JP2008152284A - Blue-violet laser photosensitive composition, image forming material using the same, imaging material and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity to laser light in a blue-violet region. <P>SOLUTION: The photopolymerizable blue-violet laser photosensitive composition comprises (A) an ethylenically unsaturated compound; (B) a sensitizer expressed by structural Formula (I); and (C) at least one or more kinds of photopolymerization initiator components selected from among hexaarylbiimidazole compounds , halogenated hydrocarbon derivatives, iodonium salts and organic borate salts. In the Formula (I), X represents an oxygen atom, a sulfur atom or NR<SP>9</SP>, each of R<SP>1</SP>to R<SP>9</SP>independently represents a hydrogen atom or a substituent, where at least one of adjacent groups in R<SP>1</SP>through R<SP>8</SP>, R<SP>5</SP>and R<SP>6</SP>, R<SP>8</SP>and R<SP>9</SP>, and R<SP>7</SP>and R<SP>9</SP>may be coupled and form a ring. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to etching for forming conductive circuits and electrode processing substrates in printed wiring boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, thin transistors, etc. The present invention relates to a blue-violet laser-sensitive composition used for resists, plating resists, etc., and particularly to a blue-violet laser-sensitive composition that is suitably used for direct drawing with blue-violet laser light in a wavelength range of 390 to 430 nm.

  Conventionally, in the formation of printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, organic electroluminescence, thin transistors, etc. After exposing the photosensitive resist material layer of the image forming material having a photosensitive resist material layer on the substrate to be processed and, if necessary, a protective layer, by irradiating with ultraviolet rays through the mask film, the mask film If the protective layer is further peeled off, the protective layer is peeled off and developed using the difference in solubility in the developer between the exposed and unexposed areas to form a pattern, and this pattern layer is masked. After the substrate to be processed is etched or plated, the resist image is removed to form the substrate to be processed. Lithography for forming a tract pattern has been 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.

  On the other hand, various light sources from ultraviolet to infrared are known as laser light. As laser light that can be used for image exposure, an argon ion laser is used from the viewpoint of output, stability, photosensitive ability, and cost. , Helium neon lasers, YAG lasers, semiconductor lasers, etc. that emit light in the visible to infrared region are promising. For example, lithography using an argon ion laser with a wavelength of 488 nm and an FD-YAG laser with a wavelength of 532 nm The law has already been put into practical use.

  However, the conventional photosensitive composition does not always have sufficient sensitivity in the direct writing method using laser light, and a semiconductor that can stably oscillate in the blue-violet region due to recent remarkable progress in laser technology. Although the laser can be used, its output is low compared to other visible regions, so the sensitivity of the photosensitive composition is not necessarily sufficient. In the lithography method as well as the direct drawing method However, at present, the level has not yet reached the level where it can be put into practical use.

As a photosensitive composition having high sensitivity to a blue-violet laser, for example, for lithographic printing, (i) it has at least one vinyl group in an aromatic ring, and at least one of its ortho and para positions is sulfur. A compound that is substituted with an atom, (ii) a titanocene compound, and (iii) a compound that reacts with at least one of a radical and an acid, and changes and retains at least one of its physical and chemical properties A photosensitive composition is disclosed. However, according to our study, since this is for lithographic printing, it is highly sensitive when the photosensitive layer is thin, but in the electronic material application, the photosensitive material is used as a resist for substrate processing. When the film thickness is increased, the sensitivity is remarkably lowered, or when the sensitivity is increased, the safe light property under a yellow light is inferior.
JP 2002-169282 A

  The present invention has been made in view of the above-described prior art. Therefore, the present invention is highly sensitive to laser light in a blue-violet region, and is particularly suitable for direct drawing with a blue-violet laser. It is an object to provide a blue-violet laser-sensitive composition. Furthermore, a highly sensitive photosensitive composition is also provided when the photosensitive material is used with a thick film as a resist for substrate processing in electronic material applications.

  The present invention includes (A) an ethylenically unsaturated compound, (B) a sensitizer represented by the following structural formula (I), and (C) a hexaarylbiimidazole compound, a halogenated hydrocarbon derivative, an iodonium salt, an organic The gist of the present invention is a photopolymerizable blue-violet laser-sensitive composition comprising at least one photopolymerization initiator component selected from borate.

(However, X represents an oxygen atom, a sulfur atom, or NR ⁹ , and R ^{1 to} R ⁹ each independently represents a hydrogen atom or an arbitrary substituent, and R ¹ to R ⁸ are adjacent to each other, R ⁵ and R ⁶ , R ⁸ and R ⁹ , and R ⁷
And R ⁹ may be bonded to form a ring. )

  The photosensitive composition of the present invention is highly sensitive to blue-violet laser light, and is particularly suitable for direct drawing with a blue-violet laser. Furthermore, when the photosensitive material is used with a thick film as a resist for substrate processing in electronic materials, it has high sensitivity characteristics.

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

  As the ethylenically unsaturated compound in the present invention, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid [in the present invention, “(meth) acrylic” Means “acrylic” or / and “methacrylic”. ], Unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene, etc. In view of the ability to expand the difference in developer solubility between the exposed part and the non-exposed part accompanying crosslinkability, it is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, An acrylate compound whose unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferred.

  The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

  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, 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, tetramethylolethane tri (meth) acrylate, trimethylol Propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide adduct (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, sorbitol penta (meth) acrylate, sorbite Hexhexa (meth) acrylate and the like, and similar crotonate, isocrotonate, maleate, itaconate, citraconate and the like.

  Further, as the esters thereof, a reaction product of an unsaturated carboxylic acid as described above with an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A or the like, or an ethylene oxide adduct or glycidyl group thereof. Reaction products with compound adducts, specifically, for example, hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A dioxyethylene di ( (Meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate, etc. Reaction product of unsaturated carboxylic acid and heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate , Tri (meth) acrylate, etc., and a reaction product of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound, specifically, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol. , Condensates of (meth) acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin, etc. Is mentioned.

  The (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group, but are represented by the following general formula (II) or (III). Those are preferred.

[In the formulas (II) and (III), R ¹⁰ represents a hydrogen atom or a methyl group, n is an integer of 1 to 25, and m is 1, 2, or 3. ]
Here, n is preferably from 1 to 10, and particularly preferably from 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, and (meth). Examples include acryloyloxyethylene glycol phosphate, which may be used alone or as a mixture.

  Specific examples of urethane (meth) acrylates include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and tetramethylol. Hydroxy (meth) acrylate compounds such as ethane tri (meth) acrylate and hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,6 Aliphatic polymers such as 11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane Cycloaliphatic polyisocyanates such as isocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Heterocyclic polyisocyanates such as aromatic polyisocyanates and isocyanurates Aneto, a reaction product of a polyisocyanate compounds and the like.

  Among them, as the urethane (meth) acrylate, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable. Is obtained, for example, by reacting a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerin with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate. Compound (i-1) or a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate” manufactured by Asahi Kasei Kogyo Co., Ltd. 21S-75E "," Duranai " 18H-70B "and other biuret types," Duranate P-301-75E "," Duranate E-402-90T "," Duranate E-405-80T ", etc. 1 molecule such as a compound (i-2) obtained by reacting a compound having an isocyanate group, or a compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like Compounds having 4 or more, preferably 6 or more isocyanate groups, such as “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaeryth 1 or more hydroxyl groups and 2 or more, preferably 3 or more (meth) acryloyl per molecule, such as tall tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It can be obtained by reacting the compound (ii) having an oxy group.

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, and particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene and ethyl acetate. It can be produced by a method of reacting at a molar ratio of 1/10 to 10/1 at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate as necessary. it can.
In the present invention, among the urethane (meth) acrylates, those represented by the following general formula (IV) are particularly preferable.

[In the formula (IV), Ra represents a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and 4 to 20 oxy groups capable of bonding to Rb, and Rb and Rc are each independently a carbon. An alkylene group having a number of 1 to 10, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, Ra, Rb, Rc and Rd may have a substituent; x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15. ]
Here, as the repeating structure of the alkyleneoxy group of Ra in the formula (IV), for example, those derived from propylenetriol, glycerin, pentaerythritol and the like, and as the repeating structure of the aryleneoxy group, for example, pyrogallol , 1,3,5-benzenetriol and the like.
Moreover, it is preferable that the carbon number of the alkylene group of Rb and Rc is respectively independently 1-5, and it is preferable that the (meth) acryloyloxy group in Rd is 1-7. Further, x is preferably 4 to 15, y is 1 to 10, and z is 1 to 10.

  Furthermore, as Ra, the following formula [wherein, k is an integer of 2 to 10. And Rb and Rc are each independently a dimethylene group, a monomethyldimethylene group or a trimethylene group, and Rd is particularly preferably represented by the following formula: .

However, Q is

  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 (A), ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable in the present invention. ) Acrylates are particularly preferred, and among the ester (meth) acrylates, ester (meth) acrylates containing a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or polyethylene oxide adduct of bisphenol A are particularly preferred.

  The sensitizer of the component (B) represented by the following structural formula (I) constituting the blue-violet laser-sensitive composition in the present invention has an appropriate absorption in the wavelength range of 390 to 430 nm, and is a blue-violet laser. It is a compound that generates a polymerization active species from the photopolymerization initiator component (C) by the interaction between the sensitizer and the photopolymerization initiator component by light irradiation.

(However, X represents an oxygen atom, a sulfur atom, or NR ⁹ , and R ^{1 to} R ⁹ each independently represents a hydrogen atom or an arbitrary substituent, and R ¹ to R ⁸ are adjacent to each other, R ⁵ and At least one of R ⁶ , R ⁸ and R ⁹ , and R ⁷ and R ⁹ may be bonded to form a ring.)
Arbitrary substituents for R ^{1 to} R ⁹ include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; cyano group; monovalent organic group and the like. Monovalent organic groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, amyl, tert-amyl, and n-hexyl. A linear or branched alkyl group having 1 to 18 carbon atoms such as a group, n-heptyl group, n-octyl group and tert-octyl group; carbon such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group, and a hexenyl group; a cyclopentenyl group, A C3-C18 cycloalkenyl group such as a rohexenyl group; a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an amyloxy group, a tert- A linear or branched alkoxy group having 1 to 18 carbon atoms such as amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, tert-octyloxy group; methylthio group, ethylthio group, n- Propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, amylthio group, tert-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, tert-octylthio group A linear or branched alkylthio group having 1 to 18 carbon atoms, such as Aryl groups having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; aralkyl groups having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group and hexenyloxy group A linear or branched alkenyloxy group having 2 to 18 carbon atoms; a linear or branched alkenylthio group having 2 to 18 carbon atoms such as a vinylthio group, a propenylthio group, or a hexenylthio group; an acyl represented by —COR ¹¹ carbamate group represented by -NHCOOR ^16;; acylamino group represented by -NHCOR ^15; amino group represented by -NR ¹³ R ^14; acyloxy group represented by -OCOR ^12; group; a carboxyl group -CONR ¹⁷ carboxylic acid ester group represented by -COOR ^19;; carbamoyl groups represented by R ¹⁸ Surufamo represented by -SO ₃ NR ²⁰ R ²¹ Le group; -SO ₃ sulfonic acid ester group represented by R ^22; 2-thienyl, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, tetrahydrothiophene And saturated or unsaturated heterocyclic groups such as dioxide groups.

R ^{11 to} R ²² each represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
These positional relationships are not particularly limited, and when having a plurality of substituents, they may be the same or different.

Examples of the case where R ¹ to R ⁸ adjacent to each other, R ⁵ and R ⁶ , R ⁸ and R ⁹ , and / or R ⁷ and R ⁹ are combined to form a ring include the following structural formulas (B- 1) to (B-25).

Although not described in the above structural formula, in each compound, at least one of R ¹ to R ⁸ , R ⁵ and R ⁶ , R ⁸ and R ⁹ , and R ⁷ and R ⁹ is bonded. The ring thus formed may have a substituent, and further, the substituent may be bonded to form a ring.
The alkyl group, alkenyl group, aryl group and heterocyclic group contained in the groups represented by R ^{1 to} R ²² may be further substituted.

In this case, examples of the substituent include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; C2-C12 alkoxy alkoxy groups such as methoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, ethoxy An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms such as a methoxymethoxy group and an ethoxyethoxymethoxy group; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group and a xylyl group (these are further substituted with a substituent). Phenoxy group, tri Aryloxy groups having 6 to 12 carbon atoms such as oxy group, xylyloxy group and naphthyloxy group; alkenyloxy groups having 2 to 12 carbon atoms such as vinyloxy group and allyloxy group; acyl groups such as acetyl group and propionyl group; cyano group A nitro group; a hydroxyl group; a tetrahydrofuryl group; an amino group; an alkylamino group having 1 to 10 carbon atoms such as an N, N-dimethylamino group and an N, N-diethylamino group; a methylsulfonylamino group, an ethylsulfonylamino group; C1-C6 alkylsulfonylamino groups such as n-propylsulfonylamino group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl Group, n-butoxycarbonyl group, etc. An alkylcarbonyloxy group having 2 to 7 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an iso-propylcarbonyloxy group, an n-butylcarbonyloxy group; C2-C7 alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group, tert-butoxycarbonyloxy group, etc. Is mentioned.
Moreover, the substituent of an alkenyl group may connect and it may become the heterocyclic structure (for example, benzothiazole structure) which makes the carbon atom of an alkenyl group the carbon atom of a ring structure.

Preferably, R ^{1 to} R ⁹ are a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aralkyl group, an alkenyloxy group, an amino group, a carboxyl group, An acyloxy group, an acylamino group, a carbamate group, a carbamoyl group, a carboxylic acid ester group, a sulfamoyl group, a saturated or unsaturated heterocyclic group, or a group in which R ¹ to R ⁸ are mutually adjacent, R ⁵ and R ⁶ , And at least one of R ⁸ and R ⁹ is preferably bonded to form a saturated or unsaturated hydrocarbon ring or heterocyclic ring. Moreover, it is preferable that any one or more of R ¹ , R ³ and R ^{5 is} an optionally substituted alkoxy group or amino group.

Particularly preferably, at ^{least one} of R ¹ , R ³ and R ^{5 is} an optionally substituted alkoxy group or amino group, and R ^{1 to} R ⁹ are a hydrogen atom, a hydroxyl group or a substituted group. Alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, aralkyl group, alkenyloxy group, carboxyl group, acyloxy group, acylamino group, carbamate group, carbamoyl group, carboxylic acid ester group, saturated or unsaturated Or at ^{least one of} R ¹ to R ⁸ , R ⁵ and R ⁶ , and R ⁸ and R ⁹ are bonded to form a saturated or unsaturated hydrocarbon ring or This is a case where a ring is formed.

When at least ^{one of} R ¹ to R ⁸ , R ⁵ and R ⁶ , and R ⁸ and R ⁹ are combined to form a saturated or unsaturated hydrocarbon ring or heterocyclic ring, the ring is formed. The ring is preferably a ring having 4 to 8 atoms.
Specific examples of the component (B) sensitizer are not necessarily limited, but examples thereof include the following structures.

  The photopolymerization initiator of component (C) constituting the blue-violet laser-sensitive composition in the present invention is photoexcited by the sensitizer when irradiated with light in the presence of the sensitizer of component (B). A radical generator that receives energy to generate active radicals and leads to polymerization of the ethylenically unsaturated compound (A), which is a hexaarylbiimidazole compound, halogenated hydrocarbon derivative, iodonium salt, organic It is at least one photopolymerization initiating component selected from borate. Among them, hexaarylbiimidazole compounds and organoborates are preferable from the viewpoints of sensitivity as a photosensitive composition, adhesion to a substrate, and storage stability, and from the viewpoint of safelight properties under a yellow light. Hexaarylbiimidazole compounds are particularly preferred.

  Specific examples of the hexaarylbiimidazole compound include 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 (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. 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. These hexaarylbiimidazole compounds are synthesized by a method disclosed in, for example, Bull. Chem. Soc. Japan; 33,565 (1960), J. Org. Chem .; 36, 2262 (1971), etc. It may be used in combination with a biimidazole compound.

  Incidentally, a hexaarylbiimidazole compound conventionally known as a photopolymerization initiator in a photosensitive composition has a melting point of 190 ° C. or higher, for example, about 196 to 202 ° C., and an X-ray diffraction with a wavelength of 1.54Å. Although it has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.925 ° in the spectrum, the hexaarylbiimidazole compound in the present invention has a solubility in a coating solvent and a photosensitive composition. In view of dispersion stability, etc., the melting point is 180 ° C. or lower, further 175 ° C. or lower, and the Bragg angle (2θ ± 0.2 °) is 21.16 ° in the X-ray diffraction spectrum with a wavelength of 1.54 mm. The most suitable hexaarylbiimidazole compound is, for example, 2,2′-bis (o-alkoxide). Rophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole and the like are mentioned, among which 2,2'-bis (o-chlorophenyl) -4,4 ', 5 5,5′-tetraphenylbiimidazole is particularly preferred.

Examples of halogenated hydrocarbon derivatives include halogen-substituted alkanes, halomethylated s-triazine derivatives, halomethylated 1,3,4-oxadiazole derivatives, and the like.
Specific examples of the halogen-substituted alkane include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, and the like.

  Among the halogenated hydrocarbon derivatives, specific examples of halomethylated s-triazine derivatives include 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 (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4, -Bis (trichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -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 (tribromomethyl) -s-triazine and the like, among which bis (trihalomethyl) -s-triazine is preferable, and 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 (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4 2,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like are particularly preferred. .

  Specific examples of the halomethylated oxadiazole derivative include 2- (p-methoxyphenyl) -5-trichloromethyl-1,3,4-oxadiazole and 2- (p-methoxystyryl)-. 5-trichloromethyl-1,3,4-oxadiazole, 2- (o-benzofuryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (β- (o-benzofuryl) vinyl) Examples include -5-trichloromethyl-1,3,4-oxadiazole.

  Examples of the iodonium salt include diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, dicyclohexyliodonium hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, dicyclohexyliodonium p-toluenesulfonate, Examples include iodonium salts such as dicyclohexyliodonium camphorsulfonate, among which diaryliodonium such as diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, and the like. Salt is preferred.

  Examples of organoborates include organoboron ammonium complexes, organoboron phosphonium complexes, organoboron sulfonium complexes or organoboron oxosulfonium complexes, organoboron iodonium complexes, organoboron transition metal coordination complexes, and the like. Examples of the anion include n-butyl-triphenylboron 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) boro Anion, n-butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris ( Alkyl-triphenylboron anions such as p-chlorophenyl) boron anion and n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) boron anion are preferred, and ammonium cations, phosphonium cations, sulfoniums as counter cations Onium compounds such as cations and iodonium cations are preferred, and organic ammonium cations such as tetraalkylammonium are particularly preferred.

  In addition to the components (A), (B), and (C), the negative photosensitive composition in the present invention improves the formability and developability as a photosensitive resist material layer on the substrate. For the purpose, it is preferable to further contain an alkali-soluble resin (D) component. Examples of the alkali-soluble resin include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide. , Maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide and other homo- or copolymers, as well as polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. In view of alkali developability, a carboxyl group-containing vinyl resin is preferred. It is.

Specific examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and styrene. , Α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 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, acetic acid Examples thereof include copolymers with vinyl compounds such as vinyl.
Among these, styrene- (meth) acrylate- (meth) acrylic acid copolymers are preferable, styrene 3 to 30 mol%, (meth) acrylate 10 to 80 mol%, (meth) acrylic acid 10 to 60 mol%. A copolymer consisting of 5 to 25 mol% styrene, 20 to 80 mol% (meth) acrylate, and 10 to 55 mol% (meth) acrylic acid is particularly preferable. In the above, (meth) acrylate includes those in which the alkyl ester moiety is substituted with a hydroxyl group or the like. These carboxyl group-containing vinyl resins preferably have an acid value of 30 to 250 KOH · mg / g and a polystyrene-equivalent weight average molecular weight of 1,000 to 300,000.

  Further, as the carboxyl group-containing vinyl-based resin, those having an ethylenically unsaturated bond in the side chain are suitable. Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate is added to the carboxyl group-containing polymer. , Α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Group epoxy group-containing unsaturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1. ] Dec-2-yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate, 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer Reaction products obtained by reacting, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, Compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1- Propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) a The ratio of the compound having two or more kinds of unsaturated groups such as chloramide and the unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned.

  In the blue-violet laser-sensitive composition of the present invention, the ethylenically unsaturated compound (A), the sensitizer (B), the photopolymerization initiator (C), and the (D) The content of each component of the alkali-soluble resin is such that (A) component is 10 to 90% by weight, (B) component is 0.05 to 20% by weight, and (C) component is based on the total amount of the photosensitive composition. 0.5 to 50% by weight, (D) component is preferably 0 to 80% by weight, (A) component is 20 to 70% by weight, (B) component is 0.1 to 10% by weight, (C More preferably, the component (1) is 1 to 30% by weight and the component (D) is 10 to 70% by weight.

  In addition, the blue-violet laser-sensitive composition of the present invention preferably further contains a polymerization accelerator (E) component for the purpose of improving photopolymerization initiation ability and the like. Examples include ester compounds of aliphatic amino acids which are monoamino monocarboxylic acids, and bipolar ion compounds. Among them, compounds represented by the following general formula (V) or (VI) are preferable.

(In the formulas (V) and (VI), R ²³ represents a hydrogen atom or an optionally substituted alkyl group, R ²⁴ represents a hydrogen atom or an optionally substituted alkyl group, An allyl group which may have a substituent, a vinyl group which may have a substituent, or an aryl group which may have a substituent, each of R ²⁵ and R ²⁶ independently represents: Represents a hydrogen atom, an optionally substituted alkyl group, a carboxyl group, or an optionally substituted aryl group, and R ²⁷ represents an optionally substituted alkyl group or a substituted group. Represents an aryl group which may have a group, and s represents an integer of 0 to 10.)

Here, R ²³ in the general formulas (V) and (VI) is a hydrogen atom or a methyl group, but R ²⁴ is a hydrogen atom, an alkyl group which may have a substituent, or a substituent. R ²⁵ and R ²⁶ may be a hydrogen atom, an alkyl group that may have a substituent, or a carboxyl group, and R ²⁷ may be a substituent. It is preferable that s is an integer of 0 to 5, respectively, which may be an alkyl group which may have a substituent or a phenyl group which may have a substituent.

Specific examples of the alkyl group which may have a substituent of R ^{24 and} the phenyl group which may have a substituent include a methyl group, an acetoxymethyl group, an ethoxycarbonylmethyl group, and allyloxy. Carbonylmethyl, ethyl, acetoxyethyl, ethoxycarbonylethyl, chloroethyl, methylsulfonylethyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-vinylpropyl, 2-hydroxy-3- Vinylethylpropyl group, 2-hydroxy-3-acryloyloxypropyl group, 2-hydroxy-3-methacryloyloxypropyl group, 2-hydroxy-3-methacryloyloxyethoxypropyl group, 2-hydroxy-3- (2′-hydroxy) -3'-methacryloyloxypropoxyethoxy Propyl, 2-hydroxy -3-p-methoxyphenoxy-propyl group, a phenyl group, p- fluorophenyl group, p- chlorophenyl group, p- bromophenyl group, p- dimethylaminophenyl group and the like, also, R ¹⁶ and Specific examples of the alkyl group which may have a substituent for R ¹⁷ include, for example, a methyl group, an ethyl group, and the like, and an alkyl group and a substituent which may have a substituent for R ^15. Specific examples of the phenyl group that may have a methyl group, ethyl group, lauryl group, phenyl group, p-ethylphenyl group, o, p-dimethylphenyl group, p-methoxyphenyl group, o, p-dimethoxyphenyl group, p-hydroxyphenyl group, o-carboxyphenyl group, p-acetylphenyl group, p-trifluoromethylphenyl group, p-fluoro Lophenyl group, p-chlorophenyl group, p-bromophenyl group, o-carboxy-p-bromophenyl group, p-dimethylaminophenyl group, 3,5-diaminophenyl group, p-cyanophenyl group, p-benzoylphenyl group , P- (p-aminobenzyl) sulfonylphenyl group and the like. Among these, as the aliphatic amino acid ester compound and the bipolar ion compound in the present invention, an N-phenylglycine ester and a bipolar ion compound are particularly preferable.

  Examples of the polymerization accelerator include amine compounds, and the amine compounds may be aliphatic, alicyclic, or aromatic amines. The amine is not limited to a monoamine, and may be a polyamine such as diamine and triamine, and may be any of a primary amine, a secondary amine, and a tertiary amine, but preferably has a pKb of 7 or less. Specific examples of the amine compound include butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, allylamine, diallylamine, triallylamine, triethanolamine, Examples thereof include aliphatic amines that may be substituted with a hydroxyl group or a phenyl group, such as benzylamine, dibenzylamine, and tribenzylamine. Among them, tribenzylamine is particularly preferable in the present invention.

  Furthermore, examples of the polymerization accelerator include 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 Polyfunctional thiol compounds such as tetrakisthiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine, or salts and esters thereof such as ammonium and sodium salts thereof Derivatives, phenylalanine, or salts such as its ammonium and sodium salts, such as amino acids or derivatives thereof having an aromatic ring of derivatives of esters. Among them, in the present invention, mercapto group-containing compounds and N-phenylglycine, or salts thereof such as ammonium and sodium salts, and derivatives such as esters are particularly preferable.

In the blue-violet laser photosensitive composition of the present invention, the content ratio of the polymerization accelerator of the component (E) is preferably 0.1 to 30% by weight with respect to the total amount of the photosensitive composition. More preferably, it is -20% by weight.
In addition, the blue-violet laser-sensitive composition in the present invention is a nonionic, anionic, cationic, amphoteric, or fluorine-based surfactant for the purpose of improving the coating property as a coating solution and the developing property. The component (F) may be contained. Specifically, for example, as the nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl are used. 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 Kind, poly Xylethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxyethylene sorbite fatty acid esters, etc., and the anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, poly Oxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters Salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, etc., and their cationic surfactants Quaternary ammonium salts, imidazoline derivatives, amine salts and the like, also, as the amphoteric surfactant, betaine type compounds, imidazolium salts, imidazolines, amino acids and the like can be mentioned, respectively.

  In this invention, it is preferable that the content rate of surfactant of the said (F) component is 0.1 to 10 weight% with respect to the whole quantity of a photosensitive composition, and it is 1 to 5 weight%. Further preferred. The negative photosensitive composition according to the present invention further includes various additives, for example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2% by weight or less based on the total amount of the photosensitive composition, 20% by weight or less of a colorant comprising an organic or inorganic dye / pigment, and 40% of a plasticizer such as dioctyl phthalate, didodecyl phthalate or tricresyl phosphate. % Or less, a sensitivity property improving agent such as a tertiary amine or thiol may be contained in a proportion of 10% by weight or less, and a dye precursor may also be contained in a proportion of 30% by weight or less.

  The blue-violet laser-sensitive composition of the present invention preferably has a spectral sensitivity maximum peak in the wavelength range of 390 to 430 nm, and more preferably has a spectral sensitivity maximum peak in the wavelength range of 400 to 420 nm. When having a maximum spectral sensitivity peak in a wavelength range less than the above range, the sensitivity of the photosensitive composition to laser light having a wavelength of 390 to 430 nm is inferior. The safe light property under the light will be inferior.

  In the present invention, the maximum peak of spectral sensitivity is, for example, described in detail in “Photopolymer Technology” (Ao Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262), etc. Light obtained by spectrally separating a photosensitive image-forming material sample having a photosensitive layer formed on the substrate surface from a light source such as a xenon lamp or a tungsten lamp using a spectral sensitivity measuring device is linearly exposed in the vertical direction with a vertical exposure wavelength. The exposure intensity is set so that it changes logarithmically in the axial direction. After exposure and exposure, an image corresponding to the sensitivity of each exposure wavelength can be obtained by developing, and an image can be formed from that image height. The maximum peak in the spectral sensitivity curve obtained by calculating the exposure energy and plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis.

Further, blue-violet laser photosensitive composition of the present invention is preferably imageable minimum exposure amount [S410] is 10 mJ / cm ² or less at a wavelength of 410 nm, further preferably at 7 mJ / cm ² or less It is particularly preferably 5 mJ / cm ² or less. If the minimum exposure amount [S410] exceeds the above range, although depending on the exposure intensity of the laser light source, the exposure time becomes longer and the practicality is lowered. Although the lower limit of the minimum exposure [S410] is preferably as small as possible, it is usually 1 mJ / cm ² or more.

The blue-violet laser-sensitive composition of the present invention has a ratio [S410 / S450] of 0.1 or less to the minimum exposure amount [S450 (mJ / cm ² )] capable of forming an image at a wavelength of 450 nm of [S410]. It is preferable that it is 0.05 or less. When this ratio [S410 / S450] exceeds the above range, it becomes difficult to achieve both the blue-violet laser sensitivity and the safelight property under a yellow lamp.

In addition, the blue-violet laser-sensitive composition of the present invention has the minimum image-forming ability at a wavelength of 450 nm with a minimum exposure amount [S450-650 (mJ / cm ² )] capable of forming an image at each wavelength of 450 nm to 650 nm. The ratio [S450-650 / S450] to the exposure amount [S450 (mJ / cm ² )] is preferably more than 1. If this ratio [S450-650 / S450] is less than the above range, it tends to be difficult to achieve both blue-violet laser sensitivity and safe light performance under a yellow lamp.

  Note that the minimum exposure amount that enables image formation at a wavelength of 410 nm [S410], the minimum exposure amount that enables image formation at a wavelength of 450 nm [S450], and the minimum exposure amount that enables image formation at wavelengths of 450 nm to 650 nm or less [ S410-450] is obtained as exposure energy capable of image formation calculated from the obtained image height in the measurement of the maximum peak of spectral sensitivity using the above-described spectral sensitivity measuring apparatus, and the developer at that time Means the minimum exposure that can form an image under optimum development conditions determined by changing development conditions such as development type, development temperature, development time, etc. The optimum development conditions are usually alkaline development at pH 11-14. A condition of immersing in the liquid at a temperature of 25 ° C. for 0.5 to 3 minutes is employed.

  The blue-violet laser-sensitive composition of the present invention is usually a photosensitive solution formed as necessary by applying it on a temporary support film as a coating solution in which the above components are dissolved or dispersed in a suitable solvent. By covering the surface of the composition layer with a coating film, the so-called dry film resist material or the like is used as the blue-violet laser-sensitive image forming material of the present invention, and the photosensitive composition layer side of the image forming material is coated with the coating film. By laminating and laminating on the substrate to be processed, or by directly applying on the substrate to be processed and exposing it as a coating solution in which the above components are dissolved or dispersed in an appropriate solvent. A blue-violet laser-sensitive image-forming material of the present invention in which a layer of the blue-violet laser-sensitive composition of the present invention is formed on a substrate, and the blue-violet laser-sensitive composition layer of the image-forming material is Scanning exposure by a laser beam of 390 to 430 nm, it is preferably used in the use form as an image forming method for revealing a negative image by development.

  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 the film has low solvent resistance or low heat resistance, for example, it has 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 Ester solvents such as ethyl, 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, alcohol solvents such as heptanol, hexanol, diacetone alcohol, furfuryl alcohol, cyclohexanone And ketone solvents such as methyl amyl ketone, highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, mixed solvents thereof, and those obtained by adding aromatic hydrocarbons thereto. 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. In particular, in the image forming material in which the blue-violet laser-sensitive composition layer of the present invention is laminated on the substrate to be processed, the thickness of the composition layer is 10 μm or more from the point of use as an etching resist or a plating resist. It is preferable that the upper limit is about 100 μm. 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 blue-violet laser-sensitive composition of the present invention is subjected to scanning exposure with a laser beam and then developed to form a resist image.
Here, examples of the laser exposure light source 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 is used. Although the light source to generate | occur | produce is preferable and it does not specifically limit, Specifically, the indium gallium nitride semiconductor laser etc. which oscillate | emit center wavelength 405nm are mentioned.

  Further, 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. Preferably 1-100 mW, more preferably 3-70 mW, oscillation wavelength, preferably 390-430 nm, more preferably 400-420 nm, beam spot diameter, preferably 0.5-30 μm, more preferably 1-20 μm, Scanning exposure is performed at a scanning speed of preferably 50 to 500 m / second, more preferably 100 to 400 m / second, and a scanning density of preferably 2,000 dpi or more, more preferably 4,000 dpi or more.

  The development after the laser scanning exposure is preferably performed 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 and the like, and used at a concentration of about 0.1 to 5 wt%.

Examples of the surfactant include the same surfactants as mentioned in the blue-violet laser-sensitive composition. Among them, nonionic, anionic, or amphoteric surfactants are preferable, and amphoteric surfactants are particularly preferable. Of these, betaine-type compounds are preferred.
The surfactant is used in a concentration of preferably 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 is usually about 10 to 50 ° C., more preferably 15 to 15 ° C. 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.

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.
(Example 1)
Each component shown in Table 1 was added to 100 parts by weight of a mixed solvent of methyl ethyl ketone / isopropanol (weight ratio 8/2), and a coating solution prepared by stirring at room temperature was prepared as a polyethylene terephthalate film (thickness) as a temporary support film. 19 μm) using an applicator so that the dry film thickness is 25 μm, dried in an oven at 90 ° C., and a polyethylene film (thickness 25 μm) as a coating film is formed on the formed photosensitive composition layer. Laminated and used as a photosensitive image forming material.

Separately, the copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm thick copper foil is buffed with “Scotch Bright SF” manufactured by Sumitomo 3M, and washed with water. And drying the surface with an air stream, preheating it to 60 ° C. in an oven, and then applying the photosensitive image-forming material obtained above on the copper foil of the copper-clad laminate to the polyethylene film. A photosensitive composition on a copper-clad laminate is obtained by laminating at a peeling surface using a hand-type roll laminator at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a lamination speed of 1.5 m / min. A material layer was created. About the obtained photosensitive composition layer, when the exposure sensitivity was measured by the method shown below, it was ² mJ / cm < ² >.

<Exposure sensitivity>
Using the laser light source (“NLHV500C” manufactured by Nichia Corporation) having a center wavelength of 405 nm and a laser output of 5 mW, the obtained photosensitive composition layer was subjected to an image plane illuminance of 2 mW, a beam spot diameter of 20 μm, and a beam scanning interval. Operation exposure was performed while changing the scanning speed, and then a 1% by weight sodium carbonate aqueous solution at 30 ° C. was sprayed as a developing solution to a pressure of 0.15 MPa, and a negative image was formed by spray development in a time twice the minimum development time. Made it appear. With respect to the obtained image, an exposure amount required for reproducing a line width of 20 μm was obtained and used as exposure sensitivity.
Furthermore, when the peak of spectral sensitivity was measured by the method shown below, it was 410 nm.

<Maximum peak of spectral sensitivity>
A sample obtained by cutting the image forming material into a size of 50 × 60 mm is 350 to 650 nm using a diffraction spectroscopic irradiation apparatus (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. Exposure was performed by irradiating the light separated in the wavelength region of 10% for 10 seconds with the exposure wavelength set linearly in the horizontal axis direction and the exposure intensity logarithmically changed in the vertical axis direction, and then 1 weight at 30 ° C. % Sodium carbonate aqueous solution as a developing solution is sprayed to 0.15 MPa, and spray development is performed in a time twice as long as the minimum developing time, whereby an image corresponding to the sensitivity of each exposure wavelength is obtained. Calculate the exposure energy that allows image formation, and read the maximum peak in the spectral sensitivity curve obtained by plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis. It was.

The Measurement of the minimum exposure amount capable of forming an image at the wavelength ^{410nm [S410 (mJ / cm 2} )] by the following method was 3 mJ / cm ^2. Further, the ratio [S410 / S450] of the minimum exposure amount [S410] capable of forming an image at a wavelength of 410 nm to the minimum exposure amount [S450 (mJ / cm ² )] capable of forming an image at a wavelength of 450 nm was measured. It was "A" when evaluated on the basis.

<S410, S410 / S450>
In the same manner as described above, the minimum exposure amount [S410 (mJ / cm ² )] capable of forming an image at a wavelength of 410 nm and image formation at a wavelength of 450 nm when the exposure is performed while changing the wavelength in the wavelength region of 350 to 650 nm and developing. The possible minimum exposure [S450 (mJ / cm ² )] was determined, and the ratio [S410 / S450] was calculated and evaluated according to the following criteria.

<Evaluation criteria of S410 / S450>
A: S410 / S450 is 0.03 or less.
B: S410 / S450 is more than 0.03 and 0.05 or less.
C: S410 / S450 is more than 0.05 and 0.1 or less.
D: S410 / S450 exceeds 0.1.
It was "A" when the safelight property under the yellow lamp was evaluated by the method shown below for the image forming material obtained separately.

<Safelight characteristics under yellow light>
The image forming material was allowed to stand for 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes under yellow light illumination (conditions in which light having a wavelength of about 470 nm or less was blocked). Scanning exposure and development processing were performed, and the standing time until the image changed compared to the above was obtained, and evaluated according to the following criteria.
A: 20 minutes or more.
B: 10 minutes or more and less than 20 minutes.
C: 1 minute or more and less than 10 minutes.
D: Less than 1 minute.

(Examples 2 to 5)
A photosensitive image forming material was prepared in the same manner as in Example 1 except that each component shown in Table 1 was used.
About the photosensitive composition of the obtained image forming material, the result measured by the method similar to Example 1 is shown in Table-2.

(Comparative Example 1)
A photosensitive image forming material was prepared in the same manner as in Example 1 except that no sensitizing dye was used, and the exposure sensitivity was measured in the same manner as described above for the photosensitive composition layer of the obtained image forming material. However, no image was obtained.

(Comparative Example 2)
A photosensitive image forming material was prepared in the same manner as in Example 1 except that the photopolymerization initiator in Example 1 was changed to the titanocene compound shown in Table 1. Regarding the photosensitive composition layer of the obtained image forming material The exposure sensitivity measured by the same method as described above was 1 mJ / cm ² , but the maximum peak of spectral sensitivity was 500 nm, [S410] was 1 mJ / cm ² , and [S410 / S450] was “D”. The light property was also inferior to “D”.

The compounds in Table 1 below are shown below.
(A-1): Kyoei Chemical Co., Ltd. light ester 9EG

(A-2): Kyoei Chemical Co., Ltd. light ester BP-6EG

(A-3): NK ester BPE-300 manufactured by Shin-Nakamura Chemical Co., Ltd.

(C-1): 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (melting point 172 ° C., X-ray diffraction spectrum having a wavelength of 1.54Å, Bragg angle ( (2θ ± 0.2 °) having a maximum diffraction peak at 21.16 °)
(C-2): n-butyl-tris (m-fluorophenyl) boron anion and tetramethylammonium cation complex (C-3): Irgacure 784 manufactured by Ciba Specialty Chemicals

(C-4): 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (melting point: 198 ° C., X-ray diffraction spectrum at a wavelength of 1.54Å, black angle ( 2θ ± 0.2 °) having a maximum diffraction peak at 9.925 °)
(D-1): Styrene / methyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (molar ratio 10/50/20/20, acid value 129 KOH / mg / g, polymerization average molecular weight 68,000)
(D-2): Styrene / methyl methacrylate / n-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate copolymer (molar ratio 11/38/8/13/25/6, acid value 130 KOH / Mg / g, weight average molecular weight 65,000)
(E-1): Dipolar ion compound of N-phenylglycine (F-1): leucocrystal violet: 0.4 parts by weight and 9-phenylacridine: 0.2 parts by weight (F-2): leucocrystal violet: 0.4 parts by weight and crystal violet: 0.025 parts by weight

Claims (8)

(A) ethylenically unsaturated compound, (B) sensitizer represented by the following structural formula (I), and (C) hexaarylbiimidazole compound, halogenated hydrocarbon derivative, iodonium salt, organoboronate A photopolymerizable photosensitive composition comprising at least one selected photopolymerization initiator component.

(However, X represents an oxygen atom, a sulfur atom, or NR ⁹ , and R ^{1 to} R ⁹ each independently represents a hydrogen atom or an arbitrary substituent, and R ¹ to R ⁸ are adjacent to each other, R ⁵ and At least one of R ⁶ , R ⁸ and R ⁹ , and R ⁷ and R ⁹ may be bonded to form a ring.) 2. The photopolymerization according to claim 1, wherein R ^{1 to} R ⁹ in the structural formula (I) each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, or a monovalent organic group. Photosensitive composition.   In the structural formula (I), an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an aryl group, an aralkyl group, an alkenyloxy group, an alkenyl group, which may be substituted with a monovalent organic group A group selected from a thio group, an amino group, an acyl group, a carboxyl group, an acyloxy group, an acylamino group, a carbamate group, a carbamoyl group, a carboxylic acid ester group, a sulfamoyl group, a sulfonic acid ester group, and a saturated or unsaturated heterocyclic group. The photopolymerizable photosensitive composition according to claim 2, wherein the photopolymerizable photosensitive composition is provided. The photosensitive composition according to claim 1, wherein any one or more of R ¹ , R ³ , and R ^{5 is} an optionally substituted alkoxy group or amino group.   (E) The photosensitive composition in any one of Claims 1-4 containing the dipolar compound of an aliphatic amino acid, or the carboxylic acid ester of an aliphatic amino acid as a polymerization accelerator.   (C) The photoinitiator is a hexaarylbiimidazole compound, The photosensitive composition in any one of Claims 1-5 characterized by the above-mentioned.   Hardened | cured material formed with the photosensitive composition in any one of Claims 1-6.   A liquid crystal display device having the cured product according to claim 7.