JP4470645B2 - Blue-violet light-sensitive photopolymerizable composition and resist image forming material - Google Patents

Description

  The present invention relates to an etching resist, a plating resist by a direct drawing method in the formation of printed circuit boards, plasma display wiring boards, liquid crystal display wiring boards, large scale integrated circuits, thin transistors, semiconductor packages and other fine electronic circuits. A blue-violet light-sensitive photopolymerizable composition and a resist image-forming material useful for forming resist images for solder resists, etc., and particularly suitable for use in the production of printed wiring boards The present invention relates to a polymerizable composition and a resist image forming material.

  Conventionally, for the formation of fine electronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, semiconductor packages, etc., for example, a layer made of a photosensitive composition is used. A dry film resist material formed on a temporary support film and having the surface of the photosensitive composition layer covered with a coating film, a resist image forming material obtained by peeling the coating film and laminating it on a substrate to be processed, or processing A resist image forming material in which a photosensitive composition layer is directly formed on a substrate and a protective layer is provided on the photosensitive composition layer as necessary, and the photosensitive composition layer is passed through a mask film on which a circuit or an electrode pattern is drawn. After image exposure, the mask film is peeled off, and further, if a temporary support film or a protective layer is provided, the protective layer, etc. are peeled off, A resist image corresponding to the circuit pattern is formed by developing using the difference in solubility in the developer in the exposed portion, and then the substrate to be processed is etched, plated, or soldered using the resist image as a resist. Lithography is widely used in which a resist image is removed after processing and the like to form a circuit or an electrode pattern drawn on a mask film on a substrate.

Also, in recent years, laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using laser light as an exposure light source is not only productive but also resolution and positional accuracy. As a laser beam that can be used for image exposure, the use of a semiconductor laser that can operate under a yellow light and that can stably oscillate in the blue-violet region with a wavelength of 390 to 430 nm is put into practical use. It has been reached. While there is a demand for an image forming material having a sensitivity capable of handling direct drawing with the blue-violet laser beam, the applicant of the present application previously disclosed an image at 1000 μJ / cm ² or less in Patent Document 1. We proposed a blue-violet laser-sensitive resist image-forming material that can be formed and has excellent yellow safelight properties.

On the other hand, not only for blue-violet photosensitivity, but for photopolymerizable compositions and resist image forming materials, such as confirmation of coating defects of the photopolymerizable composition layer, confirmation of development time, confirmation of image formation after development, etc. For the purpose, a colorant (developable visible paint) is generally added, and is usually used in a ratio of 0.01 to 20% by weight in the photopolymerizable composition (Patent Document). 1-3).
JP 2004-086122 A JP 11-167203 A JP-A-4-118211

However, in the blue-violet laser-sensitive resist image forming material described in Patent Document 1, although the sensitivity is improved by the photopolymerizable composition corresponding to the high sensitivity, the high resolution, for example, the line width Further improvement has been desired in terms of securing a fine resist image having an aspect 1 of 20 μm or less in an excellent shape.
The present invention has been made in view of the above-described prior art. Accordingly, the present invention provides a high-resolution and high-sensitivity photopolymerizable composition layer, particularly a bluish-violet photosensitive layer, in resist image formation. In a blue-violet light-sensitive photopolymerizable composition and a resist image formation, a fine resist image can be formed in forming a resist image by direct exposure using a direct drawing method and developing treatment. The purpose is to provide material.

  As a result of intensive studies to solve the above problems, the present inventor has found that the object can be achieved by including a specific small amount of a specific colorant in the photopolymerizable composition layer, and has reached the present invention. Therefore, the present invention contains 0.001 to 0.01% by weight of a colorant having an absorption maximum at 450 to 800 nm, and the blue-violet light-sensitive photopolymerizable composition and the blue-violet light-sensitive light The gist is a resist image-forming material formed of a polymerizable composition.

  In the present invention, a blue-violet photosensitive photopolymerizable composition layer in a resist image forming material is exposed by a direct drawing method and developed to form a resist image. A blue-violet light-sensitive photopolymerizable composition and a resist image-forming material that exhibit high sensitivity and high resolution and are excellent in pattern shape can be provided.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
[1] Constituent Components of Blue-violet Photosensitive Photopolymerizable Composition (Resist) The blue-violet photosensitive photopolymerizable composition of the present invention (hereinafter sometimes simply referred to as “photopolymerizable composition”). Each component will be described. The photopolymerizable composition according to the present invention comprises a specific colorant as an essential component, and further includes (A) a carboxyl group-containing polymer, (B) an ethylenically unsaturated compound, (C) a photopolymerization initiator, and (D). It is preferable to contain a sensitizing dye having an absorption maximum in the wavelength range of 355 to 430 nm, and if necessary, other additives other than the above components may be contained.

Hereinafter, each component will be described.
[1-1] Colorant (Developable Visible Paint)
In the photopolymerizable composition of the present invention, the content of the colorant having an absorption maximum at 450 to 800 nm in the photopolymerizable composition is 0.001% by weight or more, preferably 0.002% by weight or more. 0.01% by weight or less, preferably 0.008% by weight or less. If the content of the colorant is too small, operations such as confirmation of coating defects, confirmation of development time, confirmation of image formation after development, etc. are difficult to visually recognize. This is also disadvantageous for the pattern shape, and a fine pattern shape cannot be obtained.

  In the present invention, the colorant contained in the photopolymerizable composition layer has an absorption maximum of 450 to 800 nm, preferably 460 to 700 nm, more preferably 470 to 630 nm. This absorption maximum can also be obtained by directly measuring the absorption wavelength of the resist image forming material. If the wavelength of the absorption maximum of the colorant is too small, the sensitivity is disadvantageous. If it is too large, it is difficult to ensure the color density necessary for workability.

The color density necessary for workability is a resist image forming material having a layer made of a blue-violet photosensitive photopolymerizable composition on a temporary support film described later, and the photopolymerizable composition layer is covered. In a resist image forming material used by being laminated on a processed substrate, the reflection density of the resist image forming material on the processed substrate is (α), the reflection density after the image forming material is exposed is (β), and the processed substrate And (γ) is usually 1.10 ≧ (α) − (γ) ≧ 0.03, preferably 0.50 ≧ (α) − (γ) ≧ 0.05, and Usually 0.80 ≧ (β) − (α) ≧ 0.03, 0.4 ≧ preferably (β) − (α) ≧ 0.05. If (α)-(γ) is too small, it will be difficult to detect even if there is a defect or the like in the photopolymerizable composition layer of the resist image forming material, and it will also be difficult to confirm a break point for setting the development time. There arises a problem that it is difficult to confirm images after development. When (α) − (γ) is too large, the sensitivity tends to be low. On the other hand, if (β) − (α) is too small, it is difficult to confirm the exposed image, which also causes a problem in workability. When (β)-(α) is too large, it is difficult to ensure sufficient resolution.

  The colorant is not limited as long as it satisfies the above conditions, but a dye is preferable to a pigment, and examples thereof include triphenylmethane dyes. Specific examples of triphenylmethane dyes preferably used include malachite green, crystal violet, brilliant green GX, basic pure blue BO, basic cyanine BX, basic cyanine 6G, rhodamine B, rhodamine 6GCP, methyl violet, magenta and the like. .

Examples of other colorants include cyanine dyes, thiazine dyes, and xanthene dyes. Specific examples thereof include methylene blue, basic blue, rhodamine and the like.
[1-2] (A) Carboxyl Group-Containing Polymer In the present invention, the carboxyl group-containing polymer of the component (A) constituting the photopolymerizable composition that is preferred is the photopolymerizable composition on the substrate. The purpose is to improve the formability and developability as a layer. Specifically, for example, (meth) acrylic acid [in the present invention, “(meth) acryl” means “acrylic”. "And / or" methacryl ". ], A copolymer of an ethylenically unsaturated carboxylic acid monomer such as crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and a vinyl compound monomer copolymerizable therewith. As the unsaturated carboxylic acid, (meth) acrylic acid is particularly preferable.

Examples of the copolymerizable vinyl compound monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n- or i-propyl (meth) acrylate, n- or i- or t-butyl (meth). ) Alkyl (meth) acrylates such as acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
Α-substituted alkylstyrenes such as styrene, α-methylstyrene, α-ethylstyrene; and nucleus-substituted alkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,5-dimethylstyrene;
nuclear substituted hydroxystyrenes such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene;
Styrenes such as nucleus-substituted halogenated styrenes such as p-chlorostyrene, p-bromostyrene, and dibromostyrene;
And glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) Other vinyl compounds such as acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate and the like can be mentioned.

  Among these, as the carboxyl group-containing polymer of the component (A) in the present invention, each monomer of (meth) acrylic acid, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and styrenes It is preferable that it is a copolymer having a structural repeating unit derived from 1 to 50% by weight of a structural repeating unit derived from (meth) acrylic acid based on the total amount of the copolymer, and alkyl (meth) acrylates. A copolymer having 15 to 80% by weight of structural repeating units derived from 1 to 30% by weight of structural repeating units derived from hydroxyalkyl (meth) acrylates and 1 to 40% by weight of structural repeating units derived from styrenes. More preferably, it is a polymer, and 15 to 60 constituent repeating units derived from alkyl (meth) acrylates having 4 or more carbon atoms are used. Especially preferably a copolymer containing an amount%.

These copolymers preferably have an acid value of 100 to 300 mg · KOH / g and a polystyrene-equivalent weight average molecular weight of 20,000 to 150,000.
[1-3] (B) Ethylenically unsaturated compound In the present invention, the ethylenically unsaturated compound (B) constituting the preferred photopolymerizable composition is irradiated with actinic rays. The radically polymerizable ethylenically unsaturated bond that undergoes addition polymerization by the action of a photopolymerization initiating system containing a photopolymerization initiator of the component (C), which will be described later, may be crosslinked or cured in some cases. A compound having at least one.

  As the ethylenically unsaturated compound, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid Unsaturated carboxylic acids such as, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc. may be used. From the standpoint that the difference in sex can be expanded, a compound having two or more ethylenically unsaturated bonds in the molecule is preferable, and an acrylate compound in which the unsaturated bond is derived from a (meth) acryloyloxy group Particularly preferred.

  As a compound having two or more ethylenically unsaturated bonds in the molecule, typically, esters of unsaturated carboxylic acid and polyhydroxy compound, urethane of hydroxy (meth) acrylate compound and polyisocyanate compound (meta ) Acrylates, and (meth) acrylic acid or epoxy (meth) acrylates of hydroxy (meth) acrylate compounds and polyepoxy compounds.

Specific examples of the esters include unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), trimethylene. Glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylol ethane, tetramethylol ethane, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene Reaction products with aliphatic polyhydroxy compounds such as oxide adducts, diethanolamine, triethanolamine, and more specifically, for example, ethylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene 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, tetramethylol Ethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Limethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition 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, so Examples thereof include rubitol penta (meth) acrylate, sorbitol hexa (meth) acrylate and the like, and similar crotonate, isocrotonate, maleate, itaconate, citraconate and the like.

  Furthermore, as the esters, unsaturated carboxylic acids as described above, aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts or glycidyl group-containing compound adducts In particular, for example, hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate] Bisphenol A bis [trioxyethylene (meth) acrylate], bisphenol A bis [pentaoxyethylene (meth) acrylate], bisphenol A bis [hexaoxyethylene (meth) acrylate] Bisphenol A bis [glycidyl ether (meth) acrylate] and the like, and a reaction product of an unsaturated carboxylic acid as described above and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, For example, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tri (meth) acrylate, etc., and a reaction product of unsaturated carboxylic acid, polycarboxylic acid and polyhydroxy compound, specifically For example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, a condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, Condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin. It is.

  Specific examples of urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylol. Hydroxy (meth) acrylate compounds such as ethane tri (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,6 Aliphatic polymers such as 11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 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 (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates Aneto, a reaction product of a polyisocyanate compounds and the like.

  Moreover, as the epoxy (meth) acrylates, specifically, for example, (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene Glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylol Aliphatic polyepoxy compounds such as propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy Compounds, brominated phenol novolac polyepoxy compounds, aromatic polyepoxy compounds such as (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, sorbitan polyglycidyl ethers, Examples thereof include reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

In addition to the above, as other ethylenically unsaturated compounds, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, etc. Is mentioned. These ethylenically unsaturated compounds may be used alone or in combination of two or more.
As the ethylenically unsaturated compound of the above component (B), in the present invention, ester (meth) acrylates or urethane (meth) acrylates are preferable, ester (meth) acrylates are particularly preferable, and the ester ( Among the (meth) acrylates, ester (meth) acrylates having a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or a polyethylene oxide adduct of bisphenol A, and having two or more (meth) acryloyloxy groups are particularly preferred. preferable.
[1-4] (C) Photopolymerization Initiator In the present invention, the photopolymerization initiator of component (C) constituting the preferred photopolymerizable composition is a sensitizing dye of component (D) described later. A radical generator that receives photoexcitation energy of a sensitizing dye to generate an active radical when irradiated with light in the presence of the sensitizing dye, and leads to polymerization of the ethylenically unsaturated compound of component (B), for example, , Hexaarylbiimidazole compounds, titanocene compounds, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, diaryliodonium salts, organoborates, and organic peroxides. . Among them, hexaarylbiimidazole compounds, titanocene compounds, and organoborates are preferable from the viewpoint of sensitivity as a photopolymerizable composition, adhesion to a substrate, and storage stability, and hexaarylbiimidazole compounds. Compounds are particularly preferred.

As the hexaarylbiimidazole compound, specifically, for example, 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (p-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra ( p-methylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) ) -4,4 ', 5,5'-tetra o, p-dimethoxyphenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (p-methoxyphenyl) biimidazole, 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetra (p-ethoxycarbonylphenyl) 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, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra ( p-fluorophenyl) biimida 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole, 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-) Chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) biimidazole and the like. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.
[1-5] (D) Sensitizing Dye In the present invention, the sensitizing dye of component (D) constituting the photopolymerizable composition that is preferred has an absorption maximum in the wavelength range of 355 to 430 nm. Thus, while efficiently absorbing light in the blue-violet region of the wavelength region, the photoexcitation energy is transmitted to the photopolymerization initiator of the component (C), the photopolymerization initiator is decomposed, and the component (B) It is a light-absorbing dye having a sensitizing function for generating an active radical that induces polymerization of an ethylenically unsaturated compound. Here, the absorption maximum wavelength is a wavelength showing a maximum value when the sensitizing dye is dissolved in tetrahydrofuran and the absorption wavelength is measured, and the absorption maximum wavelength in the wavelength region of 355 to 430 nm is the maximum wavelength. The longest wavelength is preferred.

  Examples of the sensitizing dye include (i) a diaminobenzophenone compound having a basic skeleton represented by the following formula described in JP-A No. 2000-10277 and Japanese Patent Application No. 2002-362326, and (ii) Japanese Patent Application No. 2002. -Aminophenyl-benzimidazole / benzoxazole / benzothiazole compounds having the following formula as described in the specification of JP-362326, etc., and (iii) the basic formula of the following formula as described in Japanese Patent Application No. 2003-424180, etc. (Iv) an aminocarbostyryl compound having the following formula as a basic skeleton described in Japanese Patent Application No. 2003-392404, etc., and (v) Japanese Patent Application Laid-Open No. 2002-169282, Japanese Patent Application No. 2003. No. 374432, etc., and a merocyanine compound having a basic skeleton represented by the following formula, (vi) JP 2002-268239 A (Vii) an imide-based compound having the following formula as a basic skeleton described in Japanese Patent Application No. 2003-291606, (viii) Benzimidazole / benzoxazole / benzothiazole compounds having a basic skeleton, (ix) triazole compounds having the following formula as a basic skeleton, (x) cyanostyryl compounds having the following formula as a basic skeleton, (xi) A stilbene compound having a basic skeleton, (xii) an oxadiazole / thiadiazole compound having the following formula as a basic skeleton, (xiii) a pyrazoline compound having the following formula as a basic skeleton, and (xiv) a formula having the following formula as a basic skeleton A coumarin compound, (xv) a triphenylamine compound having a basic skeleton represented by the following formula described in Japanese Patent Application No. 2003-435212, (xvi) Japanese Patent Application No. 2003-340924 Acridone based compounds having a basic skeleton of the following formula according to Saisho like, include a carbazole-based compounds having a basic skeleton of the following formula described in (xvii) No. 2003-435312 Pat like.

In the following formulae, X and Z each independently represent a nitrogen atom, an oxygen atom, a sulfur atom, or C—R, Y represents an arbitrary linking group, and n is an integer of 1 or more. The compounds of the following formulas showing the basic skeleton are, for example, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, aralkyl groups, alkenyloxy groups, alkenyls, respectively. Substituents such as thio group, acyl group, acyloxy group, amino group, acylamino group, carboxyl group, carboxylic acid ester group, carbamate group, carbamoyl group, sulfamoyl group, sulfonic acid ester group, saturated or unsaturated heterocyclic group These substituents may further have a substituent, and a plurality of substituents may be bonded to each other to form a cyclic structure.

  Of these, dialkylaminobenzene compounds, triphenylamine compounds, acridone compounds, carbazole compounds, and the like are preferable. Among them, as the dialkylaminobenzene compound, in particular, a dialkylaminobenzophenone compound, a dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring, benzene A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to an amino group on the ring, or a dialkylaminobenzene compound having a carbostyryl skeleton is preferred.

  The dialkylaminobenzophenone compound is preferably a compound represented by the following general formula (I).

[In the formula (I), R ¹ , R ² , R ⁵ , and R ⁶ each independently represents an alkyl group which may have a substituent, and R ³ , R ⁴ , R ⁷ , and R ⁸ each independently represents an optionally substituted alkyl group or a hydrogen atom, and R ¹ and R ² , R ⁵ and R ⁶ , R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , and R ⁶ and R ⁸ may each independently form a nitrogen-containing heterocycle. ]
Here, the carbon number of the alkyl group of R ¹ , R ² , R ⁵ , and R ⁶ in formula (I), and the carbon when R ³ , R ⁴ , R ⁷ , and R ⁸ are an alkyl group The number is preferably 1-6. Further, when forming a nitrogen-containing heterocyclic ring, it is preferably a 5- or 6-membered ring, and R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , or R ⁶ and R ⁸ are 6-membered rings. It is preferable that R ¹ and R ² and R ³ and R ⁴ , and / or R ⁵ , R ⁶ , R ⁷ and R ⁸ form a julolidine ring. Particularly preferred. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred.

  Specific examples of the compound represented by the general formula (I) include compounds having the following structures.

  In addition, the heterocyclic group in the dialkylaminobenzene compound having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring includes a nitrogen atom, an oxygen atom, or a sulfur atom. Alternatively, a 6-membered ring is preferable, a 5-membered ring having a condensed benzene ring is particularly preferable, and those represented by the following general formula (II) are preferable.

[In formula (II), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and R ³ and R ⁴ each independently have a substituent. R ¹ and R ² , R ¹ and R ³ , and R ² and R ⁴ may each independently form a nitrogen-containing heterocyclic ring, , An oxygen atom, a sulfur atom, a dialkylmethylene group, an imino group, or an alkylimino group, and the benzene ring condensed to the heterocyclic ring may have a substituent. ]
Here, the carbon number of the alkyl group of R ¹ and R ² in the formula (II), and the carbon number when R ³ and R ⁴ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, it is preferably a 5- or 6-membered ring, and R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁷ , or R ⁶
And R ⁸ preferably form a 6-membered tetrahydroquinoline ring, and R ¹ , R ² , R ³ and R ⁴ , and / or R ⁵ , R ⁶ , R ⁷ and R ⁸ are julolidine rings Is particularly preferred. Furthermore, a tetrahydroquinoline ring having an alkyl group as a substituent at the 2-position or a julolidine ring containing the tetrahydroquinoline ring is particularly preferred. In addition, when X is a dialkylmethylene group, the alkyl group preferably has 1 to 6 carbon atoms, and when it is an alkylimino group, the alkyl group preferably has 1 to 6 carbon atoms.

  Specific examples of the compound represented by the general formula (II) include, for example, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl). ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2- (p-dimethylaminophenyl) -3,3-dimethyl-3H-indole, 2- (p-diethylamino) Phenyl) -3,3-dimethyl-3H-indole and below The compound of the following structure is mentioned.

  In addition to the compounds represented by the general formula (II), examples of the dialkylaminobenzene compounds having a heterocyclic group as a substituent at a carbon atom in the p-position with respect to the amino group on the benzene ring include: 2- (p-dimethylaminophenyl) pyridine, 2- (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) ) Pyrimidine, 2- (p-diethylaminophenyl) pyrimidine, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-diethylaminophenyl) -1,3 , 4-thiadiazole and the like.

  As the dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom with respect to the amino group on the benzene ring, those represented by the following general formula (III) are preferred.

[In Formula (III), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and R ³ and R ⁴ each independently have a substituent. also alkyl group, or a hydrogen atom, R ¹ and R ^2, R ¹ and R ^3, and each, independently of R ² and R ^4, may form a nitrogen-containing heterocyclic ring, R ⁹ Represents a monovalent group or a hydrogen atom, and R ¹⁰ represents a monovalent group. ]
Here, the carbon number of the alkyl group of R ¹ and R ² in the formula (III), and the carbon number when R ³ and R ⁴ are an alkyl group are preferably 1 to 6, and When forming a nitrogen heterocycle, it is preferably a 5- or 6-membered ring, but R ³ and R ⁴ are preferably hydrogen atoms. Examples of the monovalent group of R ⁹ and R ¹⁰ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, Aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino group, acylamino group, carbamate group, sulfonamido group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio Group, imino group, cyano group, and heterocyclic group. Of these, R ⁹ is preferably a hydrogen atom, and R ¹⁰ is preferably an aryl group.

  Further, as the dialkylaminobenzene compound having a carbostyril skeleton, those represented by the following general formula (IV) are preferable.

[In the formula (IV), R ¹ , R ² and R ¹¹ each independently represents an alkyl group which may have a substituent, and R ³ and R ⁴ each independently represents a substituent. An alkyl group which may have or a hydrogen atom, R ¹ and R ² , R ¹ and R ³ , and R ² and R ⁴ may each independently form a nitrogen-containing heterocycle; R ¹² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ]
Here, the carbon number of the alkyl group of R ¹ , R ² , and R ¹¹ in formula (IV), and the carbon number when R ³ , R ⁴ , and R ¹² are an alkyl group are 1-6. It is preferable that when a nitrogen-containing heterocycle is formed, a 5- or 6-membered ring is preferable, but R ³ and R ⁴ are preferably hydrogen atoms. R ¹² is preferably a phenyl group.

  In addition, as a triphenylamine compound, triphenylamine is a basic skeleton, and the three benzene rings may have a condensed ring such as a hydrocarbon ring or a heterocyclic ring, or an alkyl group or a cycloalkyl group. Alkenyl group, cycloalkenyl group, alkoxy group, alkenyloxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylate group, carbamoyl Group, amino group, acylamino group, carbamate group, sulfonamide group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio group, alkenylthio group, imino group, cyano group, nitro group, halogen atom, and heterocyclic ring May have a substituent such as a group, It may further have a substituent.

  In addition, the acridone-based compound has an acridone ring as a basic skeleton, and the two benzene rings may have a condensed ring such as a hydrocarbon ring or a heterocyclic ring, or an alkyl group, a cycloalkyl group, or an alkenyl group. , Cycloalkenyl group, alkoxy group, alkenyloxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, amino Groups, acylamino groups, carbamate groups, sulfonamido groups, sulfonic acid groups, sulfonic acid ester groups, sulfamoyl groups, alkylthio groups, alkenylthio groups, imino groups, cyano groups, nitro groups, halogen atoms, heterocyclic groups, etc. It may have a substituent, and these substituents are further substituted It may have. The hydrogen atom in the imino group may be substituted with a substituent such as an alkyl group or an acyl group.

  In addition, as a carbazole compound, etc., the carbazole ring is a basic skeleton, and the two benzene rings may have a condensed ring by a hydrocarbon ring or a heterocyclic ring, or an alkyl group, a cycloalkyl group, an alkenyl group. Group, cycloalkenyl group, alkoxy group, alkenyloxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, arylalkenyl group, hydroxy group, formyl group, carboxyl group, carboxylic acid ester group, carbamoyl group, Amino group, acylamino group, carbamate group, sulfonamide group, sulfonic acid group, sulfonic acid ester group, sulfamoyl group, alkylthio group, alkenylthio group, imino group, cyano group, nitro group, halogen atom, heterocyclic group, etc. May have a substituent, and these substituents are Substituent may have. The hydrogen atom in the imino group may be substituted with a substituent such as an alkyl group or an acyl group.

  As the sensitizing dye of the component (D), in the present invention, a dialkylaminobenzophenone compound represented by the general formula (I), an amino group on the benzene ring represented by the general formula (III) A dialkylaminobenzene compound having a substituent containing a sulfonylimino group at the p-position carbon atom, a dialkylaminobenzene compound having a carbostyryl skeleton represented by the general formula (IV), and a trialkylaminobenzene compound, Phenylamine compounds are particularly preferred.

[1-6] Other components In the present invention, in addition to the above components, the following components may be further contained.
[1-6-1] (E) Exposure visible paint agent In this invention, the exposure visible paint agent may be contained as a pigment | dye for visualizing the image formed by exposure. Examples of the exposure visible paint include leuco dyes. Specific examples of the leuco dye include, for example, tris (4-dimethylaminophenyl) methane [leuco crystal violet], tris (4-diethylamino-2-methylphenyl) methane, leucomacarite green, leucoaniline, leucomethyl violet. Among them, leuco crystal violet is preferable.

In the present invention, the (A) component carboxyl group-containing polymer constituting the preferred photopolymerizable composition, the (B) component ethylenically unsaturated compound, the (C) component photopolymerization initiator The content ratio of the sensitizing dye of the component (D) and the exposure visible paint of the component (E) is 20 to 80% by weight of the component (A) with respect to the total amount of the photosensitive composition. B) component is 20 to 80% by weight, component (C) is 0.1 to 20% by weight, component (D) is 0.01 to 10% by weight, component (E) is 0.01 to 0.5% by weight %, Particularly 0.05 to 0.8% by weight.

[1-6-2] Others In addition, the photopolymerizable composition of the present invention may contain a hydrogen-donating compound for the purpose of improving the photopolymerization initiation ability and the like. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto Mercapto group-containing compounds such as naphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopro Many officers such as pionate Thiol compounds, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or an ester thereof, a salt such as ammonium or sodium salt thereof, a derivative such as a bipolar ion compound, phenylalanine or an ester thereof, an ammonium or Examples thereof include amino acids having an aromatic ring such as a salt such as a sodium salt and derivatives thereof such as a bipolar ion compound or derivatives thereof.

In the present invention, the content of the hydrogen donating compound is preferably 5% by weight or less, more preferably 2% by weight or less, based on the total amount of the photopolymerizable composition.
Furthermore, a preferable photopolymerizable composition is a polymerization inhibitor such as a hydroquinone derivative that is a divalent phenol derivative containing a dihydroxybenzene ring, such as hydroquinone, methylhydroquinone, and p-methoxyphenol, in addition to the above components. An agent is preferably contained, and the content thereof is preferably 5 to 60 ppm with respect to the total amount of the photopolymerizable composition.

Furthermore, a preferable photopolymerizable composition includes, in addition to the above-mentioned components, a plasticizer for controlling film physical properties as a photopolymerizable composition layer, a color change agent, and an image to be processed on a substrate to be processed. Even if it contains an adhesion-imparting agent for imparting adhesion and a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a flame retardant, a solvent, a surfactant, etc. Good.
Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate, glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, tricresyl phosphate, Phosphate esters such as phenyl phosphate, amides such as benzenesulfonamide, p-toluenesulfonamide, Nn-butylacetamide, aliphatic such as diisobutyl adipate, dioctyl adipate, dioctyl azelate, dimethyl sebacate, dibutyl malate Dibasic acid esters, glycerin triacetyl, triethyl citrate, tributyl citrate, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid di Corruptible, polyethylene glycol, glycols such as polypropylene glycol may be mentioned, respectively.

Examples of the color changing agent include diphenylamine, dibenzylamine, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, and o-chloro in addition to the above-mentioned dyes. Examples of the adhesion imparting agent include aniline and the like, and examples thereof include benzimidazole, henzothiazole, benzoxazole, benzotriazole, 2-mercaptobenzothiazole, and 2-mercaptobenzoimidazole.

The above-mentioned photopolymerizable composition usually has an absorption maximum in the range of 360 to 450 nm, preferably 365 to 440 nm, and more preferably 370 to 430 nm. If the absorption maximum is too small, sufficient sensitivity cannot be obtained, and if it is too large, it is difficult to work under a yellow light.
[2] Resist image forming material The photopolymerizable composition of the present invention is applied onto a temporary support film and dried, for example, as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent. When the surface of the formed photopolymerizable composition layer is covered with a coating film, a so-called dry film resist material is formed, and when the photopolymerizable composition layer side is covered with the coating film, the coating film By laminating and laminating on the substrate to be processed, or by directly applying and drying on the substrate to be processed as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent. A resist image forming material in which a layer of a photopolymerizable composition is formed on a substrate, the photopolymerizable composition layer of the resist image forming material is exposed by a direct drawing method and developed. It is suitably used for a usage form as a forming method.

  As the temporary support film when used as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have solvent resistance, heat resistance, etc. necessary for the production of the dry film resist material, the photopolymerizable composition coating solution directly on the temporary support film Can be applied and dried to produce a dry film resist material, and even if those films have low solvent resistance, heat resistance, etc., for example, polytetrafluoroethylene film, release film, etc. First, a photopolymerizable composition layer is formed on a film having releasability, and a temporary support film having low solvent resistance or heat resistance is laminated on the layer, and then a film having releasability. A dry film resist material can also be produced by peeling the film.

  The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility with respect to the components used and gives good coating properties. For example, methyl cellosolve acetate, ethyl cellosolve acetate, etc. Cellosolve solvents, 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, dipropylene glycol dimethyl ether and other propylene glycol solvents, Butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Ester solvents such as ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as methanol, isopropanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketones such as cyclohexanone, methyl ethyl ketone Examples thereof include solvents, aromatic solvents such as toluene, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. Among these, from the standpoints of solubility, surface tension, viscosity, ease of drying, and the like, single or mixed solvents such as methyl ethyl ketone, methanol, isopropanol, and toluene are preferable. The use ratio of the solvent is usually in the range of about 0.5 to 2 times by weight with respect to the total amount of the photopolymerizable composition.

As the coating method, a conventionally known method such as a die coating method, a knife coating method, a roll coating method, a spray coating method, or a spin coating method can be used. The coating amount at that time is usually 5 μm or more in terms of dry film thickness and 10 μm or more as a dry film resist material in terms of image forming properties to be described later and workability such as subsequent etching and plating. The thickness is preferably 15 μm or more, more preferably 200 μm or less, and even more preferably 100 μm or less from the viewpoint of sensitivity and the like. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 30 to 130 ° C., and the drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. It is done.

In addition, when used as a dry film resist material or the like, it is preferable to cover the surface of the formed photopolymerizable composition layer with a coating film until it is laminated on the substrate to be processed. A conventionally known film such as a polyethylene film, a polypropylene film, or a polytetrafluoroethylene film is used.
In addition, when the photopolymerizable composition layer side of the dry film resist material is covered with a coating film, the coating film is peeled off and laminated by heating, pressing, or the like, or The substrate to be processed in producing a resist image forming material by directly applying and drying the photopolymerizable composition coating solution is exposed and developed by directly drawing the photopolymerizable composition layer formed thereon. A pattern such as a circuit or an electrode is formed on the surface by etching or plating using the image that appears by processing as a resist. Copper, aluminum, gold, silver, chromium, zinc The metal plate itself such as tin, lead and nickel may be used, but usually, for example, epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, Thermosetting resins such as enol resin, melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, resin such as thermoplastic resin such as fluorine resin, Paper, glass, and inorganic materials such as alumina, silica, barium sulfate, calcium carbonate, or composite materials such as glass cloth base epoxy resin, glass nonwoven base epoxy resin, paper base epoxy resin, paper base phenol resin Etc., and a metal foil such as metal oxide such as indium oxide, tin oxide or indium oxide doped tin oxide is heated on the surface of the insulating support having a thickness of about 0.02 to 10 mm, and pressure bonding laminate The thickness of the metal by sputtering, vapor deposition, plating, etc. Metal-clad laminate formed with 1~100μm approximately conductive layer is preferably used.

  In the case where a resist image forming material is prepared by directly applying and drying the photopolymerizable composition coating solution, polymerization of the photopolymerizable composition layer formed on the substrate to be processed by oxygen is performed. A protective layer formed by applying and drying a solution of, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, etc. on the photopolymerizable composition layer in order to prevent prohibiting action, etc. May be provided.

  Then, the resist image forming method of the present invention comprises exposing the photopolymerizable composition layer of the resist image forming material having a photopolymerizable composition layer on a substrate to be processed by a direct drawing method, developing the resist, Form an image. At that time, when the photopolymerizable composition layer is formed of the dry film resist material, the light is usually applied from the temporary support film or by directly applying the photopolymerizable composition coating liquid and drying it. In the case where a polymerizable composition layer is formed and the protective layer is provided, the exposure is usually performed by a direct drawing method from above the protective layer.

  As an exposure light source by the direct drawing method, a light source that generates light in the blue-violet region in the wavelength range of 390 to 430 nm is preferable, and among them, a light source that generates laser light in the blue-violet region is preferable. More preferred is a light source that generates. Specifically, an indium gallium nitride semiconductor laser or the like is preferable, but a laser using h-line of a UV light source is also included.

The exposure method is not particularly limited, but a scanning exposure method such as a DMD method or a polygon scan method is preferable. Further, the laser beam spot diameter is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less, in order to exhibit sufficient resolution. The lower limit is usually about 2 μm from the technical viewpoint. In scanning exposure, the exposure amount is usually 0.1 to 50 mJ / cm ² , preferably 0.
. It is 5-40 mJ / cm < ² >, More preferably, it is 1-30 mJ / cm < ² >. If the exposure amount is too low, it becomes difficult to form a high-resolution pattern, and if it is too high, a problem arises in productivity.

  In the present invention, when the photopolymerizable composition layer is formed with the dry film resist material, the development treatment after the exposure is performed by peeling off the temporary support film, or by applying the photopolymerizable composition coating solution. In the case where the photopolymerizable composition layer is formed by directly applying and drying, and having the protective layer, after removing the protective layer, an alkaline developer having a pH of 9 to 14, for example, A dilute alkaline aqueous solution of about 0.3 to 2% by weight of an alkali salt such as sodium carbonate or potassium carbonate is used. A surfactant, an antifoaming agent, an organic solvent as a development accelerator and the like may be added to the alkaline aqueous solution.

  The development is usually performed by immersing the image forming material in the developer or spraying the developer onto the image forming material, and a known developing method such as a paddle method, preferably about 10 to 50 ° C. More preferably, it is performed at a temperature of about 15 to 45 ° C. for a time of about 5 seconds to 10 minutes, preferably about 10 seconds to 2 minutes.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Examples 1-4, Comparative Examples 1-3
As the photopolymerizable composition, the following carboxyl group-containing polymer (A1), ethylenically unsaturated compounds (B1 to B2), photopolymerization initiator (C1), sensitizing dye (D1), and leuco dye (E1) In addition, a colorant (F1 to F2) was added to the following solvent (Y1) in the formulation shown in Table 1, and a coating solution prepared by stirring at room temperature to prepare a polyethylene terephthalate film (thickness) as a temporary support film 25 μm) using a 100 μm applicator in an amount that gives a dry film thickness of 25 μm, air-dried at 25 ° C. for 1 minute, and then dried in an oven at 85 ° C. for 1 minute to form a photopolymerizable composition layer A polyethylene film (thickness 25 μm) as a covering film was laminated thereon to produce a dry film resist material.

<Carboxyl group-containing polymer>
(A1) Methacrylic acid / methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / styrene copolymer (wt% = 20/35/10/10/15/10, weight average molecular weight 46, 000) (No addition of antioxidant, no addition of polymerization inhibitor)
<Ethylenically unsaturated compound>
(B1) The following compounds (containing 200 ppm of BHT as an antioxidant and 100 ppm of p-methoxyphenol as a polymerization inhibitor)
(B2) The following compounds (containing 200 ppm of BHT as an antioxidant and 100 ppm of p-methoxyphenol as a polymerization inhibitor)

<Photopolymerization initiator>
(C1) 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole <Sensitizer>
(D1) The following compound (when the sensitizing dye is diluted 60,000 times with tetrahydrofuran and the UV extinction coefficient is measured in the wavelength region of 300 to 500 nm, the absorption maximum existing at the longest wavelength is 388 nm)

（Ｆ２）マラカイトグリーン

＜溶剤＞
（Ｙ１）メチルエチルケトン
別に、厚み３５μｍの銅箔を貼り合わせたポリイミド樹脂の銅張積層基板（厚み１．５ｍｍ、大きさ２５０ｍｍ×２００ｍｍ）の銅箔表面を、住友スリーエム社製「スコッチブライトＳＦ」を用いてバフロール研磨し、水洗し、空気流で乾燥させて整面し、次いで、これをオーブンで８０℃に予熱した後、その銅張積層板の銅箔上に、前記で得られたドライフィルムレジスト材を、そのポリエチレンフィルムを剥離しながらその剥離面で、ハンド式ロールラミネーターを用いて、ロール温度１００℃、ロール圧０．３ＭＰａ、ラミネート速度１．５ｍ／分でラミネートすることにより、銅張積層基板上に光重合性組成物層が形成されたレジスト画像形成材を製造した。 <Leuco dye>
(E1) Leuco Crystal Violet <Colorant>
(F1) Crystal violet

(F2) Malachite green

<Solvent>
(Y1) Methyl ethyl ketone Separately, the surface of the copper foil of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil was applied to “Scotch Bright SF” manufactured by Sumitomo 3M Limited. Use buffol polishing, wash with water, dry with air flow and adjust the surface, then preheat it to 80 ° C. in an oven, then on the copper foil of the copper clad laminate, the dry film obtained above By laminating the resist material on the peeling surface while peeling the polyethylene film using a hand-type roll laminator at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min. A resist image forming material having a photopolymerizable composition layer formed on a laminated substrate was produced.

The resulting photopolymerizable composition layer of each resist image forming material is exposed and developed under the following exposure and development conditions, and the pattern shape of the resulting resist image is evaluated according to the following criteria: The results are shown in Table 1.
<Reflection density>
Resist image forming material (α) having a photopolymerizable composition layer on the substrate to be processed, solid-exposed with the optimum exposure selected by the following method (β), substrate to be processed (γ) The reflection density was measured with a black filter using RD918 manufactured by Macbeth.
<Exposure and development conditions>
Using a blue LD slot module “NDAV520E2” manufactured by Nichia Corporation with an oscillation wavelength of 407 nm and a rated light output of 500 mW, 4 mJ / cm ² , 5.6 mJ / cm ² , 8 mJ / cm ² , 11 mJ / cm ² , 16 mJ / cm ^2, and an exposure amount of 6 stages of 22 mJ / cm ^2, and scanning exposure an exposure pattern of 20 [mu] m of the set line (line / space = 20μm / 20μm). After 20 minutes from the exposure, the polyethylene terephthalate film is peeled off and removed, and then a 0.7 wt% sodium carbonate aqueous solution is added at 25 ° C. as a breakpoint (time until the non-exposed part is completely dissolved). Developed by spraying at 0.15 MPa with a development time of .75 times. At that time, the obtained pattern image was observed with an optical microscope, and the exposure amount at which the line width of the top portion of the collective line was closest to 20 μm at each exposure amount was determined as the optimum exposure amount.
<Development visibility>
When measuring breakpoints, the visibility of resist developed in an automatic processor is evaluated as follows.

○: The appearance until the resist is completely removed is visible and the breakpoint is measured.
Easy to do.
X: It is difficult to see the presence or absence of resist, and it is difficult to measure breakpoints.
<Visibility of exposure>
After the exposure at the optimum exposure amount, the state of the resist before development is observed and evaluated as follows.

○: The exposed pattern can be confirmed well.
X: The exposed pattern is very difficult to see.
<Resolution>
Pattern shapes obtained by exposure at the respective exposure amounts were observed with a scanning electron microscope and evaluated according to the following criteria.

A: The limit exposure amount (the exposed pattern shows no tailing and is resolved finely, but the exposure amount at which tailing is seen above, the same applies hereinafter) is three steps higher than the optimum exposure amount.
○: The limit exposure amount is two steps higher than the optimum exposure amount.
Δ: The limit exposure is one step higher than the optimum exposure.
X: The limit exposure amount is the optimum exposure amount.

  The resist image-forming material of the present invention is a direct drawing method in the formation of printed circuit boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, semiconductor packages and other fine electronic circuits. It is especially useful for forming resist images for etching resists, plating resists, solder resists, etc. by direct drawing with blue-violet laser light, especially for printed wiring board manufacturing, especially for applications that require high resolution. Is preferred.

Claims (12)

  A blue-violet light-sensitive photopolymerizable composition containing 0.001 to 0.01% by weight of a colorant having an absorption maximum at 450 to 800 nm.   The blue-violet light-sensitive photopolymerizable composition according to claim 1, wherein the colorant having an absorption maximum at 450 to 800 nm is a triphenylmethane dye.   The blue-violet light-sensitive photopolymerizable composition according to claim 1 or 2, which has an absorption maximum at 360 to 450 nm. The blue-violet light-sensitive photopolymerizable composition according to any one of claims 1 to 3, comprising the following component (A), component (B), component (C), and component (D).
(A) carboxyl group-containing polymer (B) ethylenically unsaturated compound (C) photopolymerization initiator (D) sensitizing dye having an absorption maximum in the wavelength range of 355 to 430 nm   (E) The blue-violet light-sensitive photopolymerizable composition according to any one of claims 1 to 4, comprising an exposure visible paint.   The said (A) component contains the copolymer which has each structural repeating unit derived from (meth) acrylic acid, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and styrenes. The blue-violet light-sensitive photopolymerizable composition according to any one of the above.   The blue-violet photosensitivity according to any one of claims 1 to 6, wherein the component (B) includes an ester (meth) acrylate having a polyoxyalkylene group and having two or more (meth) acryloyloxy groups. Photopolymerizable composition.   The blue-violet light-sensitive photopolymerizable composition according to any one of claims 1 to 7, comprising a hexaarylbiimidazole compound as the component (C).   The sensitizing dye as component (D) includes any compound selected from the group consisting of dialkylaminobenzene compounds, triphenylamine compounds, acridone compounds, and carbazole compounds. 2. The blue-violet light-sensitive photopolymerizable composition according to item 1.   A resist image-forming material having a layer made of the blue-violet light-sensitive photopolymerizable composition according to claim 1 on a temporary support film. A resist image forming material used by laminating a blue-violet photosensitive photopolymerizable composition layer on a substrate to be processed, wherein the resist image forming material has a reflection density of (α), and the resist image forming material When the reflection density after exposure is (β) and the reflection density of the substrate to be processed is (γ),
The resist image forming material according to claim 10, wherein (α) − (γ) ≧ 0.03 and (β) − (α) ≧ 0.03. Resist image forming material according to claim 10 or 11 is a scanning exposure 0.1~50mJ / cm ^2.