JP2006058478A - Blue-violet laser photosensitive composition, and image forming material, image forming medium and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue-violet laser photosensitive composition, an image forming material and an image forming medium having high sensitivity to a blue-violet laser, good storage stability of a photosensitive composition layer formed on a temporary supporting film, and satisfactory visible image property by exposure, and to provide an image forming method for the same. <P>SOLUTION: The blue-violet laser photosensitive composition contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator and (D) a leuco dye, wherein (C) an alkyl halide compound is contained in the photosensitive composition, a ratio S1/S2 between sensitivity S1 (mJ/cm<SP>2</SP>) upon exposure with blue-violet laser light having a wavelength of 390-430 nm and sensitivity S2 (mJ/cm<SP>2</SP>) after storage in a temperature range of 20-25°C for 3 months in a state where a layer of the composition is formed on a temporary supporting film is 0.7-1.4, and the sensitivity S1 is 0.1-100. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an etching resist or plating for forming a printed circuit board, a liquid crystal display element, a plasma display, a large scale integrated circuit, a thin transistor, a semiconductor package, a color filter, an organic electroluminescence, etc. A blue-violet laser-sensitive composition used for resists and the like, and in particular, a blue-violet laser-sensitive composition suitably used for direct drawing with blue-violet laser light in a wavelength range of 390 to 430 nm, and the use thereof The present invention relates to an image forming material, an image forming material, and an image forming method.

  Conventionally, as a photosensitive composition used for the formation of printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, conductive circuits in organic electroluminescence, electrode processing substrates, etc. The negative photosensitive composition typically comprises an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin such as a carboxyl group-containing resin, and the ethylenically unsaturated compound is polymerized by light irradiation. A composition which is cured and becomes insoluble in an alkaline developer, a phenolic hydroxyl group-containing resin such as polyvinylphenol resin and a crosslinking agent for the resin, or an acid-crosslinkable group-containing resin such as an epoxy group-containing resole resin, and a halomethylated s -A photoacid generator comprising a photoacid generator such as a triazine derivative. Compositions that are cross-linked by the generated acid and become insoluble in an alkaline developer are known, and as a positive photosensitive composition, typically, an acid-decomposable group-containing polyvinyl phenol resin such as an alkoxy group is used. A composition comprising an acid-decomposable group-containing resin such as halomethylated s-triazine derivative and the like, and being soluble in an alkali developer by being decomposed by an acid generated by the photoacid generator upon irradiation with light. Etc. are known.

  For the formation of conductor circuits, electrode processing substrates, etc., a dry film resist material in which a layer made of these photosensitive compositions is formed on a temporary support film and the surface of the photosensitive composition layer is covered with a coating film. An image-forming material obtained by peeling the coating film and laminating on the substrate to be processed, or an image in which a photosensitive composition layer is directly formed on the substrate to be processed, and a protective layer is provided thereon if necessary When the photosensitive composition layer of the forming material is image-exposed through a mask film on which a circuit or an electrode pattern is drawn, the mask film is peeled off, and a temporary support film or a protective layer is further provided. The protective layer and the like are peeled off, and the non-exposed portion as a non-image portion in the negative type and the exposed portion as a non-image portion in the positive type are dissolved and removed with an alkaline developer to the circuit pattern. The resist image is formed, and the substrate to be processed is etched or plated using the resist image as a resist. Then, the resist image is removed to form a circuit or electrode pattern drawn on the mask film on the substrate to be processed. Lithographic methods are widely used.

Furthermore, in recent years, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask film by using a laser beam 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. As the laser light, various light sources from the ultraviolet to the infrared region are known, but as laser light that can be used for image exposure, argon ions are used from the viewpoint of output, stability, photosensitive ability, and cost. 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, and materials corresponding to 365 nm UV lasers are also commercially available for printed wiring board applications.

  However, the conventional photosensitive composition still does not necessarily have sufficient sensitivity in the direct drawing method using a laser beam, and in the visible laser beam, the photosensitive composition is a safe light under a yellow light. However, there is a restriction that it is necessary to work in a dark room environment such as a red light illumination. Although it is now possible to use a semiconductor laser that can oscillate stably in the blue-violet region, its output is lower than other visible regions, so the sensitivity of the photosensitive composition In addition to remaining room for improvement in terms of surface, particularly in resist materials that are used in a state where the film thickness of the photosensitive composition layer is thick, it cannot cope with high resolution, rectangularity, etc. of the obtained image, In the direct drawing method It not yet reached a level that well be practiced even in lithography at present.

  On the other hand, as a photosensitive composition, for example, in order to improve sensitivity in a blue-violet region, the aromatic ring has at least one vinyl group, and at least one of the o-position and the p-position is a sulfur atom. Although a photopolymerizable composition for a lithographic printing plate using a substituted compound as a sensitizer and a titanocene compound as a polymerization initiator in combination (for example, see Patent Document 1) has been proposed, These photosensitive compositions also have a thickness of 10 μm or more as a resist material, particularly a photosensitive composition layer formed on a substrate to be processed through a dry film resist material. In the plating process, which is a process, the sensitivity in the blue-violet region is still improved due to the demand for increasing the plating thickness with the recent miniaturization of the wiring line width. It is intended to leave the room, whereas the sensitivity at the time of storage at room temperature when a high sensitivity is lowered.

In addition, the photosensitive composition layer is required to have sufficient exposure visibility to visually confirm that the substrate to be processed has undergone the exposure process, and has exposure visibility by combining an organic halogen compound and a leuco dye. A photopolymerizable composition for a dry film resist (for example, see Patent Document 2) has been disclosed, but sensitivity and storage stability were insufficient in the blue-violet region.
JP 2002-169282A. JP 02-48664 A.

  The present invention has been made in view of the above-described prior art, is highly sensitive to blue-violet laser, has good storage stability of the photosensitive composition layer formed on the temporary support film, and is sufficiently Another object of the present invention is to provide a blue-violet laser-sensitive composition, an image forming material, an image forming material, and an image forming method thereof that have excellent exposure and visibility.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that blue-violet laser-sensitive compositions containing a leuco dye and an alkyl halide compound have specific conditions for sensitivity before and after storage under specific environmental conditions. It is found that the above-mentioned object can be achieved by satisfying the above, preferably specifically containing a sensitizing dye having an absorption maximum at 355 to 450 nm and containing a hexaarylbiimidazole compound as a polymerization initiator. The present invention has been reached. That is, the gist of the present invention is as follows.
A blue-violet laser-sensitive composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (D) a leuco dye, wherein (C) an alkyl halide is contained in the photosensitive composition A temperature of 20 to 25 ° C. in a state in which the compound layer is included and the composition layer is formed on the temporary support film with the sensitivity S1 (mJ / cm ² ) when exposed to blue-violet laser light having a wavelength of 390 to 430 nm. The ratio S1 / S2 to the sensitivity S2 (mJ / cm ² ) after storage in a region for 3 months is 0.7 or more and 1.4 or less, and S1 is 0.1 or more and 100 or less. A blue-violet laser-sensitive composition.

  Furthermore, another gist of the present invention is a photosensitive image forming material in which a layer of the above photosensitive composition is formed on a temporary support film, and the above photosensitive image forming material on a substrate to be processed. The photosensitive image forming material laminated on the physical layer side, and the photosensitive composition layer of the photosensitive image forming material are scanned and exposed with a laser beam having a wavelength of 390 to 430 nm and developed to reveal an image. A characteristic image forming method.

  The blue-violet laser-sensitive composition of the present invention has high sensitivity and good storage stability, and has sufficient exposure visible image properties when scanned and exposed with blue-violet laser light. An image forming material capable of forming such a resist image, an image forming material, and an image forming method thereof can be provided.

The explanation of the constituent elements described below is a representative example of the embodiment of the present invention, and is not specified by these contents.
[1] Sensitivity and Storage Stability The blue-violet laser-sensitive composition of the present invention has a sensitivity S1 of 0.1 mJ / cm ² or more when exposed to blue-violet laser light having a wavelength of 390 to 430 nm, preferably 0. and at 3 mJ / cm ² or more, 100 mJ / cm ² or less, preferably 50 mJ / cm ² or less, more preferably 30 mJ / cm ² or less. Further, in the state where the composition layer is formed on the temporary support film, 20
When the sensitivity after storage in a temperature range of ˜25 ° C. for 3 months is S2 (mJ / cm ² ), S1
/ S2 is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, 1.4 or less, preferably 1.2 or less, more preferably 1.1 or less.

If S1 is too small, it becomes easy to be exposed to light under a yellow light used in a place where normal image formation is performed, and the resolution of the resist image is lowered. On the other hand, if S1 is too large, the exposure takes a long time, and the productivity is deteriorated.
When S1 / S2 is too small, the sensitivity is greatly lowered when the photosensitive composition is stored at room temperature for a long time, and the adhesion of the resist image is deteriorated. On the other hand, if S1 / S2 is too large, the sensitivity rises after storage at room temperature, and the resolution is lowered.

The sensitivity S1 and S2 are measured by the following method.
[1-1] Method for Measuring Sensitivity S1 (1) An image in which a blue-violet laser photosensitive composition having a film thickness of 20 μm formed on a temporary support film is laminated on a substrate to be processed on the photosensitive composition layer side. After forming a 20 μm line-and-space image with several levels of exposure using a blue-violet laser as a forming material, and then peeling off the temporary support film, a 0.7% sodium carbonate aqueous solution at 25 ° C. Development is performed with a developing time of 1.75 times the breakpoint (3) described later using an automatic developing machine as a developer.

(2) The line width of the obtained resist image is measured with an optical microscope or a scanning electron microscope, and the exposure amount at which the line width of the value closest to 20 μm is obtained is defined as sensitivity S1.
(3) A non-exposed image forming material obtained by laminating a blue-violet laser-sensitive composition having a thickness of 20 μm formed on a temporary support film on a substrate to be processed on the photosensitive composition layer side is the above (1 ) Using the same developer as above, and developing using an automatic developing machine under the same development conditions as the measurement of sensitivity S1 in (1) above, break the time until the photosensitive composition layer is completely removed. Points.
[1-2] Measuring method of sensitivity S2 The same image forming material used for measuring sensitivity S1 is stored at room temperature (temperature range of 20 to 25 ° C.) for 3 months, and then the same as the measurement of sensitivity S1 described above. After exposure with the exposure method and exposure conditions, development is performed with the same developer and development conditions as in the above-described sensitivity S1, and the line width of the resulting resist image is measured using an optical microscope or scanning electron microscope in the same manner as in S1. The amount of exposure obtained by measuring with the above and obtaining the line width closest to 20 μm is defined as sensitivity S2.
In addition, when storing for 3 months in the state which formed the composition layer of the blue-violet laser photosensitive composition of this invention on the temporary support film, it stores in the temperature range of 20-25 degreeC. Storage in such a temperature range is usually performed at room temperature.
[2] Component The blue-violet laser-sensitive composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) a halogenated alkyl compound, and (D) a leuco dye as essential components. Contained as. However, the halogenated alkyl compound (C) may also serve as the photopolymerization initiator (B). If necessary, (E) a sensitizing dye, (F) a carboxyl group-containing polymer, and other components can be added.

Hereinafter, each component will be described.
[2-1] (A) Ethylenically unsaturated compound The ethylenically unsaturated compound (A) in the present invention will be described later when the blue-violet laser-sensitive composition is irradiated with actinic rays (B ) A compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule that undergoes addition polymerization by the action of a photopolymerization initiating system including a photopolymerization initiator as a component, and optionally 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, polyvalent carboxylic 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, 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 Examples thereof include reactants with polyisocyanate compounds such as nates.

  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, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds and other aromatic polyepoxy compounds, sorbitan polyglycidyl ethers, Examples thereof include heterocyclic polyepoxy compounds such as triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate, and reactants with polyepoxy compounds such as polyepoxy compounds.

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 (A), ester (meth) acrylates or urethane (meth) acrylates are preferable, ester (meth) acrylates are particularly preferable, and ester (meth) acrylates are particularly preferable. Among the (meth) acrylates, it has a polyalkylene oxide group such as an ester (meth) acrylate having a polyalkylene oxide group and having two or more (meth) acryloyloxy groups, or a polyalkylene oxide adduct of bisphenol A. Particularly preferred are ester (meth) acrylates having two or more (meth) acryloyloxy groups. Further, the alkylene of the polyalkylene oxide group used here is preferably ethylene or propylene, and when used for a plating resist, it is more preferable that ethylene and propylene are mixed from the viewpoint of peelability and resolution. Preferably, the mixing may be in the same molecule as the ethylenically unsaturated compound of component (A) or in a different molecule.
[2-2] (B) Photopolymerization initiator The photopolymerization initiator of the component (B) in the present invention, when irradiated with light in the blue-violet region, efficiently absorbs light in the wavelength region and is active. When radicals are generated or light irradiation is performed in the presence of a sensitizing dye of the component (E) described later, photoexcitation energy of the sensitizing dye is received to generate an active radical, and the component (A) Radical generators for bringing ethylenically unsaturated compounds into polymerization, such as hexaarylbiimidazole compounds, titanocene compounds, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives , Diaryliodonium salts, organoborates, and organic peroxides. Among them, hexaarylbiimidazole compounds, titanocene compounds, and organoborates are preferable from the viewpoint of sensitivity as a photopolymerizable composition, adhesion to a substrate, and storage stability, and hexaarylbiimidazole compounds. Compounds are particularly preferred.

Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (o-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (p-methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (fluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra ( p-methylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) ) -4,4 ', 5,5'-tetra o, p-dimethoxyphenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (p-methoxyphenyl) biimidazole, 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetra (p-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (P-chlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra ( p-fluorophenyl) biimida 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl)- 4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) ) Biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o-chloro-p-methoxyphenyl) biimidazole, 2,2′-bis (o—) Chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) biimidazole and the like. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a halogen atom is more preferable. Particularly preferred are those in which the benzene ring bonded to the 4 ′, 5,5′-position is unsubstituted or substituted with a halogen atom or an alkoxycarbonyl group.

  Known organoborates can be used. For example, organoboron ammonium complexes, organoboron phosphonium complexes, organoboron sulfonium complexes or organoboron oxosulfonium complexes, organoboron iodonium complexes, organoboron transition metal complexes. Examples of the organic boron anion include n-butyl-triphenyl boron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, n-butyl-tris (p -Methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro-4-methylphenyl) Boron anion, n-butyl-tris (2 6-difluorophenyl) boron anion, n-butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, Alkyl-triphenylboron anions such as n-butyl-tris (p-chlorophenyl) boron anion and n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) boron anion are preferred, and the counter cation is ammonium. Onium compounds such as cation, phosphonium cation, sulfonium cation and iodonium cation are preferred, and organic ammonium cations such as tetraalkylammonium are particularly preferred.

As the titanocene compound, known compounds can be used. For example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl) , Dicyclopentadienyl 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 (Methylcyclopentadienyl) titanium bis (2,3, 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.
[2-3] (C) Halogenated alkyl compound Does the halogenated alkyl compound of component (C) in the present invention efficiently absorb light in the wavelength region when irradiated with light in the blue-violet region? Alternatively, it is a compound that receives the photoexcitation energy of the sensitizing dye when irradiated with light in the presence of the sensitizing dye of the component (E) described later and develops the leuco dye of the component (D) described later. The above-mentioned component (B) and photopolymerization initiator may also be used.

Examples of the halogenated alkyl compound include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (α-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (β-naphthyl) -1,3,4-oxadiazole, 2-tribromo Methyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (p-chlorophenyl) -1,3,4-oxadiazole, 2-tribromomethyl-5- (α -Naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5- (β-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3 4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-chlorostyryl) -1,3,4 Oxadiazole, 2-trichloromethyl-5- (p-methylstyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, 2- Tribromomethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5- (p-chlorostyryl) -1,3,4-oxadiazole, 2- Haloalkyloxadiazoles such as tribromomethyl-5- (p-methylstyryl) -1,3,4-oxadiazole;
Phenyltrichloromethylsulfone, p-methylphenyltrichloromethylsulfone, p-chlorophenyltrichloromethylsulfone, p-nitrophenyltrichloromethylsulfone, phenyltribromomethylsulfone, p-methylphenyltribromomethylsulfone, p-chlorophenyltribromomethylsulfone , Haloalkyl sulfones such as p-nitrophenyl tribromomethyl sulfone, 3,4-dibromosulfolane;
2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2- Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloro) Chill) -s-triazine, 2-(p-ethoxycarbonyl-naphthyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl)- s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis ( Haloalkyl-s-triazines such as tribromomethyl) -s-triazine;
Dichloromethane, chloroform, carbon tetrachloride, carbon tetrabromide, iodoform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-tribromoethane, 1,1,2,2-tetrabromoethane, Halogenated hydrocarbons such as 1,2,3-tribromopropane, 1,2,3,4-tetrabromobutane, hexachlorocyclopentadiene, dibromohexane, 1-chloro-2-iodoethane, 1-bromo-2-chloroethane Kind;
2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 1,3-dichloro-2-propanol, 2,3-dichloro-1-propanol, 1,3-dibromo-2-propanol, 2 Halogenated alcohols such as 1,3-dibromo-1-propanol, trichloro-tert-butanol, 1,4-dichloro-2-butanol, 1,4-dibromo-2-butanol;
1,1-dichloro-2-propanone, 1,3-dichloro-2-propanone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3- Haloalkyl ketones such as chloro-2-butanone, 3,4-dibromo-2-butanone, dibromocyclohexane;
2-bromoethyl methyl ether, 2,3-dichloro-1,4-dioxane, 2,3-dichlorotetrahydrofuran, di (2-bromoethyl) ether, 2-bromoethyl ethyl ether, 1,2-dichloroethyl ethyl ether, etc. Haloalkyl ethers of
Acetic acid-2-bromoethyl ester, bromoacetic acid ethyl ester, 2-bromopropionic acid methyl ester, 3-bromopropionic acid methyl ester, 2,3-dichloropropionic acid methyl ester, trichloroacetic acid ethyl ester, trichloroacetic acid trichloroethyl ester, etc. Halogenated carboxylic acid esters;
And halogenated amides such as 2-chloroacetamide, 2,2-dichloroacetamide, trichloroacetamide, 2,3-dibromopropionamide, 2,3-dichloropropionamide, N- (2-chloroethyl) acetamide, and the like. it can.

The halogenated alkyl compound is preferably a compound containing two or more halogen atoms, and particularly preferably a compound having two or more halogen atoms on one carbon atom.
Among these, preferred halogenated alkyl compounds are haloalkyl oxadiazoles, haloalkyl sulfones and haloalkyl-s-triazines, particularly preferably 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole. 2-trichloromethyl-5- (p-chlorophenyl) -1,3,4-oxadiazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis ( Lichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, tribromomethylphenylsulfone, 3,4-dibromosulfolane.

These halogenated alkyl compounds may be used alone or in combination of two or more.
[2-4] (D) Leuco Dye The leuco dye of the present invention is a compound that develops color by the action of the aforementioned alkyl halide compound when irradiated with actinic rays, and contains a hydrogen atom that can be easily oxidized. Or a leuco-like compound that can be oxidized to a chromogenic compound.

Specifically, for example, leuco crystal violet, leucomalachite green, tris (p-diethylaminophenyl) methane, tris (p-dimethylamino-o-methylphenyl) methane, tris (p-diethylamino-o-methylphenyl) methane, Aminotria such as bis (p-dibutylaminophenyl)-[p- (2-cyanoethyl) methylaminophenyl] methane, bis (p-dimethylaminophenyl) -2-quinolylmethane, tris (p-dipropylaminophenyl) methane Reel methanes;
Aminoxanthenes such as 3,6-bis (diethylamino) -9-phenylxanthene and 3-amino-6-dimethylamino-2-methyl-9- (o-chlorophenyl) xanthene;
Aminothioxanthenes such as 3,6-bis (diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene, 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9, Amino-9,10-dihydroacridines such as 10-dihydro-9-phenylacridine, 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine;
Aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine;
Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine;
Aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine;
Aminophenylmethanes such as bis (p-dimethylaminophenyl) anilinomethane;
Aminohydrocinnamic acids such as 4-amino-4'-dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester;
Hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine;
Amino-2,3-dihydroanthraquinones such as 1,4-bis (ethylamino) -2,3-dihydroanthraquinone;
And phenethylanilines such as N, N-diethyl-p-phenethylaniline.

Of these, aminotriarylmethanes are preferable, and leuco crystal violet and leucomalachite green are particularly preferable.
These leuco dyes may be used alone or in combination of two or more.
The blue-violet laser-sensitive composition of the present invention preferably contains the following component (E) sensitizing dye for the purpose of improving the sensitivity to light in the blue-violet region.
[2-5] (E) Sensitizing dye In the present invention, the sensitizing dye of component (E) constituting the preferred blue-violet laser-sensitive composition has an absorption maximum in the wavelength range of 355 to 430 nm. And efficiently absorbs light in the blue-violet region in the wavelength range of 390 to 430 nm, transmits the photoexcitation energy to the photopolymerization initiator of the component (B), decomposes the photopolymerization initiator, (A) A light-absorbing dye having a sensitizing function for generating an active radical that induces polymerization of the ethylenically unsaturated compound as a component. 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.

As the sensitizing dye, known ones can be used. When the image forming exposure light source is a blue-violet laser, for example, (i) JP 2000-10277 A, JP 2004-198446 A, etc. A diaminobenzophenone compound having a basic skeleton represented by the following formula:
i) an aminophenyl-benzimidazole / benzoxazole / benzothiazole compound having the following skeleton as described in JP-A-2004-198446, etc., and (iii) the following as described in Japanese Patent Application No. 2003-424180, etc. A sulfonylimino compound having a basic skeleton as a formula, (iv) an aminocarbostyryl compound having a basic skeleton as described in Japanese Patent Application No. 2003-392404, etc., (v) JP 2002-169282 A, Merocyanine compounds having the following formula as described in JP-A-2004-191938 and the like, and (vi) Thiazolidene ketone compounds having the following formula as described in JP-A-2002-268239 and the like , (Vii) an imide compound having a basic skeleton as described in Japanese Patent Application No. 2003-291606, etc., and (viii) Benzimidazole / benzoxazole / benzothiazole compound, (ix) triazole compound having the following formula as basic skeleton, (x) cyanostyryl compound having the following formula as basic skeleton, (xi) basic skeleton having the following formula (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, (xiv) a coumarin system having the following formula as a basic skeleton A compound, (xv) a triphenylamine compound having a basic skeleton as described in Japanese Patent Application No. 2004-218915, etc., and (xvi) a basic skeleton having the following formula as described in Japanese Patent Application No. 2003-340924, etc. And (xvii) a carbazole compound having a basic skeleton having the following formula described in Japanese Patent Application No. 2003-435212 and the 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.

Moreover, in the blue-violet laser-sensitive composition of the present invention, a carboxyl group-containing polymer of the following component (F) can be used for the purpose of improving the film-forming property and alkali developability.
[2-6] (F) Carboxyl Group-Containing Polymer In the present invention, the carboxyl group-containing polymer of the component (F) is improved in formability and developability as a layer of the photosensitive composition on the substrate, etc. Specifically, for example, (meth) acrylic acid [in the present invention, “(meth) acrylic” means “acrylic” and / or “methacrylic”. To do. ], A copolymer of an ethylenically unsaturated carboxylic acid monomer such as crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and a vinyl compound monomer copolymerizable therewith. As the unsaturated carboxylic acid, (meth) acrylic acid is particularly preferable.

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

The carboxyl group-containing polymer of component (F) preferably has an acid value of 100 to 300 mg · KOH / g and a polystyrene equivalent weight average molecular weight of 20,000 to 150,000.
In the present invention, the ethylenically unsaturated compound of the component (A) constituting the blue-violet laser-sensitive composition, the photopolymerization initiator of the component (B), (C) an alkyl halide compound, (D) a leuco dye Each content ratio of (B) component is 0.05-100 weight part normally with respect to 100 weight part of (A) component of a photosensitive composition, (C) component is 0.01-100 weight part, ( D) component is 0.01 to 100 parts by weight, preferably (B) component is 0.5 to 80 parts by weight, (C) component is 0.1 to 80 parts by weight, and (D) component is 0.05 to 50 parts by weight. Parts by weight.

  When the photosensitive composition contains a sensitizing dye as component (E) and / or a carboxyl group-containing polymer as component (F), component (E) is usually used with respect to 100 parts by weight of component (A). Is 0.05 to 100 parts by weight, component (F) is 0.1 to 500 parts by weight, preferably component (E) is 0.05 to 50 parts by weight, and component (F) is 1 to 40 parts by weight. is there. The sensitizing dye of component (E) is usually 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably, relative to 1 part by weight of the halogenated alkyl compound of component (C). 1 to 20 parts by weight.

In the present invention, the blue-violet laser-sensitive composition layer includes, in addition to the components (A) to (F), a hydrogen-donating compound, a polymerization inhibitor and an oxidation agent for the purpose of improving photopolymerization initiation ability. Even if it contains an inhibitor, plasticizer, colorant, adhesion promoter, surface tension modifier, stabilizer, chain transfer agent, antifoaming agent, flame retardant, solvent, surfactant, etc. Good.
[3] Photosensitive image forming material, photosensitive image forming material and image forming method The blue-violet laser-sensitive composition of the present invention is usually temporarily supported as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent. The photosensitive image forming material of the present invention as a so-called dry film resist material is obtained by coating the film on a film and drying it, and covering the surface of the photosensitive composition layer formed as necessary with a coating film. The photosensitive composition layer side of the image forming material,
By peeling the coating film and laminating it on the substrate to be processed, or by directly applying and drying on the substrate to be processed as a coating solution in which each of the above components is dissolved or dispersed in an appropriate solvent, A photosensitive image forming material of the present invention in which a layer of the blue-violet laser photosensitive composition of the present invention is formed on a substrate to be processed. The photosensitive composition layer of the image forming material has a wavelength region of 350 to 430 nm. It is preferably used in a form of use as an image forming method in which exposure is performed by a light source containing blue or blue-violet laser light, scanning exposure is preferably performed by laser light having a wavelength of 390 to 430 nm, and development processing is performed to display a negative image.

  As the temporary support film when used as an image forming material as the dry film resist material, a conventionally known film such as a polyethylene terephthalate film, a polyimide film, a polyamide film, a polypropylene film, or a polystyrene film is used. At that time, when those films have the solvent resistance and heat resistance necessary for the production of the image forming material, the photosensitive composition coating solution is directly applied onto the temporary support film. Then, the image forming material of the present invention can be prepared by drying, and even if those films have low solvent resistance or low heat resistance, for example, they have a polytetrafluoroethylene film or a release property. First, a photosensitive composition layer is formed on the film, and then a temporary support film having a low solvent resistance and heat resistance is laminated on the layer, and then the film having releasability is peeled off, thereby The image forming material of the invention can also be prepared.

  The solvent used in the coating solution is not particularly limited as long as it has sufficient solubility for the components used and gives good coating properties. For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate Cellosolve solvents such as ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, etc. Propylene glycol solvents, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, pyruvate , Ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, ester solvent such as methyl 3-methoxypropionate, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, Alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or these And those obtained by adding aromatic hydrocarbons to these. The ratio of the solvent used is usually in the range of about 1 to 20 times by weight with respect to the total amount of the photosensitive composition.

  As the coating method, conventionally known methods such as spin coating, wire bar coating, spray coating, dip coating, air knife coating, roll coating, blade coating, screen coating, and curtain coating can be used. . The coating amount in that case is 0.1-100 micrometers normally as a dry film thickness, Preferably it is the range of 0.5-70 micrometers. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably about 40 to 110 ° C., and the drying time is, for example, about 5 seconds to 60 minutes, preferably about 10 seconds to 30 minutes. It is done.

The thickness of the photosensitive composition layer formed from the photosensitive composition thus formed is not particularly limited, but is usually 0.1 μm or more, more preferably 5 μm or more, preferably 200 μm in terms of dry film thickness. Hereinafter, it is more preferably 100 μm or less. In particular, according to the blue-violet laser photosensitive composition of the present invention, high sensitivity and good storage stability can be achieved even with a photosensitive composition layer having a dry film thickness of 10 μm or more, for example, 10 to 50 μm. .

In the present invention, in the photopolymerizable negative image forming material, the photosensitive composition comprising the blue-violet laser photosensitive composition of the present invention formed on the substrate to be processed as described above. A protective layer such as an oxygen blocking layer may be formed on the layer to prevent the polymerization-inhibiting action by oxygen of the photopolymerizable composition.
What constitutes the oxygen barrier layer is a water-soluble polymer that is soluble in water or a mixed solvent of water and a water-miscible organic solvent such as alcohol or tetrahydrofuran, for example, polyvinyl alcohol, and its Partially acetalized products, cation-modified products with quaternary ammonium salts, derivatives of anion-modified products with sodium sulfonate, etc., polypinylpyrrolidone, polyethylene oxide, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc. It is done.

  Among them, polyvinyl alcohol and derivatives thereof are preferable from the viewpoint of oxygen barrier properties, etc., and from the viewpoint of adhesion to the photosensitive resist material layer, such as polyvinylpyrrolidone and vinylpyrrolidone-vinyl acetate copolymer. A vinyl pyrrolidone polymer is preferable, and the oxygen barrier layer in the present invention is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight of polyvinyl pyrrolidone polymer with respect to 100 parts by weight of polyvinyl alcohol or a derivative thereof. It is preferable to use the mixture as a mixture of parts by weight.

  The oxygen barrier layer preferably contains an organic acid such as oxalic acid or an organic acid salt such as ethylenediaminetetraacetic acid from the standpoint of imparting storability, and nonionics such as polyoxyethylene alkylphenyl ether. , Surfactants such as anionic properties such as sodium dodecylbenzenesulfonate, cationic properties such as alkyltrimethylammonium chloride, antifoaming agents, dyes, plasticizers, pH adjusters, etc., and their total The content ratio is preferably 10% by weight or less, and more preferably 5% by weight or less.

The oxygen barrier layer is formed as a solution of water or a mixed solvent of water and a water-miscible organic solvent by the same coating method as that of the photosensitive composition layer described above. It is preferably in the range of 10 to 10 g / m ² , and more preferably in the range of 1.5 to 7 g / m ² .
The photosensitive composition layer formed with the blue-violet laser-sensitive composition of the present invention is exposed to a light source having a wavelength range of 350 to 430 nm or exposure to blue-violet laser light, in particular, scanning exposure with laser light, and then development processing. As a result, a resist image is formed.

  Here, examples of the light source including a wavelength range of 350 to 430 nm include lamp light sources such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury lamp. Examples of the laser exposure light source include a He—Ne laser, an argon ion laser, a YAG laser, a He—Cd laser, a semiconductor laser, a ruby laser, and the like. In particular, a blue-violet region having a wavelength range of 390 to 430 nm. A light source that generates laser light is preferable, and is not particularly limited, and specific examples include an indium gallium nitride semiconductor laser that oscillates at a central wavelength of 405 nm.

In addition, when performing scanning exposure with laser light, the scanning exposure method is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. The output light intensity on the plate surface is preferably 1 to 100 mW, more preferably 3 to 70 mW, the oscillation wavelength is preferably 390 to 430 nm, more preferably 400 to 420 nm, and the beam spot diameter is preferably 0.5 to 30 μm, more preferably 1-20 μm, scanning speed is preferably 50-500 m / sec, more preferably 100
The scanning exposure is performed at a speed of ˜400 m / sec and a scanning density of preferably 2,000 dpi or more, more preferably 4,000 dpi or more.

The development processing after exposure is performed using an aqueous developer containing an alkali component, and preferably using an aqueous developer containing an alkali component and a surfactant.
Examples of the alkali component include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, Inorganic alkali salts such as dibasic sodium phosphate, tribasic sodium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine Organic amine compounds, quaternary ammonium salts such as tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, etc., and one or more of these are used at a concentration of about 0.1 to 5% by weight. It is done.

  As the surfactant, for example, as the nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters , Polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters Sorbite fatty acid esters, polyoxyethylene sorbite fatty acid esters and the like, and anionic surfactants include alkyl sulfonates, Kill benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates , Polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, etc., and cationic surfactants include quaternary ammonium salts , Imidazoline derivatives, amine salts and the like, and examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines and amino acids. . Of these, nonionic, anionic or amphoteric surfactants are preferred, and amphoteric surfactants, especially betaine-type compounds are preferred. The surfactant is preferably used at a concentration of 0.0001 to 20% by weight, more preferably 0.0005 to 10% by weight, and particularly preferably 0.001 to 5% by weight.

Furthermore, the developing solution can contain an organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, if necessary. Further, the pH of the developer is preferably 9 to 14, and more preferably 11 to 14.
The development treatment is preferably about 10 to 50 ° C., more preferably 15 by a known development method such as immersing the image forming material in the developer or spraying the developer on the image forming material. It is performed at a temperature of about 45 ° C. for a time of about 5 seconds to 10 minutes.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
Examples 1-2 and Comparative Examples 1-3
As the photopolymerizable composition, the following ethylenically unsaturated compounds (A1 to A2), photopolymerization initiators (B1 to B2), halogenated alkyl compounds (C1), leuco dyes (D1), sensitizing dyes (E1 to E1) E2), carboxyl group-containing polymer (F1), and other components (X1) were added to the following solvent (Y1) in the formulation shown in Table 1, and the coating solution prepared by stirring at room temperature was temporarily supported. On a polyethylene terephthalate film (thickness 16 μm) as a film, a 75 μm applicator was applied in an amount to give a dry film thickness of 20 μm, air-dried for 1 minute, and then dried in an oven at 85 ° C. for 90 seconds. A polyethylene film (thickness: 22 μm) as a coating film was laminated on the polymerizable composition layer using a laminator to prepare a dry film resist material.
<Ethylenically unsaturated compound>

<Photopolymerization initiator>
(B1) 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (B2) bis (cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium <halogenated alkyl compound>
(C1) Phenyltribromosulfone <leuco dye>
(D1) Leuco Crystal Violet <sensitizing dye>

<Carboxyl group-containing polymer>
(F1) methacrylic acid / methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / styrene copolymer (wt% = 20/35/10/10/15/10, weight average molecular weight 46, 000)
<Others>
(X1) Malachite green <solvent>
(Y1) Methyl ethyl ketone Separately, the surface of the copper foil of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil was applied to “Scotch Bright SF” manufactured by Sumitomo 3M Limited. Use buffol polishing, wash with water, dry with air flow and adjust the surface, then preheat it to 80 ° C. in an oven, then on the copper foil of the copper clad laminate, the dry film obtained above By laminating the resist material on the peeling surface while peeling the polyethylene film using a hand-type roll laminator at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min. A resist image forming material having a photopolymerizable composition layer formed on a laminated substrate was produced.

The resulting photopolymerizable composition layer of each resist image forming material was exposed and developed under the following exposure and development conditions, and the sensitivity S1, S2 and exposure visible image properties were examined, and the results are shown in Table-1. It was.
<Exposure machine>
Exposure was performed 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.
<Development conditions>
Development was carried out by spraying at 0.15 MPa using a 0.7 wt% aqueous sodium carbonate solution at 25 ° C.
<Breakpoint>
The polyethylene terephthalate film of each non-exposed resist image forming material was peeled off, and the time until the non-exposed photopolymerizable composition layer was completely dissolved under the above development conditions was examined.

<Sensitivity S1>
Each resist image forming material was scanned and exposed with an exposure pattern of 20 μm aggregated lines (line / space = 20 μm / 20 μm) by appropriately changing the exposure amount in the range of 0.01 to 150 mJ / cm ² with the above exposure machine. After 20 minutes from the exposure, the polyethylene terephthalate film was peeled and removed, and developed under the above development conditions at a development time 1.75 times the breakpoint. The obtained pattern image was observed with an optical microscope, and the exposure amount at which the line width of the top portion of the collective line was closest to 20 μm at each exposure amount was defined as sensitivity S1.
<Sensitivity S2>
After each dry film resist material is stored at room temperature (20 to 25 ° C.) for 3 months, an image forming material is prepared in the same manner as the method for obtaining the sensitivity S1, exposed and developed, and the obtained pattern image is obtained. Observed with an optical microscope, the exposure amount at which the line width of the top portion of the collective line was closest to 20 μm at each exposure amount was defined as sensitivity S2.
<Visibility of exposure>
Immediately after the exposure for obtaining the sensitivity S1, the degree of color development in the exposed portion of the photosensitive composition layer of the image forming material was visually observed and evaluated according to the following criteria.

A: The contrast between the exposed portion and the non-exposed portion is clear, and the visible image quality is good. B: The contrast between the exposed portion and the non-exposed portion is unclear. C: There is no contrast between the exposed portion and the non-exposed portion, and there is no visible image property.

  The blue-violet laser-sensitive composition of the present invention has high sensitivity and good storage stability, and has sufficient exposure visibility when scanned and exposed with blue-violet laser light. Further, according to the present invention, it is possible to provide an image forming material capable of forming such a resist image, an image forming material, and an image forming method thereof. Accordingly, the blue-violet laser-sensitive composition, image forming material, image forming material, and image forming method of the present invention include a printed wiring board, a liquid crystal display element, a plasma display, a large-scale integrated circuit, a thin transistor, a semiconductor package, Industrial applicability is very high in a wide range of fields such as etching resists and plating resists for forming conductive circuits and electrode processing substrates in color filters and organic electroluminescence.

Claims (8)

A blue-violet laser-sensitive composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (D) a leuco dye, wherein (C) an alkyl halide is contained in the photosensitive composition 20-25 ° C. in a state where the compound S is contained and the composition layer is formed on a temporary support film with a sensitivity S1 (mJ / cm ² ) when exposed to blue-violet laser light having a wavelength of 390 to 430 nm.
The ratio S1 / S2 to the sensitivity S2 (mJ / cm ² ) after storage in the temperature range of 3 months is 0.7 to 1.4 and S1 is 0.1 to 100 A blue-violet laser-sensitive composition characterized.   (E) The blue-violet laser-sensitive composition according to claim 1, comprising a sensitizing dye having an absorption maximum at 355 to 450 nm.   The sensitizing dye (E) contains at least one compound selected from dialkylaminobenzene compounds, triarylamine compounds, acridone compounds, imidazole compounds, oxazole compounds, and thiazole compounds. 2. The blue-violet laser-sensitive composition according to 2.   (B) The blue-violet laser-sensitive composition according to any one of claims 1 to 3, wherein the photopolymerization initiator is a hexaarylbiimidazole compound.   A blue-violet laser-sensitive image-forming material comprising a layer of the blue-violet laser-sensitive composition according to any one of claims 1 to 4 formed on a temporary support film.   A blue-violet laser-sensitive image forming material comprising the blue-violet laser-sensitive image forming material according to claim 5 laminated on a substrate to be processed on the blue-violet laser-sensitive composition layer side.   The blue-violet laser-sensitive image forming material according to claim 6, wherein the blue-violet laser-sensitive composition layer in the blue-violet laser-sensitive image forming material laminated on the substrate to be processed has a thickness of 10 µm or more.   The blue-violet laser-sensitive composition layer of the blue-violet laser-sensitive image forming material according to claim 6 or 7 is scanned and exposed with a laser beam having a wavelength of 390 to 430 nm, and developed to reveal an image. An image forming method.