JP4485288B2 - Blue-violet laser photosensitive composition - Google Patents

Description

  The present invention relates to an etching resist by direct drawing with a blue-violet laser beam in the formation of printed circuit boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, semiconductor packages and other fine electronic circuits. The present invention relates to a blue-violet laser photosensitive composition useful for forming a resist image for a plating resist, a solder resist, and the like, and particularly to a blue-violet laser photosensitive composition suitable for use in the production of a printed wiring board.

  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 the 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 A lithography method is widely used in which a circuit or an electrode pattern drawn on a mask film is formed on a substrate by peeling and removing a resist image after soldering or the like.

  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.

Correspondingly, various studies have been made as a blue-violet laser-sensitive composition, for example, an ethylenically unsaturated compound, a hexaarylbiimidazole compound as a polymerization initiator, and a dialkylaminobenzene compound as a sensitizing dye. Specific polymer binders in which a part of the carboxyl group of the compound and carboxyl group-containing polymer is reacted with the epoxy group of the epoxy group-containing ethylenically unsaturated compound to have an ethylenically unsaturated bond in the side chain, etc. There has also been proposed a lithographic printing plate (see, for example, Patent Document 1) using a photopolymerizable composition in combination with a photosensitive layer. However, since the photosensitive composition layer disclosed therein is used for a lithographic printing plate, when it is used for forming a resist image having a thin film thickness and a film thickness of 5 μm or more, it is based on a blue-violet laser beam. The problem is that the exposure sensitivity is not sufficient, the developability is inferior, the epoxy group-containing ethylenically unsaturated compound remains in the polymer binder, or the resist image is difficult to peel off or remove after resist processing. was there.
JP 2002-296664 A.

  The present invention has been made in view of the above-described prior art, and therefore, when used for resist image formation, the present invention is excellent in sensitivity to blue-violet laser light and developability and resist processing. It is an object of the present invention to provide a blue-violet laser-sensitive composition that is easy to peel and remove the resist image later, and is particularly suitable for direct drawing with a blue-violet laser beam.

As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by using a specific polymer as a polymer binder in the photosensitive composition, and have reached the present invention. Therefore, the gist of the present invention is a blue-violet laser-sensitive composition containing the following component (A), component (B), component (C), and component (D).
(A) ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and viewed including the respective constituent repeating units derived from styrene, further, all the structural repeat structure repeating units derived from hydroxyalkyl (meth) acrylates Carboxy group-containing copolymer (B) ethylenically unsaturated compound (C) photopolymerization initiator (D) sensitizing dye having an absorption maximum in the wavelength range of 355 to 430 nm

  The present invention, when used for resist image formation, is a photosensitive composition that is excellent in sensitivity to blue-violet laser light and developability, and that allows easy removal and removal of a resist image after resist processing, In particular, it is possible to provide a blue-violet laser photosensitive composition suitable for direct drawing with a blue-violet laser beam.

The (A) component carboxyl group-containing copolymer constituting the blue-violet laser-sensitive composition of the present invention is intended to improve the formability and developability of the photosensitive composition on the substrate as a layer. In the present invention, the carboxyl group-containing copolymer must contain constituent repeating units derived from ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and styrenes. .

  Here, in the present invention, specific examples of the ethylenically unsaturated carboxylic acid in the structural repeating unit derived from the ethylenically unsaturated carboxylic acid of the carboxyl group-containing copolymer include (meth) acrylic acid [ In the present invention, “(meth) acryl” means “acryl” or / and “methacryl”. ], Crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like. Among them, (meth) acrylic acid is preferable, and methacrylic acid is particularly preferable.

Further, as the alkyl (meth) acrylates in the structural repeating unit derived from the alkyl (meth) acrylates of the carboxyl group-containing copolymer, specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n- or i-propyl (meth) acrylate, n- or i- or t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-dodecyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate and the like, among which methyl (meth) acrylate, ethyl (meth) acrylate, n- or i- or t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like are particularly preferable preferable.

  Specific examples of the styrenes in the structural repeating unit derived from styrenes of the carboxyl group-containing copolymer include, for example, α-substituted alkylstyrenes such as styrene, α-methylstyrene, α-ethylstyrene, and the like. -Nuclear substituted hydroxystyrene such as methylstyrene, m-methylstyrene, p-methylstyrene, 2,5-dimethylstyrene, etc., o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, etc. , Nucleosubstituted halogenated styrenes such as p-chlorostyrene, p-bromostyrene, dibromostyrene and the like, among which styrene is particularly preferable.

In the present invention, the content of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid in the carboxyl group-containing copolymer is preferably 10% by weight or more with respect to all the constitutional repeating units of the copolymer. The content is particularly preferably 15% by weight or more, more preferably 50% by weight or less, and particularly preferably 35% by weight or less. If the content of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acid is less than the lower limit, the non-exposed part tends to be inferior to the developer after exposure as a photosensitive composition, whereas, if the upper limit is exceeded. The film thickness of the exposed area with respect to the developer tends to be reduced or the resolution tends to be inferior.

  Further, the content of the constitutional repeating unit derived from the alkyl (meth) acrylates in the carboxyl group-containing copolymer is preferably 15% by weight or more based on the total constitutional repeating unit of the copolymer, 30 It is particularly preferably at least wt%, more preferably at most 80 wt%, particularly preferably at most 65 wt%. When the content of the constitutional repeating unit derived from the alkyl (meth) acrylate is less than the lower limit, when the photosensitive composition is used as a dry film resist material, the tackiness is insufficient, and the production and handling as a dry film resist material. On the other hand, when the above upper limit is exceeded, the introduction of other structural repeating units is quantitatively limited, and it is difficult to balance various performances as a carboxyl group-containing copolymer. It becomes.

  Further, the content of the constitutional repeating unit derived from the styrenes in the carboxyl group-containing copolymer is preferably 1% by weight or more, preferably 5% by weight or more with respect to all the constitutional repeating units of the copolymer. It is particularly preferable that it is 40% by weight or less, particularly preferably 15% by weight or less. When the content of the structural repeating unit derived from styrenes is less than the lower limit, the photosensitive layer after exposure as a photosensitive composition or the resist image after development tends to be inferior in scratch resistance, whereas when the upper limit is exceeded, When the photosensitive composition is used as a dry film resist material, the photosensitive composition layer is liable to be cracked.

In addition, as the carboxyl group-containing copolymer in the present invention, in addition to the constituent repeating units derived from the ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and styrenes, the resolution of the resist image obtained is resolved. From the viewpoint of properties, for example, hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. look including the structure repeating unit derived from the content of the structure repeating unit derived from the hydroxyalkyl (meth) acrylates, the total structure repeating units of the copolymer state, and are 1 wt% or more, 5 virtuous Mashiku has a weight% or more, and state, and are 30 wt% or less, 20 wt% or less There's a good Masui.

  Further, as the constitutional repeating unit derived from the alkyl (meth) acrylate, it is preferable to include a constitutional repeating unit derived from an alkyl (meth) acrylate with an alkyl group having 4 or more carbon atoms, and the alkyl having 4 or more carbon atoms. It is preferable that content of the structural repeating unit derived from the alkyl (meth) acrylates based on the group is 15 to 60% by weight with respect to the total amount of the structural repeating units derived from the alkyl (meth) acrylate. In that case, the alkyl group having 4 or more carbon atoms is a linear alkyl group such as n-butyl (meth) acrylate, t-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl ( It is more preferable that it contains a branched alkyl group such as (meth) acrylate, and the ratio of both is linear alkyl group: branched alkyl group = 0.3 to 0.7: 0.7 to 0.3. A range is particularly preferred.

  In addition, as the carboxyl group-containing copolymer in the present invention, each constituent repetition derived from the ethylenically unsaturated carboxylic acids, the alkyl (meth) acrylates, the styrenes, and the hydroxyalkyl (meth) acrylates In addition to the unit, a constitutional repeating unit derived from another copolymerizable monomer may be further contained in an amount of preferably 10% by weight or less, particularly preferably 5% by weight or less. Examples of other polymerizable monomers include benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N- Methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethyl Aminoethyl (meth) acrylamide, other vinyl compounds such as vinyl acetate and the like.

  The carboxyl group-containing copolymer in the present invention preferably has an acid value of 100 to 300 mg · KOH / g, and preferably has a polystyrene equivalent weight average molecular weight of 20,000 or more. More preferably, it is more preferably 40,000 or more, more preferably 150,000 or less, still more preferably 100,000 or less, and particularly preferably 90,000 or less. If the weight average molecular weight is less than the lower limit, the film strength as the photosensitive composition layer is lowered, the developability becomes unstable, and the chipping property tends to deteriorate. The viscosity as the photosensitive composition coating solution is too high, and the coating property tends to be inferior, and the developing property tends to decrease.

  The ethylenically unsaturated compound of component (B) constituting the blue-violet laser-sensitive composition of the present invention is a photopolymerization of component (C) described later when the photosensitive composition is irradiated with actinic rays. A compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by the action of a photopolymerization initiation system containing an 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 addition, the photopolymerization initiator of the component (C) constituting the blue-violet laser-sensitive composition of the present invention is a sensitizing dye when irradiated with light in the presence of a sensitizing dye of the component (D) described later. Is a radical generator that receives the photoexcitation energy of the compound to generate active radicals and leads to polymerization of the ethylenically unsaturated compound of component (B), such as hexaarylbiimidazole compounds, titanocene compounds, halomethyl S-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, diaryliodonium salts, organic borates, and organic peroxides. Among them, hexaarylbiimidazole compounds and titanocene compounds are preferable, and hexaarylbiimidazole compounds are particularly preferable from the viewpoints of sensitivity as a photosensitive composition, adhesion to a substrate, storage stability, and the like.

  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.

  Specific examples of the titanocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium bisphenyl. Cyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6- Tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methyl Cyclopentadienyl) titanium bis (2,3,4,5,6) Pentafluorophenyl), dicyclopentadienyl-titanium-bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a biphenyl structure are preferred, and those in which the o-position of the biphenyl ring is substituted with a halogen atom are particularly preferred.

  The sensitizing dye of component (D) constituting the blue-violet laser-sensitive composition of the present invention has an absorption maximum in the wavelength region of 355 to 430 nm, and efficiently uses light in the blue-violet region of the wavelength region. Active radicals that absorb the light and transmit the photoexcitation energy to the photopolymerization initiator of the component (C), 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. 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. An aminophenyl-benzimidazole / benzoxazole / benzothiazole compound having the following formula described in the specification of JP-362326, etc. as a basic skeleton; and (iii) the following formula described in the specification of Japanese Patent Application No. 2003-17559, etc. (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 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 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.

  The (A) component carboxyl group-containing copolymer constituting the blue-violet laser-sensitive composition of the present invention, the (B) component ethylenically unsaturated compound, the (C) component photopolymerization initiator, and the above (D) Each content rate of the sensitizing dye of a component is 20-80 weight% of (A) component with respect to the whole quantity of a photosensitive composition, (B) 20-80 weight% of component, (C) component Is 0.1 to 20% by weight, and component (D) is preferably 0.01 to 10% by weight.

  The blue-violet laser-sensitive composition of the present invention may contain a hydrogen-donating compound in addition to the components (A) to (D) for the purpose of improving the photopolymerization initiation ability. Examples of the hydrogen-donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, Mercapto group-containing compounds such as β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakis Thiopropione Polyfunctional thiol compounds such as N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or salts thereof such as ammonium and sodium salts, derivatives such as dipolar ionic compounds thereof, phenylalanine, or esters thereof, and ammonium thereof And amino acid having an aromatic ring such as a salt such as sodium salt or a derivative thereof such as a bipolar ion compound or derivatives thereof. Among them, in the present invention, mercapto group-containing compounds and amino acids or derivatives thereof are preferable.

  In the blue-violet laser photosensitive composition of the present invention, the content ratio of the hydrogen-donating compound contained in addition to the components (A) to (D) is 5% by weight or less based on the total amount of the photosensitive composition. It is preferable that it is 2% by weight or less.

  Furthermore, the blue-violet laser-sensitive composition of the present invention includes, in addition to the above-mentioned components, a polymerization inhibitor for preventing thermal or temporal polymerization of the photosensitive composition, and film properties as a photosensitive composition layer. A plasticizer for controlling the color, a dye for visualizing the formed image, a color changing agent, an adhesion imparting agent for imparting adhesion of the formed image to the substrate to be processed, an antioxidant, and a surface A tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a flame retardant, a solvent, a surfactant and the like may be contained as necessary.

  Examples of the polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 2,6-di-t-butyl-p-cresol, 4-methoxy-2-hydroxybenzophenone. , Β-naphthol, naphthylamine, nitrobenzene, picric acid, p-toluidine, chloranil, phenothiazine, cuprous chloride and the like, and as a plasticizer, for example, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, etc. Phthalate esters, glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, phosphate esters such as tricresyl phosphate, triphenyl phosphate, benzenesulfonamide, -Amides such as toluenesulfonamide, Nn-butylacetamide, diisobutyl adipate, dioctyl adipate, dioctyl azelate, dimethyl sebacate, dibutyl malate and other aliphatic dibasic esters, glycerin triacetyl, triethyl citrate And glycols such as tributyl citrate, butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate, polyethylene glycol, polypropylene glycol and the like.

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 (manufactured by Orient Chemical Industries), Victoria Pure Blue BOH, Spiron Blue GN [Made by Hodogaya Chemical Co., Ltd.], rhodamine 6G and the like. Among them, leuco dyes such as leuco crystal violet are 0.01 to 1.5% by weight, particularly 0.05 to 0.5% with respect to the total amount of the photosensitive composition. It is preferably contained in an amount of 0.8% by weight, and further preferably contains 0.001 to 0.5% by weight, particularly 0.002 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 blue-violet laser-sensitive composition of the present invention is a photosensitive composition formed as necessary by coating and drying on a temporary support film as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent. When the surface of the layer is covered with a coating film, a so-called dry film resist material is formed, and when the photosensitive composition layer side is covered with the coating film, the coating film is peeled off and is applied onto the substrate to be processed. The blue-violet laser-sensitive composition is applied onto the substrate to be processed by laminating or by directly applying the solution to the substrate to be processed and then drying it as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent. An image forming method in which a blue-violet laser-sensitive composition layer of the resist image forming material is exposed to a laser beam and developed to reveal an image. It is suitably used in the use form as.

  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 the solvent resistance, heat resistance, etc. necessary for the production of the dry film resist material, the photosensitive composition coating solution is directly applied on the temporary support film. It 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 photosensitive composition layer is formed on a film having releasability, and then a temporary support film having low solvent resistance or heat resistance is laminated on the layer, and then the film having releasability is peeled off. By doing so, a dry film resist material can also be produced. In particular, when high resolution is pursued, the haze value of the temporary support film is preferably 0.01 to 1.8%, and the thickness of the temporary support film is preferably 10 to 30 μm.

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 solvent, 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 ratio of the solvent used is usually in the range of about 0.5 to 2 times by weight with respect to the total amount of the photosensitive 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 photosensitive composition layer with a coating film until it is laminated on a substrate to be processed. Conventionally known films such as polyethylene film, polypropylene film and polytetrafluoroethylene film are used. In particular, when high resolution is pursued, the surface roughness of the coating film is preferably such that Ra of the surface in contact with the photopolymerizable composition is 0.15 μm or less, and Rmax is 1.5 μm or less. The number of fish eyes having a diameter of 80 μm or more contained in the coating film is preferably 5 / m ² or less.

Further, when the photosensitive 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, pressurizing, or the like. The substrate to be processed in preparing the resist image forming material by directly applying and drying the photosensitive composition coating liquid is exposed to a laser beam and developed by exposing the photosensitive composition layer formed thereon. A pattern such as a circuit or an electrode is formed on the surface by etching or plating using the displayed image as a resist. Copper, aluminum, gold, silver, chromium, zinc, tin, lead The metal plate itself such as nickel may be used, but usually, for example, epoxy resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, phenol Resin, thermoplastic resin such as melamine resin, saturated polyester resin, polycarbonate resin, polysulfone resin, acrylic resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polyolefin resin, 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 Or by a method such as sputtering, vapor deposition, plating, etc. Metal-clad laminate formed with 00μm approximately conductive layer is preferably used.

  In the case where a resist image forming material is produced by directly applying and drying the photosensitive composition coating solution, the polymerization inhibiting action by oxygen of the photosensitive composition layer formed on the substrate to be processed For example, a protective layer formed by applying and drying a solution of, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, or hydroxyethyl cellulose is provided on the photosensitive composition layer. May be.

  Then, the photosensitive composition layer of the resist image forming material having the blue-violet laser-sensitive composition layer of the present invention on the substrate to be processed is scanned and exposed with a laser beam and developed to form a resist image. In that case, when the photosensitive composition layer is formed with the dry film resist material, the photosensitive composition is usually applied on the temporary support film or by directly applying the photosensitive composition coating liquid and drying it. When a physical layer is formed and the protective layer is provided, the photosensitive composition layer is usually subjected to scanning exposure with a laser beam from above the protective layer.

  As the laser exposure light source, a blue-violet laser light source that generates laser light in a blue-violet region with a wavelength range of 390 to 430 nm is preferable, and a light source that generates laser light with a wavelength range of 400-420 nm is more preferable. Specific examples include an indium gallium nitride semiconductor laser.

  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 the DMD method is effective for pursuing the resolution. The effect is particularly effective in this DMD type exposure method. 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 photosensitive composition layer is formed of the dry film resist material, the development treatment after the laser exposure is performed by peeling off the temporary support film, or by applying the photosensitive composition coating liquid. In the case where the photosensitive composition layer is formed by directly applying and drying, and having the protective layer, the protective layer is peeled off, and then the alkali salt of sodium carbonate, potassium carbonate or the like is added in an amount of 0. It is carried out using a dilute alkaline aqueous solution of about 3 to 2% by weight. 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 1-5
As a blue-violet laser-sensitive composition, the following carboxyl group-containing copolymers (A1 to A7), ethylenically unsaturated compounds (B1 to B4), photopolymerization initiators (C1 to C2), and sensitizing dyes (D1 to D2) ) And other components (X1 to X2) are added to the following solvent (Y1) in the formulation shown in Table 2, and the 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 such an amount that the dry film thickness is 20 μm, dried in an oven at 90 ° C. for 10 minutes, and on the formed blue-violet laser-sensitive composition layer, A polyethylene film (thickness 25 μm) was laminated to prepare a dry film resist material.

<Carboxyl group-containing copolymer>
Copolymers of (A1) to (A7) shown in Table 1 below

<Ethylenically unsaturated compound>
(B1) The following compound (B2) The following compound (B3) The following compound (B4) The following compound

<Photopolymerization initiator>
(C1) 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (C2) dicyclopentadienyl titanium bis [2,6-difluoro-3- (1 -Pyrrolyl) phenyl]

<Sensitizer>
(D1) 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)
(D2) The following compound (same as above, absorption maximum 352 nm)

<Others>
(X1) leuco crystal violet (X2) crystal violet <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 blue-violet laser-sensitive composition layer was formed was produced.

The obtained blue-violet laser-sensitive composition layer of each resist image forming material is exposed and developed under the following exposure and development conditions, and exposure sensitivity is shown below from the resolution state of the obtained image. Evaluation was performed based on the criteria, and the results are shown in Table 2.

<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, a beam spot diameter of 8 μm and an image plane light quantity of 0.4 mW / cm ² , 4.0 mJ / cm ² , 5 .6 mJ / cm ² 8.0 mJ / cm ² , 11.2 mJ / cm ² , 16.0 mJ / cm ² , and 22.3 mJ / cm ² as 6 levels of exposure, 20 μm collective line (line / space = 20 μm / 20 μm), 20 μm independent lines, and 20 μm independent space exposure patterns were scanned and exposed. 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 portion is completely dissolved). Developed by spraying at 0.15 MPa with a development time of 5 times.

<Evaluation criteria for exposure sensitivity>
The pattern images obtained at each exposure amount were observed with an optical microscope for the resolution of the collective lines, independent lines, and independent spaces, and the exposure sensitivity was evaluated according to the following criteria.
○: Collective line, independent line, independent space are all resolved.
Δ: Two of the collective line, independent line, and independent space are resolved.
X: Resolution is 1 or less among collective lines, independent lines, and independent spaces.

  Separately, the blue-violet laser-sensitive composition layer of each obtained resist image forming material is exposed and developed under the exposure and development conditions shown below, and the developability from the omission state of the obtained image, etc. Were evaluated according to the following criteria, and the results are shown in Table 2.

<Exposure and development conditions>
Under the above exposure conditions, scanning exposure was performed with the minimum exposure amount at which the evaluation of the resolution state was “◯”. 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 portion is completely dissolved). Developed by spraying at 0.15 MPa with development times of 2.times., 1.5.times., And 2.0.times.

<Development evaluation criteria>
The pattern images obtained at each development time were observed with an optical microscope for the missing state of the space portion of the pattern, the width reproduction state of the line portion, and the close contact state, and evaluated according to the following criteria.
○: The space part is completely removed, and the line part is also reproduced with a width of 17 to 23 μm.
X: The space part is not completely removed, the line part is floating, swollen and swelled, the width is narrowed to 16 μm or less, thickened to 24 μm or more, or missing.

Further, scanning exposure is performed with the minimum exposure amount at which the evaluation of the resolution state is “◯” under the above-described exposure conditions (the minimum exposure amount capable of forming an image for each comparative example), and then, a breakpoint of 1.5 is set. The resist image formed by developing with double development time was evaluated for the resist image peeling / removability by the following method, and the results are shown in Table 2.
<Resist image removal / removability>
The resist image was peeled after being immersed in a 3 wt% sodium hydroxide aqueous solution at 45 ° C. for 1 minute, and evaluated according to the following criteria.
○: The resist image can be completely removed and removed.
X: The resist image is not completely peeled or removed, or an afterimage remains.

In carrying out the above examples and comparative examples, all the operations up to the production of each resist image forming material were carried out under a red lamp, and for each of the obtained resist image forming materials, first, under a yellow lamp. Safelight properties were evaluated according to the following criteria. The results are shown in Table 2. About the thing (Examples 1-4, 6, and Comparative Examples 1-5 ) by which safelight property was confirmed, the subsequent operation | work was implemented under yellow light, and the safelight property was not excellent (Example 5) ) Was carried out under red light until the subsequent development.
<Safety property under yellow light>
The resist image-forming material is shielded from light by half of the blue-violet laser-sensitive composition layer surface, and left for 1 hour under illumination with a yellow light, 1 meter away from the light source (illuminance 150 lux), and then subjected to the above-described exposure and development conditions. The film was exposed and developed, and evaluated according to the following criteria. The results are shown in Table 2.
○: The developing time of the yellow lamp irradiation part is less than 1.05 times the developing time of the light shielding part.
(Triangle | delta); The developing time of a yellow lamp irradiation part is 1.05-times and less than 1.1 times the developing time of a light-shielding part.
X: The development time of the exposed part of the yellow light is 1.1 times or more of the development time of the light shielding part.

The blue-violet laser-sensitive organism of the present invention uses a blue-violet laser beam in the formation of 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. It is useful for forming resist images for etching resists, plating resists, solder resists, etc. by direct drawing, and is particularly suitable for the production of printed wiring boards, especially for the production of plating resist images.

Claims (8)

A blue-violet laser-sensitive composition comprising the following component (A), component (B), component (C), and component (D):
(A) ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and viewed including the respective constituent repeating units derived from styrene, further, all the structural repeat structure repeating units derived from hydroxyalkyl (meth) acrylates Carboxy group-containing copolymer (B) ethylenically unsaturated compound (C) photopolymerization initiator (D) sensitizing dye having an absorption maximum in the wavelength range of 355 to 430 nm   The content of each constituent repeating unit derived from the ethylenically unsaturated carboxylic acids, alkyl (meth) acrylates, and styrenes of the carboxyl group-containing copolymer of the component (A) is the total constituent repeating unit of the copolymer. The blue-violet laser-sensitive composition according to claim 1, which is 10 to 50% by weight, 15 to 80% by weight and 1 to 40% by weight, respectively. As the structural repeating unit derived from the alkyl (meth) acrylates of the carboxyl group-containing copolymer of the component (A), including a structural repeating unit derived from an alkyl (meth) acrylate with an alkyl group having 4 or more carbon atoms, The blue-violet laser-sensitive composition according to claim 2, wherein the content is 15 to 60% by weight based on the total amount of the structural repeating units derived from the alkyl (meth) acrylates. In the structural repeating unit derived from alkyl (meth) acrylates with an alkyl group having 4 or more carbon atoms in the carboxyl group-containing copolymer of the component (A), the alkyl group having 4 or more carbon atoms is branched from a linear alkyl group. The blue-violet laser-sensitive composition according to claim 3 , comprising an alkyl group, wherein the ratio of the two is linear alkyl group: branched alkyl group = 0.3 to 0.7: 0.7 to 0.3. object. (B) as the ethylenically unsaturated compound of the component having a polyoxyalkylene group, according to any one of claims 1 to 4 containing ester (meth) acrylates having two or more (meth) acryloyloxy group Blue-violet laser photosensitive composition. The blue-violet laser-sensitive composition according to any one of claims 1 to 5 , comprising a hexaarylbiimidazole compound as a photopolymerization initiator of component (C). As component (D) a sensitizing dye, dialkylamino benzene compounds, triphenylamine compounds, acridone based compounds, and any of claims 1 to 6 from the group consisting of carbazole-based compound containing any of the compounds selected The blue-violet laser-sensitive composition according to claim 1. The dialkylaminobenzene compound is a dialkylaminobenzophenone compound represented by the following general formula (I), a dialkylaminobenzene compound having a sulfonylimino group represented by the following general formula (III), and the following general formula (IV The blue-violet laser-sensitive composition according to claim 7 , which is any compound selected from the group consisting of dialkylaminobenzene-based compounds having a carbostyril skeleton represented by:

[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. ]

[In the 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. ]

[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. ]