JP2005227528A - Resist image forming material and resist image forming method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist image forming material which exhibits high resolution and is excellent also in production stability when a photopolymerizable composition layer sensitive to blue-violet light in the resist image forming material is exposed by a direct drawing method and developed to form a resist image, and also to provide a resist image forming method for the same. <P>SOLUTION: The resist image forming material has a layer of a photopolymerizable composition sensitive to blue-violet light on a substrate to be worked, wherein a content of an antioxidant in the photopolymerizable composition is 10-500 ppm. In the resist image forming method, the photopolymerizable composition layer of the resist image forming material is exposed by a direct drawing method and developed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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 resist image forming material useful for forming a resist image for a solder resist and the like, and a resist image forming method thereof, and particularly a resist image forming material suitable for use in manufacturing a printed wiring board, and the resist The present invention relates to an image forming method.

  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 mask film on which a photosensitive composition layer of 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, if necessary, is described with a circuit or an electrode pattern. After image exposure through, 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, and the exposed portion A resist image corresponding to the circuit pattern is formed by developing using a difference in solubility in the developer in the non-exposed portion, and then the substrate to be processed is etched, plated, or processed using this resist image as a resist. Lithography is widely used in which a resist image is removed after soldering or 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. On the other hand, as laser light that can be used for image exposure, various laser light sources from the ultraviolet region to the infrared region are known, and output, stability, photosensitive ability, and From the viewpoint of cost and the like, an argon ion laser, a helium neon laser, a YAG laser, and a semiconductor laser that emit light in the visible to infrared region are the mainstays. For example, an argon ion laser with a wavelength of 488 nm, a wavelength of 532 nm Although the FD-YAG laser has been put to practical use, the feeling for direct drawing with these visible laser beams Sex composition has poor safelight of under yellow light, there is a restriction that is required to work in a dark room environment, such as a red light illumination.

On the other hand, an ultraviolet solid laser having a wavelength of about 350 to 365 nm capable of working in a bright room environment such as yellow light illumination has been put into practical use, but this ultraviolet solid laser has a light source lifetime of 1,000. It has a short time and the narrowing of the beam diameter is limited to a line / space of about 30 to 50 μm, and it cannot be used for high resolution patterns. In addition, due to significant advances in laser technology in recent years, the lifetime of the light source has been extended to 10,000 to 20,000 hours, and the beam diameter can be narrowed down to 10 μm or less. The use of semiconductor lasers that can work and can stably oscillate in the blue-violet region of wavelength 390 to 430 nm has come to practical use. In addition, there is a demand for a photosensitive composition that has sensitivity that can be used for direct drawing with the blue-violet laser beam and that has excellent resolution, and from the viewpoint of improving the processing ability of image formation such as circuit pattern formation. While there is a demand for further higher sensitivity, the applicant of the present application previously described a photopolymerizable blue-violet laser-sensitive composition capable of forming an image at 10 mJ / cm ² or less, and thus 200 μJ / cm ² or less. A patent application was filed for the product (for example, Japanese Patent Application No. 2002-294622). In recent years, a direct drawing method using, for example, ultraviolet lamp light as a light source other than laser light has been proposed.

  However, in these direct drawing methods, although it is possible to cope with sensitivity by using a photopolymerizable composition corresponding to high sensitivity, high resolution, particularly in a state where the film thickness of the photopolymerizable composition layer is thick. It is difficult to cope with high resolution in the resist image forming material to be used, and a resist image pattern obtained by exposure and development processing is rounded, or a phenomenon called skirting occurs due to insufficient skirt cutting. It has been found that there is room for improvement in resolution. In addition, the photopolymerizable composition layer is usually formed by applying and drying a photopolymerizable composition coating solution. In the drying process, performance may vary depending on the drying conditions, and the speed is increased. It was also found that the tendency of variation becomes even larger.

  The present invention has been made in view of the above-described prior art. Therefore, the present invention exposes a blue-violet photosensitive photopolymerizable composition layer in a resist image forming material by a direct drawing method, and develops it. Thus, in forming a resist image, it is an object to provide a resist image forming material that exhibits high resolution and is excellent in manufacturing stability, and a resist image forming method thereof.

  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 amount of an antioxidant in the photopolymerizable composition, and has reached the present invention. The present invention is a resist image forming material having a layer of a blue-violet photosensitive photopolymerizable composition on a substrate to be processed, wherein the content of the antioxidant in the photopolymerizable composition is 10 to 500 ppm. The gist of the present invention is a resist image forming material and a resist image forming method in which a photopolymerizable composition layer of the resist image forming material is exposed and developed by direct drawing.

  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, thereby exhibiting high resolution and manufacturing stability. In addition, an excellent resist image forming material and a resist image forming method thereof can be provided.

  In the resist image forming material of the present invention, the content of the antioxidant in the photopolymerizable composition of the resist image forming material having a layer of a blue-violet photosensitive photopolymerizable composition on a substrate to be processed is 10 to 10. It is essential that the content is 500 ppm, and the content is 30 ppm or more and preferably 160 ppm or less.

  That is, the photopolymerizable composition of a resist image forming material having a layer of a photopolymerizable composition on a substrate to be processed includes an ethylenically unsaturated compound or a polymer binder that is an essential component in the photopolymerizable composition. In some cases, an antioxidant is added in advance in order to avoid deterioration due to oxidation, coloring, etc., and it was sometimes included in the photopolymerizable composition. Resist image forming materials that are blue-violet light-sensitive have not been commercialized yet, and those that are blue-violet light-sensitive are low in sensitivity in terms of storage and working environments as compositions. From the fact that there are no problems such as degradation due to oxidation, coloring, etc., while the addition of antioxidants to ethylenically unsaturated compounds and polymer binders was not conscious, In the present invention, Characterized in that it the antioxidant is contained specific amount.

  In the present invention, when the content of the antioxidant in the photopolymerizable composition is less than the above range, the pattern of the resulting resist image is rounded, or there is a phenomenon called tailing due to insufficient hem cutting. The problem is that the resolution is inferior, for example, and the photopolymerizable composition layer is susceptible to the drying conditions when forming the coating liquid by applying and drying the coating solution, resulting in unstable production. Occurs. On the other hand, when the above range is exceeded, the sensitivity as the photopolymerizable composition is lowered.

  In the present invention, the antioxidant is not particularly limited as long as it is usually used as an antioxidant, and typically, for example, a phenol-based amine and an amine as a primary antioxidant are used. -Based antioxidants, and sulfur-based and phosphorus-based antioxidants as secondary antioxidants, among which phenol-based and amine-based primary antioxidants are preferred, and phenol-based oxidation Inhibitors are particularly preferred.

  The phenolic antioxidant is preferably a monohydric phenol derivative containing a monohydroxybenzene ring, the monohydroxybenzene ring having at least one branched alkyl group having 4 to 6 carbon atoms in the o-position, It is particularly preferable that the monohydroxybenzene ring has a branched alkyl group having 4 to 6 carbon atoms at both o-positions. Examples of the branched alkyl group include t-butyl group, i-butyl group, t-amyl group, i-amyl group and the like.

  Specific examples of the monohydric phenol derivative in which the monohydroxybenzene ring has at least one branched alkyl group having 4 to 6 carbon atoms in the o-position include, for example, 2,6-di-t-butylphenol, 2,6-di -T-butyl-p-cresol, 2,6-di-i-butyl-p-cresol, 2,6-di-t-amyl-p-cresol, 2,6-di-t-butyl-4-ethyl Phenol, 2,4,6-tri-t-butylphenol, i-octyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, n-octadecyl-3- (3 ′ , 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, monopheno such as styrenated phenol 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6- Di-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4,4′-thiobis ( 2-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), triethylene glycol bis [3- (3′-tert-butyl-4′-hydroxy-5) '-Methylphenyl) propionate], hexamethylene glycol bis [3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 2,2 Thio-diethylenebis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4- Bisphenols such as hydroxy-hydrocinnamamide) and bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 1,1,3-tris (2′-methyl-4′-) Hydroxy-5′-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) benzene, tris ( 3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate 2,4-bis-n-octyl-6- (3 ′, 5′-di-t-butyl-4′-hydroxyanilino) -1,3,5-triazine, tetrakis [methylene-3- (3 ′ , 5'-di-t-butyl-4'-hydroxyphenyl) propionate] and other high molecular phenolic compounds such as methane.

  In the present invention, the content of the antioxidant in the photopolymerizable composition is determined by photopolymerization of a resist image forming material dissolved in acetone based on a calibration curve prepared with a standard solution such as acetone by gas chromatography. It can quantify from the measured value by the gas chromatography about the 10 weight% solution of a property composition layer.

Although it does not specifically limit as a photopolymerizable composition in this invention, It is preferable to contain the following (A) component, (B) component, and (C) component, and also (D It is particularly preferred that it contains a component.
(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

  In the present invention, the carboxyl group-containing polymer of the component (A) that constitutes a preferred photopolymerizable composition improves the formability as a layer of the photopolymerizable composition on the substrate, and developability, etc. Specifically, for example, (meth) acrylic acid [in the present invention, “(meth) acrylic” means “acrylic” and / or “methacrylic”. . ], 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). ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, α-substituted alkylstyrenes such as styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p- Methylstyrene, 2, -Nuclear substitution alkyl styrene such as dimethyl styrene, nuclear substitution such as o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, dihydroxy styrene, etc., nuclear substitution such as p-chloro styrene, p-bromo styrene, dibromo styrene Styrenes such as halogenated styrene, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) Examples include other vinyl compounds such as acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and vinyl acetate.

  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.

  In the present invention, the ethylenically unsaturated compound (B) constituting the photopolymerizable composition that is preferred in the present invention will be described later when the photopolymerizable composition is irradiated with actinic rays (C). It is a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by the action of a photopolymerization initiating system containing a component photopolymerization initiator, and in some cases, crosslinks and cures.

  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.

  In the present invention, the photopolymerization initiator (C) constituting the preferred photopolymerizable composition is irradiated with light in the presence of a sensitizing dye (D) described later, A radical generator that receives photoexcitation energy of a sensitizing dye to generate active radicals and leads to polymerization of the ethylenically unsaturated compound of component (B), for example, hexaarylbiimidazole compounds, titanocenes Examples thereof include compounds, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, diaryliodonium salts, organic borates, 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) biimidazole, 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.

  In the present invention, the sensitizing dye of component (D) that constitutes a preferred photopolymerizable composition has an absorption maximum in the wavelength region of 355 to 430 nm, and has a blue-violet region in the wavelength region. Absorbs light efficiently and transmits its photoexcitation energy to the photopolymerization initiator of the component (C) to decompose the photopolymerization initiator and induce polymerization of the ethylenically unsaturated compound of the component (B). It is a light-absorbing dye having a sensitizing function for generating active radicals. 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 following formula as described in the specification of Japanese Patent Application No. 2003-17559 (Iv) an aminocarbostyryl compound having the following formula as described in Japanese Patent Application No. 2002-365470, etc., and (v) Japanese Patent Application Laid-Open No. 2002-169282, Japanese Patent Application No. 2002. A merocyanine compound having a basic skeleton represented by the following formula described in the specification of 344555, etc., (vi) JP-A-2002-268239 (Vii) an imide-based compound having the following formula as a basic skeleton described in Japanese Patent Application No. 2003-291606, (viii) a basic formula Benzimidazole / benzoxazole / benzothiazole compounds having a skeleton, (ix) Triazole compounds having the following formula as a basic skeleton, (x) Cyanostyryl compounds having the following formula as a basic skeleton, (xi) Based on the following formula A stilbene compound having a 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 coumarin having the following formula as a basic skeleton. Compounds, (xv) triphenylamine compounds having the following formula as described in Japanese Patent Application No. 2003-435212, etc., and (xvi) Japanese Patent Application No. 2003-340924 Acridone based compounds having a basic skeleton of the following formula described in the book or the like, and 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 alkyl groups 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 tetrahydroquinoline wherein 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 A ring is preferably formed, and R ¹ , R ² , R ³ and R ⁴ , and / or R ⁵ , R ⁶ , R ⁷ and R ⁸ particularly preferably form a julolidine ring. 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.

  In the present invention, the carboxyl group-containing polymer of the component (A) constituting the preferred photopolymerizable composition, the ethylenically unsaturated compound of the component (B), the photopolymerization initiator of the component (C), And each content rate of the sensitizing dye of said (D) component is 20-80 weight% of (A) component, 20-80 weight% of (B) component with respect to the whole quantity of a photosensitive composition, (C It is preferable that the component is 0.1 to 20% by weight and the component (D) is 0.01 to 10% by weight.

  In the present invention, a photopolymerizable composition that is preferred may contain a hydrogen-donating compound in addition to the components (A) to (D) for the purpose of improving photopolymerization initiation ability. Well, as the hydrogen donating compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -Mercapto group-containing compounds such as quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, Pentaerythritol tetrakisti Polyfunctional thiol compounds such as propionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or an ester thereof, a salt such as an ammonium or sodium salt thereof, a derivative such as a bipolar ion compound thereof, phenylalanine, or an ester thereof Amino acids having an aromatic ring such as salts thereof such as ammonium and sodium salts, derivatives such as bipolar ion compounds thereof, and derivatives thereof.

  In the present invention, the preferred photopolymerizable composition has a proportion of the hydrogen-donating compound contained in addition to the components (A) to (D) of 5 to the total amount of the photopolymerizable composition. It is preferably not more than wt%, more preferably not more than 2 wt%.

  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.

Further, the preferred photopolymerizable composition includes, in addition to the above components, a plasticizer for controlling film physical properties as a photopolymerizable composition layer, a dye for visualizing an image to be formed, and a color change agent. , adhesion imparting agent for imparting adhesion to the substrate to be processed of an image formed,及beauty, surface tension modifiers, stabilizers, chain transfer agents, antifoaming agents, flame retardants, solvents, surfactants An agent or the like may be contained as necessary.

  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 dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], tris (4-diethylamino-2-methylphenyl) methane, leucomacalite green, leucoaniline, leucomethyl violet, brilliant green, Eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow , Thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl , Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue A, Phenacetalin, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue # 603 (Orient Chemical Industries), Victoria Pure Blue BOH, Spiron Blue GN [Made by Hodogaya Chemical Co., Ltd.], rhodamine 6G and the like. Among them, leuco dye such as leuco crystal violet is 0.01 to 1.5% by weight, particularly 0.05% with respect to the total amount of the photopolymerizable composition. It is preferable to contain 0.01 to 0.5% by weight, particularly 0.01 to 0.2% by weight of crystal violet, macalite green, brilliant green and the like.

  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 photopolymerizable composition of the present invention is, for example, a coating solution obtained by dissolving or dispersing each of the above components in a suitable solvent, applied onto a temporary support film and dried, and if necessary, formed photopolymerizability. By covering the surface of the composition layer with a coating film, a so-called dry film resist material is formed. If the photopolymerizable composition layer side is covered with the coating film, the coating film is peeled off and processed. Photopolymerizable composition on the substrate to be processed by laminating on the substrate 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. It is a resist image forming material on which a layer of the product is formed, and the photopolymerizable composition layer of the resist image forming material is exposed by a direct drawing method and used as a resist image forming method for development processing. Used to apply.

  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 knife coating method, a roll coating method, a spray coating method, a spin coating method or the like 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, and laser light in the wavelength range of 400 to 420 nm 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.

  Further, the exposure method is not particularly limited, but the plane scanning exposure method is preferable in view of the properties of the substrate to be processed, and a slot unit in which a plurality of semiconductor lasers are bundled to ensure sufficient throughput. The state 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 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 1-6, Comparative Examples 1-3
As the photopolymerizable composition, the following carboxyl group-containing polymer (A1), ethylenically unsaturated compound (B1 to B2), photopolymerization initiator (C1), sensitizing dye (D1 to D2), and others An antioxidant (X1 to X3), a polymerization inhibitor (addition) (X4), and a dye (X5 to X5) as components are added to the following solvent (Y1) in the formulation shown in Table 1, and room temperature is added. The coating solution prepared by stirring in step 1 was applied onto a polyethylene terephthalate film (thickness 25 μm) as a temporary support film in an amount to give a dry film thickness of 25 μm using a 100 μm applicator, and air-dried at 25 ° C. for 1 minute. Thereafter, a method of drying in an oven at 85 ° C. for 1 minute (referred to as “drying method-1”), or a method of air drying at 25 ° C. for 1 minute and then drying in an oven at 50 ° C. for 10 minutes (“drying method-2”). ”) More dried, the formed photopolymerizable composition layer on a polyethylene film as a coating film (thickness 25 [mu] m) were laminated 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 compound (with no antioxidant added, containing 100 ppm of p-methoxyphenol as a polymerization inhibitor)
(B2) The following compound (with no antioxidant added, containing 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)
(D2) The following compound (when the sensitizing dye is diluted 60,000 times with tetrahydrofuran and the UV absorption coefficient is measured in the wavelength region of 300 to 500 nm, the absorption maximum existing at the longest wavelength is 365 nm)

<Others>
Antioxidant; (X1) 2,6-di-t-butyl-p-cresol
(X2) 2,6-di-t-butylphenol
(X3) 2,2′-methylenebis (4-methyl-6-tert-butylphenol);
Polymerization inhibitor; (X4) p-methoxyphenol (addition)
Dye: (X5) Leuco Crystal Violet
(X6) Macalite Green <Solvent>
(Y1) methyl ethyl ketone

  Separately, a copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm-thick copper foil is buffed with “Scotch Bright SF” manufactured by Sumitomo 3M Limited. Then, after washing with water, drying with an air stream and leveling, and then preheating this to 80 ° C. in an oven, on the copper foil of the copper clad laminate, the dry film resist material obtained above is While peeling the polyethylene film, using a hand-type roll laminator on the peeling surface, laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min on the copper-clad laminate. A resist image forming material on which a photopolymerizable composition layer was formed 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.

<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, the exposure dose is 20 μm at three stages of exposure amounts of 8 mJ / cm ² , 11 mJ / cm ² and 16 mJ / cm ^2. The exposure pattern of the collective line (line / space = 20 μm / 20 μm) was subjected to scanning exposure. 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.

<Pattern shape>
The pattern shape obtained by exposure with the optimum exposure amount was observed with a scanning electron microscope and evaluated according to the following criteria.
◎; Rectangle with sharp corners and no skirting.
○: Rectangle and no tailing, but slightly sharp.
Δ: Rectangular but slightly skirted.
× -1; The skirt is constricted.
X-2: The skirt is intense and the part where the space part cannot be removed is also seen.
XX: The pattern is not sufficiently formed due to insufficient sensitivity.

  The resist image forming material and the resist image forming method of the present invention are used to form printed circuit boards, plasma display wiring boards, liquid crystal display wiring boards, large scale integrated circuits, thin transistors, fine electronic circuits such as semiconductor packages, and the like. Is useful for forming a resist image for an etching resist, a plating resist, a solder resist, etc. by a direct drawing method, particularly by a direct drawing method using a blue-violet laser beam. Is suitable for use in the production of a plating resist image requiring the above.

Claims (13)

A resist image forming material having a layer of a blue-violet photosensitive photopolymerizable composition on a substrate to be processed, wherein the content of the antioxidant in the photopolymerizable composition is 10 to 500 ppm. Resist image forming material. The resist image forming material according to claim 1, wherein the antioxidant is a monohydric phenol derivative containing a monohydroxybenzene ring. The resist image forming material according to claim 2, wherein the monovalent phenol derivative contains a monohydroxybenzene ring having at least one branched alkyl group having 4 to 6 carbon atoms at the o-position. The resist image forming material according to claim 3, wherein the monovalent phenol derivative contains 1 to 4 monohydroxybenzene rings having a branched alkyl group having 4 to 6 carbon atoms at both o-positions. The resist image forming material according to claim 1, wherein the photopolymerizable composition layer has a thickness of 5 μm or more. The resist image forming material according to any one of claims 1 to 5, wherein the photopolymerizable composition contains the following components (A), (B), (C), and (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 Each constituent repeating unit derived from (meth) acrylic acid, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and styrenes as the carboxyl group-containing polymer of the component (A) in the photopolymerizable composition The resist image forming material according to claim 6, comprising a copolymer having The photopolymerizable composition contains an ester (meth) acrylate having a polyoxyalkylene group and having two or more (meth) acryloyloxy groups as the ethylenically unsaturated compound of the component (B). 8. The resist image forming material according to 7. The resist image forming material according to any one of claims 6 to 8, wherein the photopolymerizable composition contains a hexaarylbiimidazole compound as a photopolymerization initiator of the component (C). The photopolymerizable composition contains any compound selected from the group consisting of dialkylaminobenzene compounds, triphenylamine compounds, acridone compounds, and carbazole compounds as the sensitizing dye of component (D). The resist image forming material according to claim 6. The resist image forming material according to claim 1, wherein the content of the polymerization inhibitor in the photopolymerizable composition is 5 to 60 ppm. 12. A resist image forming method, wherein the photopolymerizable composition layer of the resist image forming material according to claim 1 is exposed and developed by a direct drawing method. The resist image forming method according to claim 12, wherein the exposure light source is blue-violet semiconductor laser light having a wavelength range of 390 to 430 nm.