JP2006293094A - Photopolymerizable composition, image forming material and imaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition which excels in sensitivity, resolution, adhesion and developability and ensures easy stripping and removal of a resist image after resist processing when used for resist image formation, and which is particularly suitable for use in direct drawing with blue-violet laser beam or ultraviolet radiation. <P>SOLUTION: The photopolymerizable composition contains (A) an alkali-soluble resin containing constitutional repeating units derived from alicyclic unsaturated hydrocarbons, (B) an ethylenically unsaturated compound and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

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, an image forming material (a) or the like has been used for forming 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. Lithographic methods are widely used.
The image forming material (a) is a dry composition in which a photosensitive composition layer is formed by applying a coating liquid of a photosensitive composition on a temporary support film and drying it, and covering the surface of the photosensitive composition layer with a coating film. A film resist material or the like.

  The lithography method is performed according to the following procedure. First, the photosensitive image forming material (b) is produced by peeling off the coating film of the image forming material (a) and laminating it on the substrate to be processed. For the image forming material (b), the photosensitive composition coating liquid is directly applied onto the substrate to be processed and dried to form a photosensitive composition layer, and the surface of the photosensitive composition layer is protected as necessary. It is also produced by covering with a layer.

  Next, the photosensitive composition layer of the image forming material (b) on the substrate to be processed is subjected to image exposure through a mask film on which a circuit and an electrode pattern are drawn. Then, the temporary support film or the protective layer is peeled off, and a resist image corresponding to the circuit pattern is formed by developing using the difference in solubility between the exposed portion and the unexposed portion in the developer. Then, the substrate to be processed is etched, plated, or soldered using the resist image as a resist, and then the resist image is removed to form a circuit or electrode pattern drawn on the mask film on the substrate.

On the other hand, in recent years, a laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using laser light as an exposure light source is not only productive, but also resolution and positional accuracy. As a result, the use of laser light has been actively studied in the lithography method.
By the way, various light sources from the ultraviolet region to the infrared region are known as laser light. As laser light that can be used for image exposure, argon ions are used from the viewpoint of output, stability, photosensitive ability, cost, and the like. Lasers, helium neon lasers, YAG lasers, and semiconductor lasers that emit light in the visible to infrared region are the mainstays. For example, an argon ion laser with a wavelength of 488 nm and an FD-YAG laser with a wavelength of 532 nm were used. Lithography has already been put into practical use. However, these photosensitive compositions for direct drawing with visible laser light are inferior in safe light property under yellow light, and have a restriction that work in a dark room environment such as red light illumination is necessary. .

  On the other hand, the practical application of an ultraviolet solid laser having a wavelength of about 350 to 365 nm, which can be operated in a bright room environment such as yellow light illumination, has been studied. Conventional ultraviolet solid-state lasers have drawbacks such that the life of the light source is as short as about 1,000 hours, the beam diameter cannot be narrowed down so that thin lines can be drawn, and high-resolution patterns cannot be handled. However, due to the remarkable progress of laser technology in recent years, the life of the light source has been extended to 10,000 to 20,000 hours, the beam diameter can be narrowed down to 10 μm or less, and work under a yellow light is possible. Utilization of a semiconductor laser that can stably oscillate in a blue-violet region with a wavelength of 390 to 430 nm has come into 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 been proposed a lithographic printing plate using a photopolymerizable composition in combination with a photosensitive layer (Patent Document 1). However, since the photosensitive composition layer disclosed therein is for a lithographic printing plate, it is thin and has a thickness of 5 μm or more. There was a problem that the exposure sensitivity was not sufficient and the developability was poor. In addition, there is a problem that it is difficult to remove and remove the resist image after the resist processing which seems to be caused by the epoxy group-containing ethylenically unsaturated compound remaining in the polymer binder.

On the other hand, as the high-resolution image forming material (a), for example, a binder polymer containing a (meth) acrylic acid ester having a branched or cyclic saturated hydrocarbon group having 9 or more carbon atoms as a copolymerization component; A photosensitive element using a photosensitive resin composition containing an ethylenically unsaturated compound and a photopolymerization initiator has been proposed (Patent Document 2). However, the photosensitive element disclosed therein can obtain high resolution when exposed at an exposure amount of 100 mJ / cm ² or more using a high-pressure mercury lamp or the like, and direct drawing from the viewpoint of throughput. The sensitivity was insufficient.
JP 2002-296664 A JP 2004-317874 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, resolution, adhesion and developability, It is an object of the present invention to provide a photopolymerizable composition that can be easily peeled off and removed after resist processing, and particularly suitable for direct drawing by blue-violet laser light and ultraviolet light. And Another object of the present invention is to provide an image forming material and an image forming material suitable for direct drawing using blue-violet laser light and ultraviolet light, in particular, by using the photopolymerizable composition.

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. That is, the gist of the present invention is a photopolymerizable composition comprising the following components (A), (B), and (C).
(A) Alkali-soluble resin containing alicyclic unsaturated hydrocarbons as copolymerization component (B) Ethylenically unsaturated compound (C) Photopolymerization initiator Further, the present invention provides the photopolymerization on a temporary support film. Another gist of the present invention is an image-forming material characterized in that a layer of a composition is formed.

  In addition, another gist of the present invention is an image forming material in which the image forming material is laminated on a substrate to be processed on the photopolymerizable composition layer side.

  The present invention is a photopolymerizable composition that, when used for resist image formation, is excellent in sensitivity, resolution, adhesion and developability, and is easy to remove and remove a resist image after resist processing. In particular, it is possible to provide a photopolymerizable composition suitable for direct drawing using blue-violet laser light or ultraviolet light.

The constituent features of the present invention described below are representative examples of embodiments of the present invention and are not specified in these contents. In the present invention, “(meth) acryl” means “acryl” and / or “methacryl”.
[1] Photopolymerizable composition The photopolymerizable composition of the present invention comprises the following components (A), (B), and (C). Further, if necessary, it may further contain components other than those described above.

(A) Alkali-soluble resin containing alicyclic unsaturated hydrocarbons as copolymerization component (B) Ethylenically unsaturated compound (C) Photopolymerization initiator Each component will be described in detail below.
[1-1] (A) Alkali-soluble resin containing alicyclic unsaturated hydrocarbons as copolymerization component The alkali-soluble resin (A) constituting the photopolymerizable composition of the present invention is on the substrate. It is intended to improve the formability, resolution, adhesion, developability, releasability, etc. as a layer of the photopolymerizable composition. In the present invention, alicyclic unsaturated hydrocarbons are used. It is essential to contain it as a copolymerization component (containing structural repeating units derived from alicyclic unsaturated hydrocarbons).

Specific examples of the alicyclic unsaturated hydrocarbons include cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cycloocta Unsubstituted monocyclic alicyclic unsaturated hydrocarbons having 5 to 20 carbon atoms, such as dienes;
1-chloro-1-cyclopentene, 2-cyclohexen-1-ol, 3-bromocyclohexene, 1-methyl-1-cyclohexene, 4-methyl-1-cyclohexene, 3-cyclohexene-1-methanol, 3-methyl-2 -Cyclohexen-1-ol, 6-methyl-3-cyclohexene-1-methanol, 4-cyano-1-cyclohexene, 1-morpholino-1-cyclohexene, terpinen-4-ol, α-terpinene, γ-terpinene, α Substituted monocyclic alicyclic unsaturated hydrocarbons having 5 to 20 carbon atoms, such as terpineol, 1-phenyl-1-cyclohexene, 4-phenyl-1-cyclohexene;
Examples thereof include unsubstituted or substituted polycyclic alicyclic unsaturated hydrocarbons having 6 to 20 carbon atoms such as norbornene, dicyclopentadiene, α-pinene, and compounds represented by the following structural formula.

  Among them, unsubstituted or alkyl group-substituted monocyclic alicyclic unsaturated hydrocarbons having 5 to 20 carbon atoms and unsubstituted or alkyl group-substituted bicyclic alicyclic unsaturated groups having 6 to 20 carbon atoms Hydrocarbons are preferred, unsubstituted or alkyl group-substituted monocyclic alicyclic unsaturated hydrocarbons having 6 to 12 carbon atoms, and unsubstituted or alkyl group-substituted bicyclic alicycles having 7 to 15 carbon atoms Formula unsaturated hydrocarbons are more preferable, and cyclohexene, norbornene, dicyclopentadiene, and compounds represented by the following structural formulas are particularly preferable.

  In the alkali-soluble resin (A), the copolymer component having an alkali-soluble group includes o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy- ethylenically unsaturated phenols containing a phenolic hydroxyl group such as α-methylstyrene, p-hydroxy-α-methylstyrene; (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, Examples include ethylenically unsaturated carboxylic acids containing a carboxyl group such as citraconic acid. Among them, ethylenically unsaturated carboxylic acids containing a carboxyl group are preferable, and (meth) acrylic acid is particularly preferable.

  In addition, as the alkali-soluble resin in the present invention, in addition to the constituent repeating units derived from the alicyclic unsaturated hydrocarbons and the copolymerization component having the alkali-soluble group, the resolution of the resist image obtained is obtained. For example, hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. It preferably contains derived structural repeating units.

  In the present invention, the content of the constitutional repeating unit derived from the alicyclic unsaturated hydrocarbons in the alkali-soluble resin is preferably 1% by weight or more based on the total constitutional repeating unit of the copolymer, The amount is particularly preferably 2% by weight or more, more preferably 30% by weight or less, and particularly preferably 20% by weight or less. If the content of the structural repeating unit derived from the alicyclic unsaturated hydrocarbons is less than the lower limit, the exposed portion swells during development and the resolution tends to decrease. Since the hydrophobicity of the portion is increased, the developability is deteriorated and a residue tends to be easily generated.

  Further, the content of the constitutional repeating unit derived from the ethylenically unsaturated carboxylic acids in the alkali-soluble resin is preferably 10% by weight or more, more preferably 15% by weight or more based on the total constitutional repeating unit of the copolymer. Is 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 photopolymerizable composition tends to be inferior in the non-exposed part with respect to the developer after exposure, whereas the upper limit is exceeded. Then, the film thickness of the exposure part with respect to a developing solution arises, or it tends to be inferior in resolution.

Further, the content of the constitutional repeating unit derived from the hydroxyalkyl (meth) acrylates in the alkali-soluble resin is preferably 1% by weight or more with respect to all the constitutional repeating units of the copolymer, and is preferably 5% by weight. The above is particularly preferable, and it is preferably 30% by weight or less, and particularly preferably 20% by weight or less.
The repeating unit constituting the alkali-soluble resin of the component (A) in the present invention is a repeating unit derived from the alicyclic unsaturated hydrocarbons, ethylenically unsaturated carboxylic acids, and hydroxyalkyl (meth) acrylates. In addition, methyl (meth) acrylate, ethyl (meth) acrylate, n- or i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, 2-ada Alkyl (meth) acrylates such as ntil (meth) acrylate; and / or styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,5-dimethyl Styrenes such as styrene, p-chlorostyrene, p-bromostyrene, dibromostyrene and the like may be contained.

  Alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-adamantyl (meta ) Acrylate and the like are particularly preferable, and the content of the structural repeating unit derived from the alkyl (meth) acrylates in the alkali-soluble resin is preferably 15% by weight or more based on the entire structural repeating unit of the copolymer. 30% by weight or more is particularly preferable, 80% by weight or less is preferable, and 65% by weight or less is particularly preferable. When the content of the constitutional repeating unit derived from alkyl (meth) acrylates is too small, tackiness is insufficient in the case of using a photopolymerizable composition as a dry film resist material, and production and handling as a dry film resist material On the other hand, if it is too much, the introduction of other constitutional repeating units is quantitatively restricted, and it tends to be difficult to balance various performances as a carboxyl group-containing copolymer. Become.

  As the styrenes, styrene and α-methylstyrene are particularly preferable, and the content of the constitutional repeating unit derived from the styrenes in the alkali-soluble resin is 1% by weight or more with respect to all the constitutional repeating units of the copolymer. It is preferably 5% by weight or more, more preferably 40% by weight or less, and particularly preferably 15% by weight or less. If the content of the constitutional repeating unit derived from styrenes is too small, the photopolymerizable composition tends to be inferior in the scratch resistance of the photosensitive layer after exposure or the resist image after development. When the polymerizable composition is used as a dry film resist material, cracks tend to occur in the photopolymerizable composition layer when the polymerizable composition is used as a dry film resist material.

In the present invention, the alkali-soluble resin 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, preferably 30,000 or more. 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. When the weight average molecular weight is too small, the film strength as the photopolymerizable composition layer is lowered, and the developing property tends to be unstable or the chipping property is deteriorated. The viscosity as the polymerizable composition coating solution is too high, resulting in poor applicability and a tendency to deteriorate developability.
[1-2] (B) Ethylenically unsaturated compound The ethylenically unsaturated compound (B) constituting the photopolymerizable composition of the present invention is obtained when the photopolymerizable composition is irradiated with actinic rays. In addition, at least one radically polymerizable ethylenically unsaturated bond that undergoes addition polymerization by the action of a photopolymerization initiating system containing a photopolymerization initiator of the component (C) described later, and in some cases crosslinks and cures in the molecule. It is a compound that has.

  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)
Examples thereof include epoxy (meth) acrylates of acrylic acid or 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 2-14), propylene glycol, polypropylene glycol (addition number 2-14), 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, and triethanolamine, 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, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,6 Aliphatic polymers such as 11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates Aneto, a reaction product of a polyisocyanate compounds and the like.

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

In addition to the above, as other ethylenically unsaturated compounds, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, etc. Is mentioned. These ethylenically unsaturated compounds may be used alone or in combination of two or more.
As the ethylenically unsaturated compound of the above component (B), in the present invention, ester (meth) acrylates or urethane (meth) acrylates are preferable, ester (meth) acrylates are particularly preferable, and the ester ( Among the (meth) acrylates, ester (meth) acrylates having a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or a polyethylene oxide adduct of bisphenol A, and having two or more (meth) acryloyloxy groups are particularly preferred. preferable.
[1-3] (C) Photopolymerization initiator The photopolymerization initiator of component (C) constituting the photopolymerizable composition of the present invention is coexisting with a sensitizing dye of component (D) described later. A radical generator that receives photoexcitation energy of a sensitizing dye and generates an active radical when it is irradiated with light, and leads to polymerization of the ethylenically unsaturated compound of component (B), Examples thereof include arylbiimidazole compounds, titanocene compounds, halomethylated 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 photopolymerizable 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 (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (p-methylphenyl) -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 ( -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.
[1-4] Sensitizing dye The photopolymerizable composition of the present invention contains (D) a sensitizing dye having an absorption maximum in the wavelength range of 355 to 430 nm in order to make it highly sensitive to blue-violet laser light. can do. The sensitizing dye of component (D) efficiently absorbs light in the blue-violet region of the wavelength region, transmits the photoexcitation energy to the photopolymerization initiator of component (C), and transmits the photopolymerization initiator. It is a light-absorbing dye having a sensitizing function for decomposing and generating active radicals that induce polymerization of the ethylenically unsaturated compound of the component (B). 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 JP-A No. 2004-198446, and (ii) JP-A No. 2004. -Aminophenyl-benzimidazole / benzoxazole / benzothiazole compounds having the following formula as described in the specification of JP-A-198446, etc., and (iii) the following formula as described in JP-A-2004-252421, etc. as the basic skeleton (Iv) an aminocarbostyryl compound having a basic skeleton represented by the following formula described in JP-A No. 2004-221958 and the like, (v) JP-A No. 2002-169282, JP-A No. 2004-2004 A merocyanine compound having a basic skeleton represented by the following formula described in the specification of 191938, etc .; (vi) JP 2002-268239 A (Vii) an imide-based compound having the following formula as a basic skeleton described in Japanese Patent Application No. 2003-291606, (viii) Benzimidazole / benzoxazole / benzothiazole compounds having a basic skeleton, (ix) triazole compounds having the following formula as a basic skeleton, (x) cyanostyryl compounds having the following formula as a basic skeleton, (xi) A stilbene compound having a basic skeleton, (xii) an oxadiazole / thiadiazole compound having the following formula as a basic skeleton, (xiii) a pyrazoline compound having the following formula as a basic skeleton, and (xiv) a formula having the following formula as a basic skeleton A coumarin compound, (xv) a triphenylamine compound having the following skeleton as described in Japanese Patent Application No. 2004-218915, etc., and (xvi) Japanese Patent Application No. 2003-340924 Acridone based compounds having a basic skeleton of the following formula according to Saisho like, include a carbazole-based compounds having a basic skeleton of the following formula described in (xvii) No. 2004-218915 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 ³ , R ⁴ , R ⁷ and R ⁸ each independently represents an alkyl group which may have a substituent, and R ⁵ , R ⁶ , R ⁹ and R ¹⁰ each independently represents an alkyl group which may have a substituent, or a hydrogen atom, R ³ and R ⁴ , R ⁷ and R ⁸ , R ³ and R ⁵ , R ⁴ and R ⁶
, R ⁷ and R ⁹ , and R ⁸ and R ¹⁰ may each independently form a nitrogen-containing heterocycle. ]
Here, the carbon number of the alkyl group of R ³ , R ⁴ , R ⁷ and R ⁸ in the formula (I), and the carbon when R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are alkyl groups, The number is preferably 1-6. Further, when forming a nitrogen-containing heterocycle, it is preferably a 5- or 6-membered ring, and R ³ and R ⁵ , R ⁴ and R ⁶ , R ⁷ and R ⁹ , or R ⁸ and R ¹⁰ are 6-membered rings. It is preferable that R ³ and R ⁴ and R ⁵ and R ⁶ , and / or R ⁷ , R ⁸ , R ⁹ and R ¹⁰ 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 the formula (II), R ³ and R ⁴ each independently represent an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently have a substituent. R ³ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁶ may each independently form a nitrogen-containing heterocycle, and X represents , 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 ³ and R ⁴ in formula (II), and the carbon number when R ⁵ and R ⁶ are alkyl groups are preferably 1 to 6, and When forming a nitrogen heterocycle, a 5- or 6-membered ring is preferable, and R ³ and R ⁵ , or R ⁴ and R ⁶ preferably form a 6-membered tetrahydroquinoline ring, and R ³ It is particularly preferable that R ⁴ , R ⁵ and R ⁶ 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 the formula (III), R ³ and R ⁴ each independently represents an optionally substituted alkyl group, and R ⁵ and R ⁶ each independently represent a substituent. also alkyl group, or a hydrogen atom, R ³ and R ^4, R ³ and R ^5, and each, independently of R ⁴ and R ^6, may form a nitrogen-containing heterocycle, R ¹¹ Represents a monovalent group or a hydrogen atom, and R ¹² represents a monovalent group. ]
Here, the carbon number of the alkyl group of R ³ and R ⁴ in the formula (III), and the carbon number when R ⁵ and R ⁶ are alkyl groups are preferably 1 to 6, and When forming a nitrogen heterocycle, it is preferably a 5- or 6-membered ring, but R ⁵ and R ⁶ are preferably hydrogen atoms. Examples of the monovalent group of R ¹¹ and R ¹² 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. Among these, R ¹¹ is preferably a hydrogen atom, and R ¹² 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 formula (IV), R ³ , R ⁴ and R ¹³ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently represents a substituent. An alkyl group which may have, or a hydrogen atom, R ³ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁶ may each independently form a nitrogen-containing heterocycle; R ¹⁴ 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 ³ , R ⁴ , and R ¹³ in formula (IV), and the carbon number when R ⁵ , R ⁶ , and R ¹⁴ are alkyl groups are 1-6. It is preferable that when a nitrogen-containing heterocyclic ring is formed, a 5- or 6-membered ring is preferable, but R ⁵ and R ⁶ are preferably hydrogen atoms. R ¹⁴ 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 group And may have a substituent such as , May further have a substituent, preferably one represented by the following general formula (V) or (VI).

(In the above general formulas (V) and (VI), the rings A to E each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and ring A and ring B, ring D and ring E may be bonded to each other to form a bonded ring containing N. In the general formula (VI), the linking group L represents a linking group containing an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring. The linking groups L and N are bonded by the aromatic hydrocarbon ring or aromatic heterocyclic ring, and n represents an integer of 2 or more.)
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 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. Group may be substituted, and those 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 Triphenylamine compounds represented by the general formula (V) or (VI) are particularly preferred.

The carboxyl group-containing copolymer of component (A) constituting the photopolymerizable composition of the present invention, the ethylenically unsaturated compound of component (B), the photopolymerization initiator of component (C), and ( Each content ratio of the sensitizing dye of component D) is 20 to 80% by weight of component (A), 20 to 80% by weight of component (B), and component (C) with respect to the total amount of the photopolymerizable composition. Is 0.1 to 20% by weight, and component (D) is preferably 0.01 to 10% by weight.
[1-5] Hydrogen Donating Compound In addition to the components (A) to (D), the photopolymerizable composition of the present invention contains a hydrogen donating compound for the purpose of improving photopolymerization initiation ability. The hydrogen donating compound may include, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto -4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, mercapto group-containing compounds such as pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane Tristhioglyconate, pentaerythritol tetrakis Polyfunctional thiol compounds such as thiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or salts thereof such as ammonium and sodium salts, derivatives such as bipolar compounds thereof, phenylalanine, or esters 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. Among them, in the present invention, mercapto group-containing compounds and amino acids or derivatives thereof are preferable.

In the photopolymerizable 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 photopolymerizable composition. It is preferable that it is 2% by weight or less.
[1-6] Other components Furthermore, the photopolymerizable composition of the present invention includes, in addition to the above-mentioned components, a polymerization inhibitor and a photopolymerization for preventing thermal or temporal polymerization of the photopolymerizable composition. A plasticizer for controlling film physical properties as a composition layer, a dye for visualizing an image to be formed (visible paint), a color change agent, and adhesion of the formed image to a substrate to be processed May contain, as necessary, an adhesion imparting agent, an antioxidant, a surface tension modifier, a stabilizer, a chain transfer agent, an antifoaming agent, a flame retardant, a solvent, a surfactant, and the like. .

  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 visible paints include tris (4-dimethylaminophenyl) methane [leuco crystal violet], tris (4-diethylamino-2-methylphenyl) methane, leucomacarite green, leucoaniline, leucomethyl violet, and 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, meta Nyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, parame Lured, 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 [ Manufactured 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 to 0.5% with respect to the total amount of the photopolymerizable composition. It is preferably contained in an amount of 0.8% by weight, and further preferably contains 0.001-0.5% by weight, particularly 0.002-0.2% by weight of crystal violet, macalite green, brilliant green and the like.

Examples of the color changing agent include, in addition to the visible colorant, for example, diphenylamine, dibenzylamine, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, o Examples of the adhesion-imparting agent include benzimidazole, henzothiazole, benzoxazole, benzotriazole, 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole.
[2] Image Forming Material and Image Forming Material The photopolymerizable composition of the present invention comprises the image forming material of the present invention (hereinafter sometimes referred to as image forming material (a) in the section [2]). Can be used to form. The image forming material (a) is usually formed on a temporary support film as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent, dried, and if necessary, a photosensitive composition layer formed. It is formed by covering the surface with a coating film. Examples of such an image forming material (a) include a dry film resist material.

  In addition, the image forming material (a) can be used to form the image forming material of the present invention (hereinafter also referred to as image forming material (b) in Chapter [2]). . There are usually two types of image forming materials (b). One is prepared by peeling off the coating film when the photosensitive composition layer side of the image forming material (a) is covered with a coating film and laminating it on a substrate to be processed. The other is created by the following procedure. (1) A coating solution in which each component of the photopolymerizable composition is dissolved or dispersed in an appropriate solvent; (2) directly coated on the substrate to be processed and dried; (3) on the substrate to be processed. A layer of the photopolymerizable composition of the present invention is formed.

The image forming material (b) is suitably used in the following image forming method. That is, the photosensitive composition layer of the image forming material (b) is scanned and exposed with a laser beam and developed to reveal an image.
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. 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 solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether and other propylene glycol solvents, Butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Ester solvents such as ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as methanol, isopropanol, heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketones such as cyclohexanone, methyl ethyl ketone Examples thereof include solvents, aromatic solvents such as toluene, highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. Among these, from the standpoints of solubility, surface tension, viscosity, ease of drying, and the like, single or mixed solvents such as methyl ethyl ketone, methanol, isopropanol, and toluene are preferable. The use ratio of the solvent is usually in the range of about 0.5 to 2 times by weight with respect to the total amount of the photopolymerizable composition.

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

In addition, when used as a dry film resist material or the like, it is preferable to cover the surface of the formed photopolymerizable composition layer with a coating film until it is laminated on the substrate to be processed. A conventionally known film such as a polyethylene film, a polypropylene film, or a polytetrafluoroethylene film is used. In 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.

  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 to a laser beam to develop the photopolymerizable composition layer formed on the substrate. By performing etching processing or plating processing using the image that appears as a resist, patterns such as circuits and electrodes are formed on the surface thereof, copper, aluminum, gold, silver, chromium, zinc, Although it may be a metal plate itself such as tin, lead, nickel, etc., 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 photopolymerizable composition layer of the resist image forming material having the photopolymerizable composition layer of the present invention on the substrate to be processed is scanned by laser light or collectively exposed by a mercury lamp through a mask. After exposure to a desired pattern, development processing is performed to form a resist 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. When the polymerizable composition layer is formed and has the protective layer, the photopolymerizable composition layer is usually exposed from above the protective layer.

  As the exposure light source, a laser light source is preferable, and examples thereof include a HeNe laser, an argon ion laser, a YAG laser, a HeCd laser, a semiconductor laser, and a ruby laser. In particular, laser light in a blue-violet region having a wavelength range of 390 to 430 nm. A blue-violet laser light source that generates light is preferable, and a light source that generates laser light having a wavelength range of 400 to 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 photopolymerizable composition layer is formed from the dry film resist material, the development treatment after the laser exposure is performed by peeling off the temporary support film or applying the photopolymerizable composition. When the photopolymerizable composition layer is formed by directly applying and drying the liquid, and having the protective layer, after removing the protective layer, an alkali salt such as sodium carbonate or potassium carbonate Of about 0.3 to 2% by weight of dilute alkaline aqueous solution. 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.
[1] Preparation of Examples 1 to 3 and Comparative Examples 1 to 3 [1-1] Preparation of Dry Film Resist Material As the photopolymerizable composition, the following alkali-soluble resins (A1 to A4) and ethylenically unsaturated compounds (B1 to B2), photopolymerization initiator (C1), sensitizing dye (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 in step 1 was applied on a polyethylene terephthalate film (thickness 25 μm) as a temporary support film in an amount of 20 μm using a 100 μm deep applicator, and the oven at 90 ° C. Was dried for 10 minutes, and a polyethylene film (thickness: 25 μm) as a coating film was laminated on the formed photopolymerizable composition layer to prepare a dry film resist material.

<Alkali-soluble resin>
Resins (A1) to (A4) shown in Table 1 below

  <Ethylenically unsaturated compound>

<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 (absorption maximum 351 nm present at the longest wavelength 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)

<Visible paint>
(X1) leuco crystal violet (X2) crystal violet <solvent>
(Y1) Production of Methyl Ethyl Ketone [1-2] Image Forming Material 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 was added to Sumitomo 3M. Polished with Scotch Bright SF made by the company, washed with water, dried by air flow and leveled, and then preheated to 80 ° C. in an oven, on the copper foil of the copper clad laminate Using the hand-type roll laminator, the dry film resist material obtained above was peeled off from the polyethylene film, using a hand-type roll laminator, at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min. Was laminated to produce an image forming material in which a photopolymerizable composition layer was formed on a copper clad laminate.
[2] Evaluation of Examples 1 to 3 and Comparative Examples 1 to 2 [2-1] Exposure / Development The photopolymerizable composition layers of the obtained image forming materials were subjected to the following exposure / development conditions. Exposure and development processing were performed.

<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, an image plane light quantity of ² mW / cm ² , 8.0 mJ / cm ² , 11.3 mJ / Cm ² 16.0 mJ / cm ² , 22.6 mJ / cm ² , 32.0 mJ / cm ² , and 45.3 mJ / cm ² , 64.0 mJ / c
As exposure doses in 7 stages of m ² , scanning exposure was performed on line-and-space (line width: space width = 1: 1) of 10 μm to 30 μm and independent lines of 10 μm to 30 μm. After 20 minutes from the exposure, the polyethylene terephthalate film is peeled off and removed, and then a 1% by weight sodium carbonate aqueous solution at 32 ° C. is double the break point (time until the non-exposed area is completely dissolved). Development was carried out by spraying at 0.3 MPa for the development time.
[2-2] Exposure Sensitivity, Resolution, Adhesiveness Pattern images obtained at each exposure dose were observed with an optical microscope for the resolution of line-and-space and independent lines, and exposure sensitivity and resolution were as follows. The adhesion was evaluated and the results are shown in Table 2.

The exposure amount obtained by resolving 20 μm line and space as 1: 1 was defined as exposure sensitivity.
In the above exposure sensitivity, the resolution was the minimum resolved line and space.
Among the independent lines obtained at each exposure amount, the narrowest remaining line width was defined as adhesion.

  The blue-violet laser photosensitive composition, blue-violet laser image forming material, and blue-violet laser image forming material of the present invention are printed wiring board, plasma display wiring board, liquid crystal display wiring board, large-scale integrated circuit, thin transistor, and semiconductor. It is useful for forming resist images for etching resists, plating resists, solder resists, etc. by direct drawing with blue-violet laser light in the formation of fine electronic circuits such as packages, and is particularly used for the production of printed wiring boards. Therefore, industrial applicability is extremely high.

Claims (9)

A photopolymerizable composition comprising the following component (A), component (B), and component (C).
(A) Alkali-soluble resin containing alicyclic unsaturated hydrocarbons as copolymerization component (B) Ethylenically unsaturated compound (C) Photopolymerization initiator   The photopolymerizable composition according to claim 1, wherein the alkali-soluble resin (A) contains an alicyclic unsaturated hydrocarbon and an ethylenically unsaturated carboxylic acid as a copolymerization component.   The photopolymerizable composition according to claim 1, comprising a hexaarylbiimidazole compound as a photopolymerization initiator of the component (C).   The photopolymerizable composition according to any one of claims 1 to 3, further comprising (D) a sensitizing dye having an absorption maximum in a wavelength range of 355 to 430 nm.   The sensitizing dye of component (D) is any one or more compounds selected from the group consisting of dialkylaminobenzene compounds, triphenylamine compounds, acridone compounds, and carbazole compounds. Photopolymerizable composition. 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 photopolymerizable composition according to claim 5, comprising any one or more compounds selected from the group consisting of dialkylaminobenzene-based compounds having a carbostyril skeleton represented by the formula:

[In the formula (I), R ³ , R ⁴ , R ⁷ and R ⁸ each independently represents an alkyl group which may have a substituent, and R ⁵ , R ⁶ , R ⁹ and R ¹⁰ each independently represents an alkyl group which may have a substituent, or a hydrogen atom, R ³ and R ⁴ , R ⁷ and R ⁸ , R ³ and R ⁵ , R ⁴ and R ⁶
, R ⁷ and R ⁹ , and R ⁸ and R ¹⁰ may each independently form a nitrogen-containing heterocycle. ]

[In the formula (III), R ³ and R ⁴ each independently represents an optionally substituted alkyl group, and R ⁵ and R ⁶ each independently represent a substituent. also alkyl group, or a hydrogen atom, R ³ and R ^4, R ³ and R ^5, and each, independently of R ⁴ and R ^6, may form a nitrogen-containing heterocycle, R ¹¹ Represents a monovalent group or a hydrogen atom, and R ¹² represents a monovalent group. ]

[In formula (IV), R ³ , R ⁴ and R ¹³ each independently represents an alkyl group which may have a substituent, and R ⁵ and R ⁶ each independently represents a substituent. An alkyl group which may have, or a hydrogen atom, R ³ and R ⁴ , R ³ and R ⁵ , and R ⁴ and R ⁶ may each independently form a nitrogen-containing heterocycle; R ¹⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ] The photopolymerizable composition according to claim 5, wherein the triphenylamine-based compound is any compound selected from the group represented by the following general formula (V) or (VI).

(In the above general formulas (V) and (VI), the rings A to E each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and ring A and ring B, ring D and ring E may be bonded to each other to form a bonded ring containing N. In the general formula (VI), the linking group L represents a linking group containing an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring. The linking groups L and N are bonded by the aromatic hydrocarbon ring or aromatic heterocyclic ring, and n represents an integer of 2 or more.)   An image forming material, wherein a layer of the photopolymerizable composition according to any one of claims 1 to 7 is formed on a temporary support film.   An image forming material, wherein the image forming material according to claim 8 is laminated on the substrate to be processed on the photopolymerizable composition layer side.