Ratio [S₁/ S
₂] Is in the range of 1 to 5, and the ratio [S₁/
S₂] Is preferably 1 to 3, and is 1 to 2.
More preferable. This exposure energy ratio [S₁/ S ₂〕But
If the above range is exceeded, it is difficult to achieve the object of the present invention.
Becomes

Here, the exposure energy ratio [S ₁
/ S ₂ ] is satisfied, it is basically necessary that the photopolymerizable composition constituting the photopolymerizable composition layer is sufficient to satisfy the ratio. It should also be taken into consideration that the optimum conditions for satisfying the ratio are adopted as conditions for forming the polyvinyl alcohol layer, and image exposure and development.

Regarding the polyvinyl alcohol layer,
Using polyvinyl alcohol used as the oxygen barrier layer of this type photopolymerizable image-forming material, as a solution of water or a mixed solvent of water and a water-miscible organic solvent such as tetrahydrofuran, the photopolymerization described below. It is formed by the same coating method as in the formation of the volatile composition layer, and its coating amount is 0.5 to 2 μm as a dry film thickness. Regarding the conditions such as image exposure and development processing, the conditions described later as the conditions such as image exposure and development processing of the photopolymerizable image forming material of the present invention are adopted, and the details thereof will be described later.

The composition of the photopolymerizable composition constituting the photopolymerizable composition layer of the photopolymerizable image forming material of the present invention is not particularly limited as long as the above-mentioned exposure energy ratio [S ₁ / S ₂ ] is satisfied. Although not a thing, the following (A) component, (B) component,
A photopolymerizable composition containing the component (C) and the component (D) is preferable. (A) Alkali-soluble resin (B) Ethylenically unsaturated compound (C) Sensitizing dye (D) Photopolymerization initiator

Here, the alkali-soluble resin as the component (A) is used as a binder for each component after the component (B) described later for the purpose of improving the coating property and the developability of the photopolymerizable composition. Suitable examples of the alkali-soluble resin include a carboxyl group-containing vinyl resin and an epoxycarboxylate resin.

Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid [here,
Here, "(meth) acrylic" means "acrylic" and / or "methacrylic". ], 2-succinyloxyethyl (meth) acrylate, (meth)
2-Maleoyloxyethyl acrylate, 2-phthaloyloxyethyl (meth) acrylate, 2-hexahydrophthaloyloxyethyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. And unsaturated carboxylic acid homopolymers thereof with styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate,
Hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid chloride, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile , (Meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide,
Examples thereof include copolymers with vinyl compounds such as N, N-dimethylaminoethyl (meth) acrylamide, allyl glycidyl ether, crotonic acid glycidyl ether, and vinyl acetate.

Further, as the carboxyl group-containing vinyl resin, a resin having an ethylenically unsaturated bond in a side chain is preferable. Specifically, for example, a carboxyl group-containing polymer is added to allyl glycidyl ether, glycidyl ( (Meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester An aliphatic epoxy group-containing unsaturated compound such as, or an alicyclic epoxy group-containing unsaturated compound such as 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. 90 mol%, preferably 30 to 70
The reaction product obtained by reacting about mol%, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) ) Acrylate, compounds having two or more kinds of unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate , 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide and other compounds having two or more unsaturated groups, and (meth) acrylic acid and other unsaturated carboxylic acids, or further unsaturated carboxylic acids The ester is a proportion of the former compound having an unsaturated group. 10 to 90 mol%, preferably and the like reaction product obtained by copolymerizing such that about 30 to 80 mol%.

The epoxy carboxylate resin is a resin obtained by modifying an epoxy resin with an unsaturated carboxylic acid and an acid anhydride. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, The epoxy groups of epoxy resins such as bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and trisphenol epoxy resin have (meth) acrylic acid, 2-succinyloxyethyl (meth) acrylate, and (meth) acrylic acid. Two
-Unsaturation of maleoyloxyethyl, 2-phthaloyloxyethyl (meth) acrylate, 2-hexahydrophthaloyloxyethyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. Unsaturated carboxylic acid-added epoxy resin obtained by ring-opening addition of carboxylic acid, succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride , An acid anhydride modified product modified with an acid anhydride such as methylendomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

These alkali-soluble resins have an acid value of 2
It is preferably 0 to 200 mg · KOH / g, 30
More preferably, it is about 180 mg · KOH / g.
The weight average molecular weight by gel permeation chromatography is preferably 2,000 to 200,000, more preferably 3,000 to 150,000.

Among the above alkali-soluble resins, in the present invention, epoxycarboxylate-based resins are preferable, from the viewpoints of sensitivity as a photopolymerizable composition, resolution, adhesion to a substrate, and the like. Epoxy group 1
An unsaturated carboxylic acid is preferably added in an amount of 0.8 to 1.2 equivalents per equivalent so that one monomer unit has one or more unsaturated groups. Further, a phenol novolac epoxy resin or a cresol novolac epoxy resin is used as the epoxy resin, (meth) acrylic acid is added as the unsaturated carboxylic acid, and further, an epoxycarboxylate modified with tetrahydrophthalic anhydride or hexahydrophthalic anhydride. Resins are particularly preferable.

Further, the ethylenically unsaturated compound as the component (B) is used when the photopolymerizable composition is exposed to actinic rays.
At least one radically polymerizable ethylenically unsaturated double bond capable of undergoing addition polymerization by the action of the photopolymerization initiation system of the component (C) and the component (D) described later, and optionally crosslinking and curing, in the molecule. In addition to the monomer, it also includes a dimer, a trimer, and other oligomers.

The ethylenically unsaturated compound in the present invention is a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, Unsaturated carboxylic acids such as citraconic acid, and their alkyl esters, (meth)
It may be acrylonitrile, (meth) acrylamide, styrene, etc., but it is not ethylenic because it can expand the difference in polymerizability, crosslinkability, and solubility of developer between exposed and unexposed areas. A compound having two or more saturated bonds in the molecule is preferable, and an acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferable.

As the compound having two or more ethylenically unsaturated bonds in the molecule, typically, an ester of an unsaturated carboxylic acid and a polyhydroxy compound, a hydroxy (meth) acrylate compound and a polyisocyanate compound are used. Urethane (meth) acrylates, epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound, (meth) acrylamides of (meth) acrylic acid and polyamine compound, and Examples thereof include (meth) acryloyloxy group-containing phosphates.

Specific examples of the esters include unsaturated carboxylic acids such as those mentioned above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol and tetra. Methylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane,
Trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, reaction products with aliphatic polyhydroxy compounds such as triethanolamine, specifically, For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth ) Acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Propane ethylene oxide-added tri (meth) acrylate, trimethylol propane propylene oxide-added tri (meth) acrylate, glycero Rudi (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide-added tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol Tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

Further, as the ester thereof, a reaction product of the above-mentioned unsaturated carboxylic acid and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, specifically, for example, hydroquinone Di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth)
Acrylate, etc., and an unsaturated carboxylic acid as described above,
A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate. Acrylate and the like, or a reaction product of an unsaturated carboxylic acid, a polycarboxylic acid and a polyhydroxy compound, specifically, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) acrylic Examples thereof include a condensate of an acid, maleic acid and diethylene glycol, a condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, a condensate of (meth) acrylic acid, adipic acid, butanediol and glycerin.

Specific examples of the urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate. Hydroxy (meth) acrylate compounds such as tetramethylolethane tri (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1 , 6,11-Undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane Aliphatic polyisocyanates, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, alicyclic polyisocyanates such as bicycloheptane triisocyanate, p- phenylene diisocyanate,
2,4-Tolylene diisocyanate, 2,6-Tolylene diisocyanate, Xylylene diisocyanate, Tetramethyl xylylene diisocyanate, 4,4'-Diphenylmethane diisocyanate, Tolidine diisocyanate, 1,5-Naphthalene diisocyanate, Tris (isocyanatophenylmethane) And aromatic polyisocyanates such as tris (isocyanatophenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, and reaction products with polyisocyanate compounds.

Specific examples of the epoxy (meth) acrylates include (meth) acrylic acid,
Alternatively, a hydroxy (meth) acrylate compound as described above and (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, Aliphatic poly, such as (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Epoxy compound, "Celoxide 2000" manufactured by Daicel Chemical Co., Ltd., "20
21 "," Same 2080 "," Same 3000 "," Eporide GT300 "," Same GT400 "and other alicyclic polyepoxy compounds, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m -, P-) cresol novolac polyepoxy compound, bisphenol A polyepoxy compound,
Aromatic polyepoxy compound such as bisphenol F polyepoxy compound, sorbitan polyglycidyl ether, heteroglyceride polyepoxy compound such as triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like, and polyepoxy compound such as Reaction products and the like can be mentioned.

As the (meth) acrylamides, specifically, for example, a reaction product of (meth) acrylic acid and an aliphatic polyamine compound such as methylenediamine, ethylenediamine, diethylenetriamine and hexamethylenediamine, Specifically, for example, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, hexamethylenebis (meth) acrylamide, etc.
Further, a reaction product of (meth) acrylic acid and an aromatic polyamine compound such as xylylenediamine, specifically, for example, xylylenebis (meth) acrylamide and the like can be mentioned.

The (meth) acryloyloxy group-containing phosphates include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate,
(Meth) acryloyloxyethylene glycol phosphate and the like can be mentioned.

Among the above ethylenically unsaturated compounds, in the present invention, a reaction product of an unsaturated carboxylic acid and an aliphatic polyhydroxy compound is used in view of sensitivity, resolution and the like as a photopolymerizable composition. And the ester having 3 or more (meth) acryloyloxy groups in the molecule is preferable, and particularly, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethyl Methylolpropane tri [(meth) acryloyloxypropyl] ether, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol pen (Meth) acrylate, dipentaerythritol hexa (meth) acrylate are preferable.

Further, the sensitizing dye of the component (C) efficiently absorbs the light when the photopolymerizable composition is irradiated with an actinic ray, and the photoexcitation energy of the sensitizing dye of the component (D) described later. A compound having a sensitizing function of transmitting to a photopolymerization initiator to decompose the component (D) and generate an active radical that induces the polymerization of the ethylenically unsaturated compound of the component (B). In the present invention, , A light absorbing dye having an absorption maximum in the wavelength range of 750 to 1200 nm is preferable.

Examples of the light-absorbing dyes include "chemistry of functional dyes" (edited by Higaki, 1981, published by CMC), "special function dyes" (edited by Ikemori and Hitotani, 1
986, published by CMC), "Dye Handbook" (edited by Taiga / Hirashima / Matsuoka / Kitao, published by Kodansha),
Exciton Inc. , 750 to 120 described in the catalog of laser dyes issued by Japan Photosensitized Dye Research Institute in 1995, etc.
Dyes having an absorption maximum in the wavelength region of 0 nm, and JP-A Nos. 2-2074, 2-2075, and 2-2076.
No. 3, No. 3-26593, No. 3-63285, No. 3-
97589, 3-97590, 3-97591.
Examples thereof include dyes having absorption in the infrared region described in each of the publications such as No.

As the light absorbing dyes, specifically,
For example, a structure in which hetero atoms such as a nitrogen atom, an oxygen atom, or a sulfur atom are bound by a polymethine (-CH =) _n chain, and the hetero atom forms a hetero ring, and the hetero ring is formed through the polymethine chain. Quinoline-based (so-called,
Cyanine type), indole type (so-called indocyanine type), benzothiazole type (so-called thiocyanine type),
Pyrylium series, thiapyrylium series, squarylium series,
Croconium dyes, azurenium dyes in a broad sense, so-called cyanine dyes, and so-called polymethine dyes having a structure in which an acyclic heteroatom is bonded via a polymethine chain, and merocyanine dyes, naphtholactam dyes, pentacene dyes , Oxyindolizine dye, quinoid dye,
Aminium dyes, diimmonium dyes, indoaniline dyes, anthraquinone dyes, nickel-thio complex dyes, phthalocyanine dyes, naphthalocyanine dyes, and the like, among which, cyanine dyes, polymethine dyes, and phthalocyanines Dyes and naphthalocyanine dyes are preferable, and phthalocyanine dyes are particularly preferable.

The phthalocyanine dye is preferably a phthalocyanine dye of a phthalocyanine complex salt having a structure represented by the following general formula (I).

[0032]

[Chemical 1]

[In the formula (I), M represents a central metal forming a phthalocyanine complex salt, the benzene ring may have a substituent, and the substituents are linked to each other to form a condensed ring. In that case, the fused ring may further have a substituent. ]

Here, M in the formula (I) is, for example, Ia group, Ib group, IIa group, IIb group, IIIa group of the periodic table,
IIIb, IVa, IVb, Va, Vb, VIb, VIIb
Group, various metal atoms of group VIII, and the like, and as the substituent of the benzene ring and the condensed ring, for example, an alkyl group having about 1 to 10 carbon atoms which may further have a substituent,
Similarly, an alkoxy group having about 1 to 15 carbon atoms, a carboxyl group, a vinyl group, an acryloyl group,
Examples include phenyl group, phenoxy group, alkylthio group, phenylthio group, amino group, silyl group, hydroxyl group, nitro group, cyano group, halogen atom, etc. It may be the same or different.

Examples of such phthalocyanine dyes include those disclosed in JP-A-64-60660 and JP-A-1.
-100171, JP-A-3-31247,
JP-A-4-15263, JP-A-4-15264, JP-A-4-15265, and JP-A-4-152
Phthalocyanine compounds described in Japanese Patent No. 66, JP-A-2-
Alkyl phthalocyanine compounds described in JP-A-138382, JP-A-3-77840 and JP-A-3-100
Acyloxy phthalocyanine compound described in JP-A No. 066, 1994, alkoxy phthalocyanine compound described in JP-A-4-348168, JP-A-60-23451, JP-A-61-215662, and JP-A-61-2.
15663, JP-A-63-270765,
JP-A-1-287175, JP-A-2-43269
Japanese Patent Laid-Open No. 2-2968685, Japanese Patent Laid-Open No. 3-4
3461, JP-A-3-265664, JP-A-3-265665, naphthalocyanine compounds, JP-A-1-108264, JP-A-1-10
Examples thereof include the dinaphthalocyanine compound described in Japanese Patent No. 8265.

Among the above, in the present invention, M represented by the general formula (I) is Ib group such as copper, IIb group such as zinc, IIIb group such as aluminum, IVb group such as tin, and vanadium. Etc.
A complex salt having a Va group metal atom as a central metal and having the same substituent on each of four benzene rings or four naphthalene rings as condensed rings is preferable, and preferable phthalocyanine dyes thereof. Is the absorption maximum (λ _max )
And the molar extinction coefficient (ε) at the absorption maximum (λ _max ) will be specifically exemplified below. In the following examples, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0037]

[Chemical 2]

[0038]

[Chemical 3]

[0039]

[Chemical 4]

[0040]

[Chemical 5]

[0041]

[Chemical 6]

[0042]

[Chemical 7]

[0043]

[Chemical 8]

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

[0047]

[Chemical 12]

Further, the photopolymerization initiator of the component (D), when irradiated with light in the presence of the sensitizing dye of the component (C),
A radical generator that generates an active radical that induces the polymerization of the ethylenically unsaturated compound as the component (B),
Examples thereof include halogenated hydrocarbon derivatives, hexaarylbiimidazole compounds, titanocene compounds, organic boron complexes, carbonyl compounds, and organic peroxides.

Examples of the halogenated hydrocarbon derivatives include, for example, JP-A No. 53-133428, British Patent No. 1388492, Wakabayashi et al .; Bull. Chem. Soc. Jap.
an; 42, 2924 (1969), FC Schaefer et al .; J. Org. Chem .; 29, 15
27 (1964) and the like, specifically, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl), for example, -S-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'.
-Dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p -Methoxyphenyl) -2,4-
Butadienyl] -4,6-bis (trichloromethyl)-
s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-s-triazine, 2- (p-i-propyloxystyryl) ) -4,6-Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4-
(2-Ethoxyethyl) naphthyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Acenaphthyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s- Triazine, 2-methoxy-4-methyl-6-trichloromethyl-s-triazine, 2,4,6
-Tris (tribromomethyl) -s-triazine, 2-
Methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, 2-amino-4-methyl-6-
Examples thereof include tribromomethyl-s-triazine, and among them, a bis (trichloromethyl) -s-triazine compound is preferable.

The hexaarylbiimidazole compounds are, for example, the compounds described in Japanese Patent Publication No. 6-29285, specifically 2,2 '.
-Bis (o-chlorophenyl) -4,4 ', 5,5'-
Tetraphenyl biimidazole, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetra (p-
Chlorophenyl) biimidazole, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (o, p-dibromophenyl)
Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-Tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o
-Bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) ) Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-
Bromophenyl) -4,4 ', 5,5'-tetra (o-
Chloro-p-methoxyphenyl) biimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenyl biimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, etc. are mentioned.

Examples of the titanocene compounds are, for example, JP-A-59-152396 and JP-A-61-15.
1197, JP-A-63-41484, JP-A-2-2
49, JP-A-2-4705, JP-A-5-83588.
Compounds described in each publication, specifically, for example,
Dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), dicyclopentadienyl titanium bis (2,6-difluorophenyl), di Cyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,2
3,5,6-Tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluoro) Phenyl),
Di (methylcyclopentadienyl) titanium bis (2,4,6-trifluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,5,6)
-Tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis [2,6-difluoro-3- (1 -Pyrrolyl)
Phenyl] and the like.

Examples of the organic boron complexes are, for example, JP-A-8-21713 and JP-A-9-10624.
No. 2, JP-A-9-188685 and JP-A-9-1886.
No. 86, Japanese Patent Laid-Open No. 9-188710, and Kun.
z, Martin ”Rad Tech'98.Proceeding April 19-22,199
8, Chicago "and the like, organoboron ammonium complexes, JP-A-6-1576232 and JP-A-6-175561.
And organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-175564, JP-A-6-175553 and JP-A-6-1755.
54, organic boron iodonium complexes described in JP-A-9-188710, etc., organic boron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, and JP-A7-1.
28785, JP-A-7-140589, JP-A-7-
Examples thereof include organic boron transition metal coordination complexes described in JP-A-292014 and JP-A-7-306527.

Specific examples of the carbonyl compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone. , Benzophenone derivatives such as Michler's ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy -1-Methylethyl- (p
-Isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-
2-methylphenylpropanone, 2-methyl- (4'-
Acetophenone derivatives such as (methylthio) phenyl) -2-morpholino-1-propanone, thioxanthone, 2
-Thioxanthone derivatives such as ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone, ethyl p-dimethylaminobenzoate, p-diethylamino Examples thereof include benzoic acid ester derivatives such as ethyl benzoate.

Specific examples of the organic peroxides include methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide,
Ketone peroxide such as 3,3,5-trimethylcyclohexanone peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-tolu Diacyl peroxide such as oil peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -bis ( t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,
1-bis (t-butylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) -3,3,5-
Peroxyketals such as trimethylcyclohexane and 2,2-bis (t-butylperoxy) butane, t-butylperoxyacetate, t-butylperoxyoctate, t-butylperoxypivalate, t-butylperoxy Neodecanoate, t-butylperoxy-
Alkyl peresters such as 3,5,5-trimethylhexanoate, t-butylperoxylaurate and t-butylperoxybenzoate, di-2-ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxide Oxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl)
Peroxydicarbonates, peroxycarbonates such as t-butylperoxyisopropylcarbonate, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ −
Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4
4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, 3,
Examples thereof include 3 ', 4,4'-tetra (aminoperoxycarbonyl) benzophenone, carbonylbis (t-butylperoxydihydrogen 2 phthalate), carbonylbis (t-hexylperoxy dihydrogen 2 phthalate) and the like.

In the present invention, as the photopolymerization initiator of the component (D), s-triazine compounds as halogenated hydrocarbon derivatives and organic boron complexes are preferable among the above, and particularly, the following general formula The organic boron complex represented by (II) is preferable.

[0056]

[Chemical 13]

[In Formula (II), R ¹ , R ² , R ³ , and R ⁴
Are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent which may have a substituent. A good aryl group, an alicyclic group which may have a substituent,
Or, it represents a heterocyclic group which may have a substituent, and these substituents may be linked to each other to form a cyclic structure, and X ⁺ represents a counter cation. ]

Here, R ¹ , R ² in the formula (II),
When R ³ and R ⁴ are alkyl groups or alicyclic groups, the number of carbon atoms is about 1 to 10, carbon atoms when R ³ and R ⁴ are alkenyl groups, alkynyl groups, or alicyclic groups are about 3 to 20, and aryl. When it is a group, it preferably has about 6 to 30 carbon atoms, and the aryl group is particularly preferably a phenyl group. Moreover, examples of the substituents include an alkyl group, an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, a hydroxyl group, an amino group, and a halogen atom.

In the formula, ^{three of} R ¹ , R ² , R ³ , and R ⁴ are aryl groups which may have a substituent, and one is an alkyl group which may have a substituent. Certain triarylalkylboron complexes are preferred.

Specific examples of preferable anions in these organic boron complexes include, for example, n-butyl-triphenylboron anion, n-butyl-tris (p-methylphenyl) boron anion, and n-butyl-tris (2,2).
4,6-trimethylphenyl) boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n
-Butyl-tris (m-chlorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (m-fluorophenyl)
Boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n-butyl-tris (2,4,6-trifluorophenyl) boron Anion,
n-Butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (m
-Trifluoromethylphenyl) boron anion, n-butyl-tris (3,5-di-trifluoromethylphenyl) boron anion, n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion , N-
Hexyl-tris (m-fluorophenyl) boron anion and the like can be mentioned.

The counter cation X ⁺ is, for example, an ammonium cation, a phosphonium cation, an arsonium cation, a stibonium cation, an oxonium cation, a sulfonium cation, a selenonium cation, a stannonium cation or an iodonium cation. Examples thereof include onium compounds and transition metal coordination cations. Among them, ammonium cations are preferable, and tetraalkyl (C 1-10) ammonium cations are particularly preferable.

Among the organic boron complexes represented by the above general formula (II), the organic boron complex preferred in the present invention is
Specific examples will be given below. In the following example, M
e represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

[0063]

[Chemical 14]

[0064]

[Chemical 15]

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

The photopolymerizable composition preferably used in the present invention is an alkali-soluble resin as the component (A), an ethylenically unsaturated compound as the component (B), a sensitizing dye as the component (C), and The component (D) contains a photopolymerization initiator, and the content ratio of each of the components is 100% of the component (A).
The component (B) is 5 to 70 parts by weight, the component (C) is 1 to 30 parts by weight, and the component (D) is 1 to 1 part by weight.
It is preferably 40 parts by weight, and the component (B) is 10
More preferably, the amount of the component (C) is 2 to 25 parts by weight, and the amount of the component (D) is 5 to 30 parts by weight.
When the components (B), (C), and (D) are less than the above ranges, the photopolymerizable composition tends to have insufficient sensitivity and resolution, while when the amounts exceed the above ranges, photopolymerization tends to be insufficient. As a result, problems such as impaired uniformity of the composition are likely to occur.

The photopolymerizable composition may, if necessary, have a coating property improving agent such as a nonionic, anionic, cationic, amphoteric, or fluorine-containing surfactant, a defoaming agent, a visible agent, etc. Additives such as an image imparting agent, a colorant, an adhesion improver, a developability improver, an ultraviolet absorber and a polymerization stabilizer may be added.

The photopolymerizable image-forming material of the present invention is usually prepared by dissolving or dispersing each component of the photopolymerizable composition in a suitable solvent, coating the solution on a substrate, and then heating and drying. , Is formed by forming a layer of the photopolymerizable composition on the substrate. As the image forming material, a photopolymerizable image forming material for forming a conductor circuit by forming a photopolymerizable composition as a resist material layer on the conductive layer of a substrate having a conductive layer on the surface of an insulating base material. Is preferred.

Here, examples of the insulating base material of the substrate include thermosetting resins such as epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol resin, and melamine resin, saturated polyester resin, polycarbonate resin. , Polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, fluororesin and other thermoplastic resins, paper, glass, and alumina, silica, barium sulfate, calcium carbonate, etc. Examples of the inorganic material include composite materials represented by glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin and the like. The thickness of these insulating base materials is usually about 0.02 to 10 mm.

As the constituent material of the conductive layer formed on the surface of these insulating base materials, for example, copper, gold, silver, chromium, zinc, tin, aluminum, lead, nickel, indium oxide, tin oxide, indium oxide doped. Tin oxide (ITO),
Examples of the method for forming a conductive layer on the surface of the insulating base material include a method such as heating the foil of the metal by heat-bonding, or by sputtering, vapor-depositing, or plating the metal. To be taken. The thickness of these conductive layers is usually about 1 to 100 μm.

The solvent for coating on the above-mentioned substrate is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve, Cellosolve solvent such as ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol solvent such as dipropylene glycol dimethyl ether,
Butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-
Hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, ester solvents such as methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone, methyl amyl ketone, etc. Examples thereof include ketone solvents, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, mixed solvents thereof, and further aromatic hydrocarbons added thereto. The use ratio of the solvent is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photopolymerizable composition.

As the coating method, conventionally known methods such as spin coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating and curtain coating are used. be able to. The coating amount at that time is preferably about 1 to 15 μm as a dry film thickness, and particularly preferably about 2 to 12 μm. In addition, the drying at that time, for example, using a hot air circulation type oven, a hot plate,
It is preferable that the temperature is about 40 to 120 ° C. and the time is about 10 seconds to 10 minutes.

In the present invention, the light source for imagewise exposing the photosensitive composition layer of the image forming material is carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, HeNe laser, argon. Ion laser, YA
Examples of the laser light source include G laser, HeCd laser, semiconductor laser, ruby laser, and the like.
A light source that generates a near-infrared laser beam in a wavelength range of 1200 nm, and further in a wavelength range of 750 to 900 nm is preferable, and examples thereof include a solid laser such as a ruby laser, a YAG laser, and a semiconductor laser. A long-life semiconductor laser or YAG laser is preferable.
These laser light sources are focused on a beam, and scanning exposure is performed based on image data, and then development processing is performed with an alkali developing solution to form an image.

Also, the scanning exposure method is not particularly limited, and examples thereof include a flat surface scanning exposure method, an outer surface drum scanning exposure method, and an inner surface drum scanning exposure method. Exposure intensity is preferably 1 MW / cm ² or more, more preferably 1.5 MW / cm
² or more, and the beam spot diameter is preferably 2 to 30
[mu] m, more preferably 4 to 20 [mu] m, scanning speed is preferably 50 to 500 m / sec, more preferably 100 to 4
00 m / sec, scanning density, preferably 2,000 dpi
Above, more preferably, scanning exposure is performed at 4,000 dpi or more.

Examples of the alkaline developer in the developing treatment include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium carbonate. Inorganic alkali salts such as sodium bicarbonate, potassium carbonate, sodium diphosphate, sodium triphosphate, ammonium diphosphate, ammonium triphosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, Monoethylamine, diethylamine,
Organic amine compounds such as triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and diisopropanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like 4
An aqueous solution of a graded ammonium salt or the like is used. Among them, alkali metal silicates such as inorganic silicates such as sodium silicate and potassium silicate are preferable.

The alkali concentration in the alkali developer is preferably about 0.05 to 3% by weight, more preferably about 0.1 to 2% by weight, and the pH is preferably about 8 to 13. If necessary, anionic, nonionic, amphoteric surfactants and organic solvents such as alcohols can be added to the developer.

The development treatment is carried out by immersion development, spray development, spin development, brush development, ultrasonic development or the like, preferably at a temperature of about 15 to 35 ° C. for a time of about 5 seconds to 3 minutes. After development, it is dried, and then, if necessary, for the purpose of improving the adhesiveness of the formed image.
The post-baking treatment is performed in the temperature range of about 00 to 250 ° C.

[0080]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The components (A), (B), (C), (D) and other components of the photopolymerizable compositions used in the following Examples and Comparative Examples are shown below.

<Component (A)> (A-1) An epoxy acrylate comprising the following repeating constitutional units, which is obtained by ring-opening addition of acrylic acid to the epoxy group of a phenol novolac epoxy resin and then modified with hexahydrophthalic anhydride. Resin (PC manufactured by Nippon Kayaku
R-0172 ") (A-2) An epoxy acrylate resin composed of the following repeating constitutional units, which is modified by hexahydrophthalic anhydride after ring-opening addition of acrylic acid to the epoxy group of cresol novolac epoxy resin (Showa High polymer company "P
R-300 ") (A-3) An epoxy acrylate resin composed of the following repeating constitutional units, which is obtained by ring-opening addition of acrylic acid to the epoxy group of bisphenol F epoxy resin and then modifying with hexahydrophthalic anhydride (Japan Kayaku Co., Ltd. "ZFR-
1124 ")

[0082]

[Chemical 19]

(A-4) Reaction product obtained by reacting styrene (50 mol%)-acrylic acid (50 mol%) copolymer with 3,4-epoxycyclohexylmethyl acrylate (carboxyl of acrylic acid component). 50 mol% of the groups react)

<Component (B)> (B-1) Pentaerythritol triacrylate <(C) Component> (C-1) Phthalocyanine dye (C-2) Coumarin dye shown in Specific Example R11; 7-diethylamino -4-
Methyl coumarin

<Component (D)> (D-1) Organic Boron Complex shown in Specific Example B16 (D-2) Organic Boron Complex shown in Specific Example B27 (D-3) Titanocene Compound; Dicyclopentadienyl Titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] (D-4) hexaarylbiimidazole compound; 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-Tetraphenylbiimidazole (D-5) acetophenone derivative; [1- (4-morpholinoenyl) -2-dimethylamino-2-benzyl-1
-Butan-1-one <Other ingredients> (Other-1) Ethyl violet

Examples 1 to 8 A copper-clad laminated substrate (manufactured by Mitsubishi Gas Chemical Co., Inc.) having a conductive layer of electrolytic copper foil having a thickness of 18 μm on the surface of a glass cloth base material epoxy resin insulating base material having a thickness of 0.2 mm was used. Used on the copper foil, (A) component, (B) component, (C) component, (D) shown in Table 1.
By coating the coating liquid prepared by stirring 330 parts by weight of the components and other components at room temperature with propylene glycol monomethyl ether acetate using a wire bar and drying in a convection oven at 70 ° C. for 2 minutes, the film thickness A photopolymerizable image forming material for forming a conductor circuit having a 2 μm photopolymerizable composition layer was prepared.

For each of the obtained image-forming materials, a wavelength of 830
exposure device using a semiconductor laser of nm (Creo
500 mJ / c at a beam spot diameter of 15 μm using a “Trend Setter 3244T” manufactured by the same company.
Scanning exposure was carried out at various exposure energies of m ² or less, and then 1% at 25 ° C. in 0.8 wt% sodium carbonate aqueous solution.
A scanning line image was formed by developing by dipping for a minute. At that time, the inhibition of polymerization inhibition by oxygen, the resolution and the adhesion to the substrate of the photopolymerizable composition layer were evaluated by the methods described below, and the results are shown in Table 1.

<Prevention of Polymerization Inhibition by Oxygen> The reflection density before and after development in the image area was measured using a reflection densitometer (“RD-514” manufactured by Macbeth Co.), and the residual image area was calculated based on the following formula. The film ratio was calculated, and the exposure energy [S ₁ (mJ / cm ² )] required for the remaining film ratio to reach 50% was evaluated. On the other hand, on the photopolymerizable composition layer of the photopolymerizable image forming material obtained above, a 10 wt% aqueous solution of polyvinyl alcohol (“G-03C” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was further added to the photopolymerizable composition. In the case where a polyvinyl alcohol layer having a film thickness of 1 μm was formed by coating and drying in the same manner as in the formation of the composition layer, image exposure was performed in the same manner as described above, and then the polyvinyl alcohol layer was removed and development processing was performed. At this time, the exposure energy [S ₂ (mJ / cm ² )] required for the remaining film ratio of the exposed portion to reach 50% was evaluated by similarly calculating the remaining film ratio of the image portion, and the ratio [S ₁ / S ₂ ] was calculated. Residual film rate (%) in image area = [(reflection density of image area after development-reflection density of support surface) / (reflection density of plate surface before development-reflection density of support surface)] × 100

<Resolution> Scanning lines having different line widths and images of the intervals are formed, and the minimum scanning line and the width of the interval are defined as the resolution. <Adhesion to Substrate> When a grid-like cut is made in the image part and Cellotape (registered trademark) is adhered and peeled off, the image part without peeling is "good", and the one causing peeling in the image part "Poor"

Separately, each photopolymerizable image-forming material obtained above was evaluated for safelight property by the following method, and the results are shown in Table 1. <Safe light property> 1. Immediately below the white fluorescent lamp ("Neolmi Super FLR-40" manufactured by Mitsubishi Electric Corporation) as the image forming material.
After leaving for 1 hour with the photopolymerizable composition layer facing up at a position of 5 m, image exposure and development treatment were performed in the same manner as above, and the sensitivity with the image forming material before leaving and the dissolution time of the unexposed area were compared. However, the case where no difference was observed was defined as “good”, and the case where a difference occurred was defined as “poor”.

Comparative Examples 1-2 Components (A), (B) and (C) shown in Table 1
Component (D) and other components are cyclohexanone 330
Evaluation was performed in the same manner as in the above-mentioned examples except that the coating liquid prepared in addition to parts by weight was used, and image exposure was performed using a spectral sensitometer having a xenon lamp having a wavelength of 365 nm as a light source. The results are shown in Table 1.

[0092]

[Table 1]

[0093]

INDUSTRIAL APPLICABILITY According to the present invention, the effects of polymerization inhibition by oxygen in the photopolymerizable composition layer are suppressed, and the resolution and the safelight property are excellent, and therefore, handling in a bright room is possible. It is possible to provide a photopolymerizable image forming material and an image forming method which are excellent in adhesion to a substrate.

Continued front page    F-term (reference) 2H025 AA01 AA02 AB11 AB13 AB15                       AB20 AC08 AD01 BC13 BC42                       CA00 CA41 CB42 CC11 DA04                       FA10 FA17

Claims (7)

[Claims] 1. A photopolymerizable image forming material having a layer of a photopolymerizable composition on a substrate, wherein the exposure energy required for the residual film ratio of the exposed portion to be 50% when imagewise exposed and developed. S ₁ (mJ / cm ² )] and a polyvinyl alcohol layer having a thickness of 0.5 to 2 μm is formed on the photopolymerizable composition layer, and image exposure is performed under the same conditions to remove the polyvinyl alcohol layer. 50% of the remaining film in the exposed area when developed
Exposure energy [S ₂ (mJ / c
m ² )] ratio [S ₁ / S ₂ ] is in the range of 1 to 5. Photopolymerizable image forming material. 2. The film thickness of the photopolymerizable composition layer is 1 to 15 μm.
The photopolymerizable image forming material according to claim 1. 3. A photopolymerizable composition comprising the following component (A):
The photopolymerizable image forming material according to claim 1, which comprises the component (B), the component (C), and the component (D). (A) Alkali-soluble resin (B) Ethylenically unsaturated compound (C) Sensitizing dye (D) Photopolymerization initiator 4. The photopolymerizable image forming material according to claim 3, which contains, as the alkali-soluble resin as the component (A), an acid anhydride modified product of an unsaturated carboxylic acid-added epoxy resin. 5. A sensitizing dye as the component (C), which comprises 750 to 750.
The photopolymerizable image forming material according to claim 3 or 4, which contains a phthalocyanine dye having an absorption maximum in a wavelength range of 1200 nm. 6. The photopolymerizable image forming material according to claim 3, which contains an organic boron complex as a photopolymerization initiator of the component (D). 7. The photopolymerizable composition layer of the photopolymerizable image forming material according to claim 1, which is 750 to 1200.
An image forming method comprising scanning exposure with a near-infrared laser beam in a wavelength range of nm, and then developing with an alkali developing solution.