JP2008181143A - Blue-violet laser-sensitive composition, and image forming material, photosensitive image forming material and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue-violet laser-sensitive composition having high sensitivity to a light source or blue-violet laser light including a wavelength region of 350-430 nm, particularly suitable for use in direct drawing with a blue-violet laser, and having high sensitivity even when a photosensitive material is used in an increased thickness as a resist for substrate working in electronic material use. <P>SOLUTION: The blue-violet laser-sensitive composition contains one or more of specific amine derivatives having an aromatic hydrocarbon ring or an aromatic heterocycle as a sensitizer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to etching for forming conductive circuits, electrode processing substrates, etc. 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. A blue-violet laser which is a photosensitive composition used for a resist, a plating resist, a storage material such as a DVD, a CD-R, and the like, and is particularly suitable for direct drawing with a blue-violet laser beam in a wavelength range of 390 to 430 nm The present invention relates to a photosensitive composition, an image forming material using the blue-violet laser photosensitive composition, a photosensitive image forming material, and an image forming method.

  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, in lithographic printing, JP-A-2002-169282 discloses (1) having at least one vinyl group in an aromatic hydrocarbon ring, A compound in which at least one of the position and the para-position is substituted with a sulfur atom, (2) a titanocene compound, and (3) at least one of its physical and chemical properties reacting with at least one of a radical and an acid A photosensitive composition containing a compound in which the change is retained is disclosed. However, according to our study, this is a lithographic printing application, so if the film thickness of the photosensitive layer is small, the sensitivity is high. However, in the electronic material application, the film thickness of the photosensitive material is increased as a resist for substrate processing. When used, the sensitivity is remarkably lowered, or when the sensitivity is increased, the safe light property under a yellow light is inferior.

Japanese Patent Publication No. 6-29285 discloses a photopolymerization initiator comprising a nitrogen-containing aromatic hydrocarbon ring compound substituted with a dialkylaminophenyl group and a hexaarylbiimidazole. As a result of this technological advancement, further improvement in sensitivity that matches blue-violet lasers has been desired.
JP 2002-169282 A Japanese Examined Patent Publication No. 6-29285

  The present invention has been made in view of the above-described prior art, and has a high sensitivity to light in the blue-violet region, and in particular, a blue-violet laser photosensitive composition suitable for use in direct drawing with a blue-violet laser. And an image forming material, a photosensitive image forming material, and an image forming method using the blue-violet laser photosensitive composition. The present invention also provides a highly sensitive blue-violet laser-sensitive composition and a blue-violet laser-sensitive composition when the photosensitive material is used with a thick film as a resist for substrate processing in electronic material applications. It is an object of the present invention to provide an image forming material, a photosensitive image forming material, and an image forming method.

  The blue-violet laser-sensitive composition of the present invention is characterized by containing one or more of sensitizers represented by the following general formulas (I) to (III).

（上記一般式（Ｉ）〜（III）において、環Ａ〜Ｇはそれぞれ独立に芳香族炭化水素環又は芳香族複素環を基本骨格とするものであり、環Ａと環Ｂ、環Ｄと環Ｅ、環Ｆと環Ｇは互いに結合してＮを含む結合環を形成していても良い。
上記一般式（II）において、連結基Ｌは、芳香族炭化水素環及び／又は芳香族複素環を含む連結基を表し、連結基ＬとＮとは該芳香族炭化水素環又は芳香族複素環で結合しており、ｎは２以上の整数を表す。
一般式（III）において、Ｒは置換基を有していても良いアルキル基を表す。
なお、環Ａ〜Ｇ及び連結基Ｌは置換基を有していても良く、これらの置換基同士が互いに結合して環を形成していても良い。）

(In the above general formulas (I) to (III), the rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the ring A and ring B, the ring D and ring E, Ring F and Ring G may be bonded to each other to form a bonded ring containing N.
In the general formula (II), the linking group L represents a linking group containing an aromatic hydrocarbon ring and / or an aromatic heterocycle, and the linking groups L and N are the aromatic hydrocarbon ring or aromatic heterocycle. And n represents an integer of 2 or more.
In general formula (III), R represents an alkyl group which may have a substituent.
Rings A to G and linking group L may have a substituent, and these substituents may be bonded to each other to form a ring. )

  The image forming material of the present invention is characterized in that such a layer of the blue-violet laser-sensitive composition of the present invention is formed on a temporary support film.

  The photosensitive image forming material of the present invention is characterized in that such a photosensitive image forming material of the present invention is laminated on the substrate to be processed on the photosensitive composition layer side.

  In the image forming method of the present invention, the photosensitive composition layer of the photosensitive image forming material of the present invention is scanned and exposed with a laser beam having a wavelength of 390 to 430 nm, and developed to reveal a negative image. It is characterized by.

  The image-forming material of the present invention is highly sensitive to a light source including a wavelength region of 350 to 430 nm or a blue-violet laser beam, particularly to a blue-violet laser beam, and more particularly to a blue-violet laser beam. Suitable for direct drawing. 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.

  Hereinafter, embodiments of the present invention will be described in detail.

  The blue-violet laser-sensitive composition of the present invention is not particularly limited as long as it has the specific sensitizer represented by the general formulas (I) to (III). The image forming material of the present invention having a photosensitive resist material layer formed of a photosensitive composition may be either a negative type or a positive type.

  In the case of the negative type, the blue-violet laser-sensitive composition of the present invention comprises (A) an ethylenically unsaturated compound, (B) a sensitizer represented by the general formulas (I) to (III), and (C ) It is preferably made of a photopolymerizable photosensitive composition containing a photopolymerization initiator.

Further, in the case of the negative type, the blue-violet laser-sensitive composition of the present invention includes (B) the following (N-1) in addition to the sensitizers represented by the general formulas (I) to (III). , (N-2), and (N-3) may be a light amplification type photosensitive composition.
(N-1) Alkali-soluble resin (N-2) Cross-linking agent that acts on alkali-soluble resin under acidic conditions (N-3) Photoacid generator

On the other hand, in the case of the positive type, the blue-violet laser-sensitive composition of the present invention includes (B) the following (P-1) in addition to the sensitizers represented by the general formulas (I) to (III). And a photosensitive composition containing the component (P-2).
(P-1) Acid-decomposable group-containing polymer (P-2) Photoacid generator

  Below, the compounding composition of the blue-violet laser photosensitive composition of this invention is demonstrated according to the type of photosensitive composition.

<Negative photopolymerizable photosensitive composition>
The blue-violet laser photosensitive composition of the present invention as a negative photopolymerizable photosensitive composition includes the following components (A) to (C), and further described later (D) and (E) as necessary. , (F) component.

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

  Examples of the ethylenically unsaturated compound in the present invention include a compound having one ethylenically unsaturated bond in the molecule, for example, (meth) acrylic acid [in the present invention, “(meth) acryl” means “acrylic”. And / or methacryl ". ], 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. From the viewpoint of crosslinkability and the difference in developer solubility between exposed and non-exposed areas accompanying it, it is preferable that the compound has 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.

  Examples of the esters include unsaturated carboxylic acid as described above, ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, tetramethylene glycol. , Neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylol ethane, tetramethylol ethane, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine Reaction products with aliphatic polyhydroxy compounds such as triethanolamine, such as ethylene glycol di (meth) acrylate, diethylene Recall 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, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meth) acrylate, Lyserol 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, sorbitol hexa (meth) acryl And the like, and similar crotonates, isocrotonates, maleates, itaconates, citraconates and the like.

  Further, as the esters, 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 such as 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 deoxyoxyethylene di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate, etc. Reaction product of boric acid and heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, etc. Also, a reaction product of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, or (meth) acrylic acid, maleic acid and diethylene glycol. Examples include condensates, condensates of (meth) acrylic acid, terephthalic acid, and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  The (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group. Among them, the following general formula (A-1) or (A-2) ) Is preferred.

（式（Ａ−１）及び（Ａ−２）中、Ｒｚは水素原子又はメチル基を示し、ｊは１〜２５の整数、ｋは１、２、又は３である。）

(In formulas (A-1) and (A-2), Rz represents a hydrogen atom or a methyl group, j is an integer of 1 to 25, and k is 1, 2, or 3.)

  Here, j is preferably 1 to 10, particularly 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) Examples thereof include acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

  The urethane (meth) acrylates include, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylol ethanetri (meth) Hydroxy (meth) acrylate compounds such as acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, 1,6,11-undecatriisocyanate Aliphatic polyisocyanates such as 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane , Cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate and other alicyclic polyisocyanates, 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. Aromatic polyisocyanates, heterocyclic polyisocyanates such as isocyanurates The reaction products of the 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 " 3 in one molecule such as biuret type such as “18H-70B”, adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T”, “Duranate E-405-80T”, etc. Compound (i-2) obtained by reacting the above compound having an isocyanate group, or compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate, etc. Compounds having 4 or more, preferably 6 or more isocyanate groups in the molecule, such as “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc., one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy in one molecule It can be obtained by reacting the compound (ii) having a 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 or 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 (A-3) are particularly preferable.

（式（Ａ−３）中、Ｒａはアルキレンオキシ基又はアリーレンオキシ基の繰り返し構造を有し、且つＲｂと結合し得るオキシ基を４〜２０個有する基を示し、Ｒｂ及びＲｃは各々独立して炭素数が１〜１０のアルキレン基を示し、Ｒｄは（メタ）アクリロイルオキシ基を１〜１０個有する有機残基を示し、Ｒａ、Ｒｂ、Ｒｃ、及びＲｄは置換基を有していても良く、ｘは４〜２０の整数、ｙは０〜１５の整数、ｚは１〜１５の整数である。）

(In the formula (A-3), Ra represents a group having a repeating structure of an alkyleneoxy group or an aryleneoxy group and 4 to 20 oxy groups capable of binding to Rb, and Rb and Rc are each independently An alkylene group having 1 to 10 carbon atoms, Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups, and 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 (A-3), for example, those derived from propylene triol, 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 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. X is preferably 4 to 15, y is 1 to 10, and z is 1 to 10.

  In particular, Ra is preferably represented by the following formula, and Rb and Rc are each independently preferably a dimethylene group, a monomethyldimethylene group, or a trimethylene group, and Rd is represented by the following formula. It is preferred that

  In addition, as the epoxy (meth) acrylates, 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) trimethylolpropane polyglycidyl ether, Aliphatic polyepoxy compounds such as (poly) glycerol polyglycidyl ether and (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy compounds, Aromatic phenol novolak polyepoxy compounds, (o-, m-, p-) cresol novolak polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds and other aromatic polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl Examples thereof include reactants with polyepoxy compounds such as heterocyclic polyepoxy compounds such as isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

  In addition to the above, other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate. Is mentioned.

  These ethylenically unsaturated compounds may be used alone or in combination of two or more.

  As the ethylenically unsaturated compound of component (A), ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and ester (meth) acrylates are particularly preferable. Among the ester (meth) acrylates, ester (meth) acrylates containing a polyoxyalkylene group such as polyethylene glycol, polypropylene glycol, or a polyethylene oxide adduct of bisphenol A are particularly preferable.

(B) Sensitizer The blue-violet laser-sensitive composition of the present invention contains one or more sensitizers represented by the following general formulas (I) to (III) as (B) the sensitizer. contains. The sensitizers represented by the following general formulas (I) to (III) have moderate absorption in the wavelength range of 390 to 430 nm, and are irradiated by a light source or a blue-violet laser beam including the wavelength range of 350 to 430 nm. A compound that effectively generates a polymerization active species from a photopolymerization initiator of the component (C) described later.

（上記一般式（Ｉ）〜（III）において、環Ａ〜Ｇはそれぞれ独立に芳香族炭化水素環又は芳香族複素環を基本骨格とするものであり、環Ａと環Ｂ、環Ｄと環Ｅ、環Ｆと環Ｇは互いに結合してＮを含む結合環を形成していても良い。
上記一般式（II）において、連結基Ｌは、芳香族炭化水素環及び／又は芳香族複素環を含む連結基を表し、連結基ＬとＮとは該芳香族炭化水素環又は芳香族複素環で結合しており、ｎは２以上の整数を表す。
一般式（III）において、Ｒは置換基を有していても良いアルキル基を表す。
なお、環Ａ〜Ｇ及び連結基Ｌは置換基を有していても良く、これらの置換基同士が互いに結合して環を形成していても良い。）

(In the above general formulas (I) to (III), the rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the ring A and ring B, the ring D and ring E, Ring F and Ring G may be bonded to each other to form a bonded ring containing N.
In the general formula (II), the linking group L represents a linking group containing an aromatic hydrocarbon ring and / or an aromatic heterocycle, and the linking groups L and N are the aromatic hydrocarbon ring or aromatic heterocycle. And n represents an integer of 2 or more.
In general formula (III), R represents an alkyl group which may have a substituent.
Rings A to G and linking group L may have a substituent, and these substituents may be bonded to each other to form a ring. )

  In the general formulas (I) to (III), the aromatic hydrocarbon rings represented by the rings A to G include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, an indene A ring etc. are mentioned. Examples of the aromatic heterocycle represented by rings A to G include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole. And a ring, a pyran ring, a thiadizole ring, an oxadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Preferred as the aromatic hydrocarbon rings A to G are a benzene ring, a naphthalene ring and an anthracene ring, and more preferred is a benzene ring. Moreover, as an aromatic heterocyclic ring of the rings A to G, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, and a thiazole ring are preferable, and a furan ring, a thiophene ring, and a pyrrole ring are more preferable.

  Rings included in ring A, ring B, ring D, ring E, ring F, ring G, and linking group L may be bonded to each other to form a condensed ring containing N. As an example in this case, Is an example of forming a carbazole ring containing an N atom to which each ring is bonded. When a carbazole ring is formed, any of the rings A to G is exceptionally not a ring structure and may be an arbitrary substituent, but in that case, it may preferably have a substituent. It is an alkyl group.

  Each of the rings A to G may have an arbitrary substituent at an arbitrary position, and these substituents may be bonded to each other to form a ring.

  In the general formula (II), the linking group L is a linking group containing one or more aromatic hydrocarbon rings and / or aromatic heterocycles, and N is an aromatic hydrocarbon ring of the linking group L. Or it is directly bonded to the aromatic heterocycle.

  Examples of the aromatic hydrocarbon ring and aromatic heterocyclic ring contained in the linking group L include the same as those exemplified as the aromatic hydrocarbon ring and aromatic heterocyclic ring of rings A to G. The aromatic hydrocarbon ring contained in the linking group L is preferably a benzene ring, a naphthalene ring or an anthracene ring, and more preferably a benzene ring. The aromatic heterocyclic ring contained in the linking group L is preferably a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, an oxazole ring, a thiazole ring, a thiadizole ring, or an oxadiazole ring, and more preferably a furan ring. Thiophene ring and pyrrole ring.

、アミン基、Ｏ原子、Ｓ原子、ケトン基、チオケトン基、−Ｃ（＝Ｏ）Ｏ−、アミド基、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｓｉ、Ｂなどの金属原子、芳香族炭化水素環基、芳香族複素環基（不飽和複素環基）、非芳香族複素環基（飽和複素環基）、及びこれらの任意の組み合わせなどを挙げることができる。 When the linking group L contains two or more aromatic hydrocarbon rings and / or aromatic heterocycles, these rings may be directly connected, or a divalent or higher valent linking group (note that this linking group). Is not limited to a divalent or higher group, but may include a divalent or higher atom). In this case, examples of the divalent or higher valent linking group include known ones, such as an alkylene group,

, Amine group, O atom, S atom, ketone group, thioketone group, —C (═O) O—, amide group, Se, Te, P, As, Sb, Bi, Si, B and other metal atoms, aromatic Examples thereof include a hydrocarbon ring group, an aromatic heterocyclic group (unsaturated heterocyclic group), a non-aromatic heterocyclic group (saturated heterocyclic group), and any combination thereof.

、アミン基、Ｏ原子、Ｓ原子、ケトン基、−Ｃ（＝Ｏ）Ｏ−、アミド基、芳香族炭化水素環基、芳香族複素環基、−Ｃ＝Ｎ−、−Ｃ＝Ｎ−Ｎ＝、飽和もしくは不飽和の複素環基であり、さらに好ましいのは炭素数が１〜３のアルキレン基、−ＯＣＨ_２Ｏ−、−ＯＣＨ_２ＣＨ_２Ｏ−、−Ｏ−、ケトン基、ベンゼン環基、フラン環基、チオフェン環基、ピロール環基である。また、前記一般式（II）において、ｎは好ましくは２〜５である。 Preferred as the linking group that can be sandwiched between the aromatic hydrocarbon ring and / or the aromatic heterocyclic ring contained in the linking group L is an alkylene group,

, Amine group, O atom, S atom, ketone group, —C (═O) O—, amide group, aromatic hydrocarbon ring group, aromatic heterocyclic group, —C═N—, —C═N—N =, A saturated or unsaturated heterocyclic group, more preferably an alkylene group having 1 to 3 carbon atoms, —OCH ₂ O—, —OCH ₂ CH ₂ O—, —O—, a ketone group, a benzene ring A group, a furan ring group, a thiophene ring group, and a pyrrole ring group. In the general formula (II), n is preferably 2 to 5.

  In the linking group L, it is desirable to have an absorption maximum and appropriate absorption in the wavelength region of 350 to 430 nm by adjusting the combination of the aromatic hydrocarbon ring or aromatic heterocyclic ring and the unsaturated linking group.

  The ring contained in the linking group L and the linking group for linking the rings may have an arbitrary substituent at an arbitrary position, and these substituents may be linked to each other to form a ring.

  Examples of the optional substituent that the rings A to G and the linking group L may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; a cyano group; a monovalent organic group, and the like. Examples of the monovalent organic group include the following.

Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, n-hexyl group, n-heptyl group, n -C1-C18 linear or branched alkyl group such as octyl group, tert-octyl group, etc.C3-C18 cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc. C2-C18 linear or branched alkenyl group such as a group, propenyl group, hexenyl group, etc. Cycloalkenyl group such as cyclopentenyl group, cyclohexenyl group, etc. Methoxy group, ethoxy group, n-propoxy group , Iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, amyloxy group , A tert-amyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, a tert-octyloxy group, etc., a linear or branched alkoxy group having 1 to 18 carbon atoms, a methylthio group, an 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- C1-C18 linear or branched alkylthio group such as octylthio group C6-C18 aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, etc. C7-C18 carbon atom such as benzyl group and phenethyl group Aralkyl group of carbon such as vinyloxy group, propenyloxy group, hexenyloxy group C2-C18 linear or branched alkenyloxy group such as vinylthio group, propenylthio group, hexenylthio group, etc. C2-C18 linear or branched alkenylthio group -Acyl group represented by COR ¹¹ Carboxyl group the carbamoyl group represented by carbamate group -CONR ¹⁷ R ¹⁸ represented by an acylamino group -NHCOOR ¹⁶ represented by an amino group -NHCOR ¹⁵ represented by an acyloxy group -NR ¹³ R ¹⁴ represented by -OCOR ¹² - Carboxylic acid ester group represented by COOR ¹⁹ —Sulphamoyl group represented by SO ₃ NR ²⁰ R ²¹ —Sulfonic acid ester group represented by SO ₃ R ²² —Group represented by C═NR ²³ —C═N -NR ²⁴ R ^25, a group represented by a 2-thienyl group, 2-pyridyl group, furyl group, oxazolyl group, benzoxazolyl group, a thiazolyl group, Benzochia Lil group, a morpholino group, a pyrrolidinyl group, a heterocyclic group, saturated or unsaturated, such as tetrahydrothiophene dioxide group

R ^{11 to} R ²⁵ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. In the above substituent group, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, and alkenylthio group are further substituted with a substituent. May be.

  There are no particular restrictions on the substitution positions of these substituents in the rings A to G and the linking group L, and when there are a plurality of substituents, these may be the same or different. Also good.

Rings A to G and linking group L are unsubstituted or substituted as a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituted group. An alkenyl group which may be substituted, an aryl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, an alkenyloxy group which may be substituted, an alkenylthio which may be substituted group, may be substituted amino group, an optionally substituted acyl group, a carboxyl group, a group represented by -C = NR ^23, the group represented by ^{-C = N-NR 24 R 25} , saturated Alternatively, it is preferably substituted with an unsaturated heterocyclic group, and more preferable substituents in the case of having a substituent include a halogen atom, a cyano group, an optionally substituted alkyl group, a substituent. A cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an alkoxy group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, A good amino group, a group represented by —C═NR ²³ , a group represented by —C═N—NR ²⁴ R ²⁵ , and a saturated or unsaturated heterocyclic group.

In the case where the above-mentioned optional substituents that the rings A to G and the linking group L may have are further substituted with arbitrary substituents, preferred examples of this substituent include
C1-C10 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, etc. Methoxymethoxy group, ethoxymethoxy group, propoxymethoxy Group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group, etc., alkoxy alkoxy group having 2 to 12 carbon atoms such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, ethoxymethoxymethoxy group, ethoxyethoxymethoxy group, etc. C3-C15 alkoxy alkoxy alkoxy group C6-C12 aryl groups, such as a phenyl group, a tolyl group, a xylyl group (these may be further substituted by the substituent).
C6-C12 aryloxy group such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group, etc. C2-C12 alkenyloxy group such as vinyloxy group, allyloxy group Acyl group such as acetyl group, propionyl group, cyano group Nitro group Hydroxyl group Tetrahydrofuryl group Amino group N, N-dimethylamino group, C1-C10 alkylamino group such as N, N-diethylamino group Methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group C1-C6 alkylsulfonylamino group such as fluorine atom, chlorine atom, bromine atom, etc. Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, etc. Charcoal Alkylcarbonyl group having 2 to 7 carbon atoms such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, etc. C2-C7 alkoxycarbonyloxy group such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group, tert-butoxycarbonyloxy group vinyl And a straight chain or branched alkenyl group having 2 to 18 carbon atoms such as a group, a propenyl group and a hexenyl group.

  The sensitizers represented by the general formulas (I) to (III) used in the present invention have an appropriate absorption in the wavelength range of 390 to 430 nm, and therefore have a wavelength of 300 to 430 nm, preferably 350 to 430 nm. It is preferable to have an absorption maximum in the region. Therefore, the molecule preferably has 4 or more aromatic hydrocarbon rings and / or aromatic heterocycles, and more preferably has 5 or more aromatic hydrocarbon rings and / or aromatic heterocycles. .

  Specific examples of the sensitizer represented by the general formulas (I) to (III) are shown below, but are not limited thereto.

  The sensitizers represented by the general formulas (I) to (III) may be used alone or in combination of two or more. Further, other sensitizing dyes may be used in combination as long as the performance of the present invention is not impaired. For example, several types may be mixed and used for the purpose of improving the solubility.

  As other dyes that can be used in combination with the sensitizer according to the present invention, known dyes can be used. Preferred examples include dialkylaminophenyl compounds, merocyanine compounds, sulfoimino compounds, carbostyril compounds, Stilbene compounds, cyanostyryl compounds, imidazole / thiazole / oxazole compounds, triazole compounds, oxadiazole / thiadiazole compounds, coumarin compounds, imide compounds, pyrazoline compounds, thiazolidene ketone compounds, acridone compounds Compounds and the like. Specific examples thereof include compounds described as fluorescent brighteners in “New dyeing course, Vol. 1, dyes and pigments” (Terzo Asahara, Masao Nanjo, Kyoritsu Shuppan), JP-B-6-29285, JP-A-14 The compounds described in JP-A Nos. 268239, 14-169282, and 12-10277 are used.

(C) Photopolymerization initiator The photopolymerization initiator (C) is an active radical that receives photoexcitation energy of a sensitizer when irradiated with a sensitizer (B). A radical generator that causes polymerization of the ethylenically unsaturated compound of component (A), which is a hexaarylbiimidazole compound, a halogenated hydrocarbon derivative, an iodonium salt, an organic borate, and It is at least one photopolymerization initiation component selected from titanocene compounds. Among these, hexaarylbiimidazole compounds, organoborates, and titanocene compounds are preferable from the viewpoints of sensitivity as a photosensitive composition, adhesion to a substrate, and storage stability, and are safe under yellow light. A hexaarylbiimidazole compound is particularly preferred from the viewpoint of light properties.

  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) bi Imidazole, 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) biimidazo 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, for example, by the method disclosed in Bull. Chem. Soc. Japan; 33,565 (1960), J. Org. Chem .; 36, 2262 (1971), etc. May be used in combination with a biimidazole compound.

  In addition, the 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. The spectrum has a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.925 °. The hexaarylbiimidazole compound in the present invention has a solubility in a coating solvent and a photosensitive composition. In view of dispersion stability, the melting point is 180 ° C. or lower, further 175 ° C. or lower, and the Bragg angle (2θ ± 0.2 °) 21.16 in the X-ray diffraction spectrum with a wavelength of 1.54 mm. It is optimal to have a maximum peak at °, and examples of the optimal hexaarylbiimidazole compound include 2,2′-bis ( -Chlorophenyl) -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, among which 2,2′-bis (o-chlorophenyl) -4,4 ′, 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.

  Among the halogenated hydrocarbon derivatives, examples of the halogen-substituted alkane include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, and the like.

  Among the halogenated hydrocarbon derivatives, examples of the halomethylated s-triazine derivative 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 (to Chloromethyl) -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 (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis ( Lichloromethyl) -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- And bis (tribromomethyl) -s-triazine and the like. Among them, bis (trihalomethyl) -s-triazine is preferable, and 2-methyl-4,6-biazine is preferable. (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) -4,6-bis (Trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like are particularly preferable.

  Examples of the halomethylated 1,3,4-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) -5-trichloromethyl-1,3,4-oxadiazole and the like.

  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.

  Examples of the titanocene compound include 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), dicyclopenta Dienyltitanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium bis ( 2,3,4,5,6-pentafluorofe Le), 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.

(D) Alkali-soluble resin The blue-violet laser photosensitive composition of the present invention as a negative-type photopolymerizable photosensitive composition is applied to the substrate in addition to the components (A), (B), and (C). For the purpose of improving the formability and developability of the photosensitive resist material layer, it is preferable to further contain (D) an alkali-soluble resin. Examples of the alkali-soluble resin of component (D) include (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide and the like. Single or copolymer, as well as polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. Among them, in terms of alkali developability, carboxyl group-containing vinyl type Resins are preferred.

  As the carboxyl group-containing vinyl resin, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, styrene, α-methylstyrene , Styrenes such as 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 (Meth) acrylates such as N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethyl Examples thereof include amides such as aminoethyl (meth) acrylamide and copolymers with vinyl compounds such as vinyl acetate.

  Among these, styrenes- (meth) acrylates- (meth) acrylic acid copolymers are preferable, styrenes 1-30 mol%, (meth) acrylates 10-80 mol%, (meth) acrylic acid 10 A copolymer consisting of ˜60 mol% is more preferred, and a copolymer consisting of 2 to 25 mol% styrenes, 20 to 70 mol% (meth) acrylates, and 15 to 55 mol% (meth) acrylic acid is particularly preferred. .

  Of these, styrenes are effective in securing image strength, but are preferably used in an amount of about 2 to 15 mol% in the copolymer.

  For example, when the blue-violet laser-sensitive composition of the present invention is used as a dry film, it is necessary to ensure adhesion with a support film or a cover film, and butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate It is preferable to contain the compound which has a C3-C12 alkyl group, such as, in a copolymer, and it is preferable that the ratio uses 5-20 mol% in a copolymer.

  In addition, these carboxyl group-containing vinyl resins have an acid value of 30 to 300 mg-KOH / g, a gel-permeation chromatography (hereinafter abbreviated as “GPC”) measurement, and a polystyrene-reduced weight average molecular weight (hereinafter referred to as “ It is preferably abbreviated as “weight average molecular weight Mw by GPC measurement”) of 1,000 to 300,000.

  In particular, when used as a dry film resist, if the acid value of the alkali-soluble resin having a carboxyl group in the present invention is too low, development will be poor, and if it is too high, damage to the resist during development will increase. -KOH / g is preferable, and 100 to 250 mg-KOH / g is particularly preferable. In addition, if the molecular weight is too small, the strength when the photosensitive composition is made into a film becomes weak, developability is unstable, and when used as a film, problems such as worsening chipping properties are seen, On the other hand, if it is too large, problems such as poor development or a problem that the viscosity of the photosensitive solution becomes too large to cause a problem in handling occur. Therefore, the weight average molecular weight Mw by GPC measurement is 10,000 to 200,000. It is preferable that it is 20,000-100,000.

  Further, the carboxyl group-containing vinyl resin may have an ethylenically unsaturated bond in the side chain. For example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl is added to the carboxyl group-containing polymer. (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. Saturated compounds, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl Reaction obtained by reacting an alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate with a carboxyl group-containing polymer in an amount of 5 to 90 mol%, preferably about 30 to 70 mol%. Products and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) Compounds having two or more unsaturated groups such as acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl croto Nate, vinyl (meth) acrylamide, etc. 10 to 90 mol of the compound having the above unsaturated group and unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester in the former compound having an unsaturated group %, Preferably a reaction product obtained by copolymerization so as to be about 30 to 80 mol%.

  In the present invention, the alkali-soluble resin may be used singly or in combination of two or more, but when two or more alkali-soluble resins are used in combination, the acid of the conversion average value thereof is used. It is preferable that the value and the weight average molecular weight Mw by GPC measurement are in the above ranges.

(E) Polymerization accelerator The blue-violet laser-sensitive composition of the present invention may further contain a polymerization accelerator (E) component for the purpose of improving the photopolymerization initiation ability. Examples of the polymerization accelerator include an aliphatic amino acid ester compound which is an aliphatic monoaminomonocarboxylic acid, and a dipolar ion compound. Among them, in the following general formula (E-1) or (E-2): Those represented are preferred.

（式（Ｅ−１）及び（Ｅ−２）中、Ｒ⁵¹は水素原子、又は置換基を有していても良いアルキル基を表し、Ｒ⁵²は水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアリル基、置換基を有していても良いビニル基、又は置換基を有していても良いアリール基を表し、Ｒ⁵³及びＲ⁵⁴は各々独立して、水素原子、置換基を有していても良いアルキル基、カルボキシル基、又は置換基を有していても良いアリール基を表し、Ｒ⁵⁵は置換基を有していても良いアルキル基、又は置換基を有していても良いアリール基を表し、ｓは０〜１０の整数を表す。）

(In formulas (E-1) and (E-2), R ⁵¹ represents a hydrogen atom or an alkyl group which may have a substituent, and R ⁵² may have a hydrogen atom or a substituent. A good 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 ⁵³ and R ⁵⁴ represents Independently, it represents a hydrogen atom, an optionally substituted alkyl group, a carboxyl group, or an optionally substituted aryl group, and R ⁵⁵ represents an ^optionally substituted alkyl. Represents an aryl group which may have a group or a substituent, and s represents an integer of 0 to 10.)

Here, R ⁵¹ in the general formulas (E-1) and (E-2) is a hydrogen atom or a methyl group, but R ⁵² is a hydrogen atom or an alkyl group which may have a substituent. Or a phenyl group which may have a substituent, and R ⁵³ and R ⁵⁴ are a hydrogen atom, an alkyl group which may have a substituent, or a carboxyl group ^. Is an alkyl group which may have a substituent or a phenyl group which may have a substituent, and s is preferably an integer of 0 to 5, respectively.

The alkyl group which may have a substituent of R ^{52 and} the phenyl group which may have a substituent include, for example, a methyl group, an acetoxymethyl group, an ethoxycarbonylmethyl group, an allyloxycarbonylmethyl group, ethyl Group, acetoxyethyl group, ethoxycarbonylethyl group, chloroethyl group, methylsulfonylethyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-vinylpropyl group, 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′-methacryloyl) Oxypropoxyethoxy) propyl group 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. Examples of the alkyl group which may have a substituent for R ⁵³ and R ⁵⁴ include a methyl group and an ethyl group. Examples of the alkyl group which may have a substituent of R ⁵⁵ and the phenyl group which may have a substituent include, for example, a methyl group, an ethyl group, a lauryl group, a phenyl group, and a 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 -Fluorophenyl group, p-chlorophenyl group, p-bromophenyl group, o-carboxy-p-bromophenyl group, p-dimethylaminophenyl group, 3,5-diaminophenyl group, p-cyanophenyl group, p-benzoyl A phenyl group, p- (p-aminobenzyl) sulfonylphenyl group, etc. are mentioned.

  Among these, an ester of an aliphatic amino acid and a dipolar compound are particularly preferably an ester of N-phenylglycine and a dipolar compound.

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

  Further, 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, trimethylol propane 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 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.

(F) Surfactant The blue-violet laser-sensitive composition of the present invention is nonionic, anionic, cationic, amphoteric, fluorine-based, etc. for the purpose of improving the coating property as a coating solution and the developing property. The surfactant (F) component may be contained, for example, as the nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ether , 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 , Polyoxy Ethylene sorbitan fatty acid esters, sorbite fatty acid esters, polyoxyethylene sorbite fatty acid esters, etc., and anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxy Ethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfates, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters , Polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates and the like, and as the cationic surfactant, Quaternary ammonium salts, imidazoline derivatives, amine salts and the like, As the amphoteric surfactant, betaine type compounds, imidazolium salts, imidazolines, amino acids and the like can be mentioned, respectively.

  In the blue-violet laser photosensitive composition of the present invention of a negative photopolymerizable photosensitive composition, the ethylenically unsaturated compound (A), the sensitizer (B), and the photopolymerization (C) Each content ratio of the initiator, the alkali-soluble resin of the component (D), the polymerization accelerator of the component (E), and the surfactant of the component (F) is (A ) Component is 10 to 90% by weight, component (B) is 0.05 to 20% by weight, component (C) is 0.5 to 50% by weight, component (D) is 0 to 80% by weight, component (E) Is preferably 0 to 30% by weight, component (F) is preferably 0.1 to 10% by weight, component (A) is 20 to 70% by weight, component (B) is 0.1 to 10% by weight, C) Component 1-30 wt%, (D) Component 10-70 wt%, (E) Component 0-20 wt%, (F) Component 1- And even more preferably wt%.

  In addition, the blue-violet laser photosensitive composition of the present invention in the case of a negative photopolymerizable photosensitive composition further includes various additives such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl. A thermal polymerization inhibitor such as -p-cresol, 2% by weight or less based on the total amount of the photosensitive composition, a colorant comprising an organic or inorganic dye / pigment is also 20% by weight or less, dioctyl phthalate, didodecyl phthalate, A plasticizer such as tricresyl phosphate is also contained in a proportion of 40% by weight or less, a sensitivity property improving agent such as tertiary amine or thiol is also contained in a proportion of 10% by weight or less, and a dye precursor is also contained in a proportion of 30% by weight or less. Also good.

<Negative light amplification type photosensitive composition>
The blue-violet laser photosensitive composition of the present invention as a negative light-amplifying photosensitive composition includes (B) a sensitizer represented by the general formulas (I) to (III), and the following (N- 1), (N-2), and (N-3) components. (B) About a sensitizer, it is as having described in description of the above-mentioned negative type photopolymerizable photosensitive composition.

(N-1) Alkali-soluble resin The alkali-soluble resin (N-1) is not particularly limited as long as the unexposed portion becomes alkali-soluble during development and elutes into an alkali developer. Phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof are used. Among these, those containing a polymer unit having a phenolic hydroxyl group are particularly preferred, and novolak resins or polyvinylphenols are preferred.

  As novolak resins, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcin, pyrogallol, bisphenol, bisphenol-A, trisphenol, o-ethylphenol, m-ethyl At least one of aromatic hydrocarbons such as phenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol and the like in the form of an acidic catalyst, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, Examples include aldehydes such as furfural and polycondensation with at least one aldehyde or ketone selected from ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Paraformaldehyde and paraaldehyde may be used in place of formaldehyde and acetaldehyde, respectively.

  As the novolak resin, those having a weight average molecular weight Mw by GPC measurement of 1,000 to 15,000, preferably 1,500 to 10,000 are used.

  As the novolac resin, more preferably, at least one phenol selected from o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and resorcin is formaldehyde, acetaldehyde, propion. Examples thereof include novolak resins polycondensed with at least one selected from aldehydes such as aldehydes. Among them, the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcin is 70-100: 0-30: 0-20: 0-20-20-20 in molar ratio. A novolak resin which is a polycondensate of phenols and aldehydes is preferred. Of the aldehydes, formaldehyde is particularly preferable.

  Polyvinylphenols include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene Examples thereof include hydroxystyrenes alone or two or more polymers. Hydroxystyrenes may have a substituent such as a halogen such as chlorine, bromine, iodine, fluorine or an alkyl group having 1 to 4 carbon atoms in the benzene ring. Accordingly, as polyvinylphenols, halogen or The polyvinyl phenol which may have a C1-C4 alkyl group is mentioned.

  Polyvinylphenols are usually obtained by polymerizing hydroxystyrenes which may have a substituent alone or in the presence of a radical polymerization initiator or a cationic polymerization initiator. Such polyvinylphenols may be partially hydrogenated to reduce the absorbance of the resin. Further, a resin in which a part of the OH groups of the polyvinylphenols is protected with a t-butoxycarbonyl group, a pyranyl group, a furanyl group, or the like may be used. The weight average molecular weight Mw by GPC measurement of polyvinylphenols is 1,000 to 100,000, preferably 1,500 to 50,000. More preferable examples of the polyvinylphenol include polyvinylphenol which may have an alkyl group having 1 to 4 carbon atoms in the benzene ring, and unsubstituted polyvinylphenol is particularly preferable.

  If the molecular weight of the alkali-soluble resin is smaller than the above range, a sufficient coating film as a resist cannot be obtained. It tends to be impossible.

  Of the alkali-soluble resins described above, unsubstituted polyvinyl phenol and novolak resin are particularly preferable.

(N-2) Crosslinking agent that acts on alkali-soluble resin under acidic conditions As crosslinking agent (N-2) that acts on the alkali-soluble resin of component (N-1) under photoacidic conditions, the alkali-soluble resin used Although it will not specifically limit if it is a compound which carries out a crosslinking reaction, As an example, the compound which made formalin act on melamine, a benzoguanamine, glycoluril, or urea, those alkyl modified compounds, an epoxy compound, a resole compound, etc. are mentioned.

  As an example of a compound in which formalin is allowed to act on melamine or an alkyl-modified product thereof, specifically, Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, Mitsui Cyanamid Co., Ltd. 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, Nikarak (registered trademark) E-2151, Sanwa Chemical Co., Ltd., MW-100LM, MX- 750LM.

  Examples of the compound in which formalin is allowed to act on benzoguanamine or the alkyl-modified product thereof include Cymel (registered trademark) 1123, 1125, 1128 manufactured by Mitsui Cyanamid Co., Ltd. Examples of the alkyl-modified product include Cymel (registered trademark) 1170, 1171, 1174, 1172 manufactured by Mitsui Cyanamid Co., Ltd., and Nikalac (registered trademark) MX-270 manufactured by Sanwa Chemical Co., Ltd. Examples of the compound in which formalin is allowed to act on urea or an alkyl-modified product thereof include UFR (registered trademark) 65 and 300 manufactured by Mitsui Cyanamid Co., Ltd. and Nicarak (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd.

  Examples of epoxy compounds include novolak epoxy resins (manufactured by Toto Kasei Co., Ltd., YDP N-638, 701, 702, 703, 704, etc.), amine epoxy resins (manufactured by Toto Kasei Co., Ltd., YH-434, etc.), and bisphenol A epoxy resins. (Japan Epoxy Resin, Epicoat 825, 826, 827, 828, 1001, 1002, 1003, 1055, 1004, 1007, 1009, 1010, etc.), sorbitol (poly) glycidyl ether, (poly) glycerol (poly) glycidyl ether , Pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate, allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, Uryl alcohol glycidyl ether, adipic acid glycidyl ether, phthalic acid glycidyl ether, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycidyl phthalimide, (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl Examples include ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, and butyl glycidyl ether.

Among these, particularly preferred compounds include compounds having —N (CH ₂ OR ⁶⁰ ) ₂ group (wherein R ⁶⁰ represents an alkyl group or a hydrogen atom) in the molecule. Specifically, a compound obtained by allowing formalin to act on urea or melamine or an alkyl-modified product thereof is particularly preferable.

(N-3) Photoacid generator The photoacid generator (N-3) is the same as the photoacid generator (P-2) used in the positive photosensitive composition described later, Of these, halomethylated s-triazine derivatives are preferred.

  In the blue-violet laser photosensitive composition of the present invention, which is a negative light-amplifying photosensitive composition, the crosslinking agent (N-2) is usually 1 to 80 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (N-1). The photoacid generator (N-3) is usually used in a proportion of 0.001 to 30 parts by weight, preferably 0.005 to 10 parts by weight. The (B) sensitizer is used in an amount of about 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C-1).

  If the amount of the crosslinking agent (N-2) is less than the above range, a sufficient crosslinking effect cannot be obtained and the resist pattern tends to be defective. On the other hand, when the amount of the cross-linking agent is larger than this range, the resist coating characteristics tend to be lowered. Moreover, when the amount of the (N-3) photoacid generator is less than this range, the sensitivity tends to be low. When the amount of the photoacid generator is larger than this range, the resist pattern becomes an inverted trapezoid due to a decrease in the transparency of the resist film due to the photoacid generator, and the resolution tends to decrease. (B) When the amount of the sensitizer is less than this range, the sensitivity is lowered, and when it is larger, the resolution is lowered.

  The blue-violet laser photosensitive composition of the present invention, which is a negative type photoamplifying photosensitive composition, is a polymerization accelerator similar to that described above as the component (E) of the negative type photopolymerizable photosensitive composition. For the purpose of improving storage stability, may be contained in the same amount as the amount of the negative photopolymerizable photosensitive composition, and the component (F) of the negative photopolymerizable photosensitive composition is described above. For the purpose of improving developability, the same surfactant as that prepared may be contained in the same amount as the amount of the negative photopolymerizable photosensitive composition.

<Positive photosensitive composition>
The blue-violet laser photosensitive composition of the present invention as a positive photosensitive composition contains (B) a sensitizer and the following (P-1) and (P-2) components. (B) About a sensitizer, it is as having described in description of the above-mentioned negative type photopolymerizable photosensitive composition.

(P-1) Acid-decomposable group-containing polymer The (P-1) component acid-decomposable group-containing polymer will be described later when the photosensitive composition is irradiated with actinic rays (P-2). The polymer is not particularly limited as long as it is a polymer containing an acid-decomposable group that is decomposed by an acid generated by the component photoacid generator and imparts alkali solubility to the polymer itself.

  Examples of the acid-decomposable group include alkoxy groups having 1 to 15 carbon atoms such as methoxy group, ethoxy group, i-propoxy group, and t-butoxy group, methoxymethoxy group, dimethoxymethoxy group, ethoxymethoxy group, 1- C2-C15 alkoxyalkoxy groups such as methoxyethoxy group, 1-ethoxyethoxy group, 1-propoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 1-ethoxypropoxy group, methoxycarbonyl 2-15 alkoxycarbonyloxy groups such as oxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, ethoxycarbonyloxymethoxy Group, n-propo An alkoxy group at least at the terminal, such as a C2-C15 alkoxycarbonyloxyalkoxy group such as a sicarbonyloxymethoxy group, i-propoxycarbonyloxymethoxy group, n-butoxycarbonyloxymethoxy group, t-butoxycarbonyloxymethoxy group, etc. Group which has.

  Examples of the polymer containing an acid-decomposable group include etherification of at least a part of phenolic hydroxyl groups of phenolic hydroxyl group-containing resins such as phenolic resins such as novolak resins and resol resins, and polyvinylphenol resins. A resin in which the acid-decomposable group is introduced by esterification is preferred. Among them, in the present invention, a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin or a novolac resin is more preferable, and a resin in which the acid-decomposable group is introduced into a polyvinylphenol resin is particularly preferable.

  Here, the novolak resin is, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, Propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, 4,4'-biphenyldiol, 2 , 2-bis (4′-hydroxyphenyl) propane and the like, under an acid catalyst, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and furfural (forma Paraformaldehyde may be used instead of dehydride, and paraaldehyde may be used instead of acetaldehyde.) Or a resin obtained by polycondensation with at least one of ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The resol resin is a resin that has been polycondensed in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin. These novolak resins and resol resins preferably have a weight average molecular weight Mw by GPC measurement of 1,000 to 15,000, particularly preferably 1,500 to 10,000.

  Polyvinylphenol resins include, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2 Hydroxystyrenes such as-(m-hydroxyphenyl) propylene and 2- (p-hydroxyphenyl) propylene (note that these are halogen atoms such as chlorine, bromine, iodine and fluorine on the benzene ring, or carbon numbers 1 to 4 In which the alkyl group may be substituted as a substituent. These polyvinyl phenol resins preferably have a weight average molecular weight Mw by GPC measurement of 1,000 to 100,000, particularly preferably 1,500 to 50,000.

  Moreover, as a polymer containing the said acid-decomposable group, the resin which esterified at least one part of the carboxyl group of carboxyl group-containing vinyl resin and introduce | transduced the said acid-decomposable group can be mentioned as a preferable thing, for example. . As the carboxyl group-containing vinyl resin, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, 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) ) Vinyl compounds such as acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, vinyl acetate These carboxyl group-containing vinyl resins preferably have a weight average molecular weight Mw by GPC measurement of 1,000 to 300,000.

(P-2) Photoacid generator The photoacid generator of component (P-2) is a compound that generates an acid when the photosensitive composition is irradiated with actinic rays. Halogen-containing compounds such as alkanes and halomethylated s-triazine derivatives, onium salts, sulfone compounds and the like are preferred, and among them, halomethylated s-triazine derivatives are particularly preferred in the present invention.

  Here, among the halogen-containing compounds, examples of the halogen-substituted alkane include dichloromethane, trichloromethane, 1,2-dichloroethane, 1,2-dibromoethane, and the like.

  Among the halogen-containing compounds, examples of the halomethylated s-triazine derivative 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 (trichloro) Methyl) -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 (trick (Romethyl) -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) -4,6-bis (tri (Rolomethyl) -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- And bis (tribromomethyl) -s-triazine and the like. Among them, 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 (trichloro Methyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloro) Particularly preferred are methyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of the onium salts include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, diphenyliodonium camphorsulfonate, dicyclohexyliodonium. Hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, icyclohexyl salt such as dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenyls Honiumu p- toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

  Examples of the sulfone compounds include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, bis (α-naphthylsulfonyl) methane, and bis (β- Bis (sulfonyl) methane compounds such as naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) ) Methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, phenylcal Carbonyl (sulfonyl) methane compounds such as bonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) Diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane compounds , Phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, phenyl Carbonyl (sulfonyl) diazomethane compounds such as carbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane Etc.

  In the blue-violet laser photosensitive composition of the present invention which is a positive photosensitive composition, the acid-decomposable group-containing polymer of the component (P-1) and the photoacid generator of the component (P-2) Each content is preferably 1 to 50 parts by weight of the photoacid generator of component (P-2) with respect to 100 parts by weight of the acid-decomposable group-containing polymer of component (P-1). More preferably, it is -30 weight part. The content ratio of (B) sensitizer is preferably 1 to 30 parts by weight, and 5 to 20 parts by weight, with respect to 100 parts by weight of the acid-decomposable group-containing polymer of component (P-1). More preferably, it is part.

  The blue-violet laser photosensitive composition of the present invention, which is a positive photosensitive composition, improves the coating properties when forming a photosensitive resist material layer on a substrate and the developability of the photosensitive resist material layer. For the purpose, it may contain nonionic, anionic, cationic, amphoteric, and fluorine-based surfactant (P-3) components. The same thing as what was mentioned as surfactant of the (F) component of an adhesive composition can be mentioned, The content rate is 100 weight part of the acid-decomposable group containing polymer of the said (P-1) component. On the other hand, it is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight.

  Regardless of the type of photosensitive composition, the blue-violet laser photosensitive composition of the present invention preferably has a maximum spectral sensitivity peak in the wavelength range of 390 to 430 nm, and in the wavelength range of 400 to 420 nm. It is further preferable to have a maximum peak of spectral sensitivity. When having a maximum peak of spectral sensitivity in a wavelength range less than the above range, the sensitivity to a light source or blue-violet laser light containing a wavelength range of 350 to 430 nm as the photosensitive composition is inferior, while the wavelength range exceeding the above range When it has, it will be inferior in the safe light property under a yellow light.

  In the present invention, the maximum peak of spectral sensitivity is, for example, as described in detail in “Photopolymer Technology” (Aoyama 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 apparatus 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 images can be formed from the 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. When this minimum exposure amount [S410] exceeds 10 mJ / cm ² , although depending on the exposure intensity of the light source used, 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.

Further, the blue-violet laser-sensitive composition of the present invention has a ratio [S410] / [S450] of [S410] to the minimum exposure amount [S450] (mJ / cm ² ) capable of forming an image at a wavelength of 450 nm of 0. It is preferably 1 or less, and more preferably 0.05 or less. If this ratio [S410] / [S450] is greater than 0.1, it is difficult to achieve both light sensitivity to a light source including a wavelength region of 350 to 430 nm or blue-violet laser light and safe light property under a yellow lamp. Become.

Further, the blue-violet laser-sensitive composition of the present invention can form an image 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 more than 450 nm and not more than 650 nm. The ratio [S450-650] / [S450] to the minimum exposure [S450] (mJ / cm ² ) is preferably larger than 1. When this ratio [S450-650] / [S450] is 1 or less, it tends to be difficult to achieve both a light sensitivity including a wavelength range of 350 to 430 nm or a blue-violet laser beam and a safelight property under a yellow lamp. It becomes.

  The minimum exposure amount that can form an image at a wavelength of 410 nm [S410], the minimum exposure amount that can be imaged at a wavelength of 450 nm [S450], and the minimum exposure amount that can form an image at a wavelength of 450 nm to 650 nm. [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 development at that time This means the minimum exposure that can form an image under optimum development conditions determined by changing development conditions such as the type of solution, development temperature, development time, etc. The optimum development conditions are usually alkaline of pH 11-14. Conditions for immersing in a developer at a temperature of 25 ° C. for 0.5 to 3 minutes are employed.

  The blue-violet laser-sensitive composition of the present invention is usually a photosensitive composition formed as necessary by applying it on a temporary support film as a coating solution obtained by dissolving or dispersing the above components in an appropriate solvent. By covering the surface of the physical layer with a coating film, the photosensitive image forming material of the present invention as a so-called dry film resist material or the like is formed, and the coating film is peeled off from the photosensitive composition layer side of the image forming material. This is applied to the substrate to be processed by laminating on the substrate to be processed, or by directly applying the components to the substrate to be processed as a coating solution in which each component is dissolved or dispersed in a suitable solvent. The photosensitive image forming material of the present invention having a layer of the blue-violet laser photosensitive composition of the present invention formed thereon. The photosensitive composition layer of the image forming material is a light source or a blue-violet color having a wavelength range of 350 to 430 nm. Les Exposed by Heather light, preferably, to scanning exposure with a laser beam having a wavelength 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 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 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. 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. Below, more preferably 100 μm or less. In particular, according to the blue-violet laser photosensitive composition of the present invention, high sensitivity 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 addition, the absorbance at the exposure wavelength of the entire photosensitive composition layer formed of the blue-violet laser photosensitive composition of the present invention is usually in the range of 0.05 to 3, particularly preferably in the range of 0.2 to 1. When exposing with the exposure amount of about 2-16 mJ / cm < ² >, 0.2-0.5 is the most preferable. If the absorbance is less than 0.05, the resolution becomes low due to the influence of halation. In particular, when it exceeds 3, light is absorbed only in the upper part, and the adhesion tends to be lowered.

  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. On the layer, a protective layer such as an oxygen blocking layer for preventing the polymerization-inhibiting action due to oxygen of the photopolymerizable composition, or a light transmittance adjusting layer for adjusting the wavelength region of the maximum peak of the spectral sensitivity described above May be formed.

  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 standpoint of oxygen barrier properties, etc., and from the standpoint 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 it as a mixture in which parts by weight are mixed.

  The oxygen barrier layer preferably contains an organic acid such as oxalic acid or an organic acid salt such as ethylenediaminetetraacetic acid from the viewpoint of imparting preservability, and nonion such as polyoxyethylene alkylphenyl ether. , Anionic properties such as sodium dodecylbenzenesulfonate, cationic properties such as alkyltrimethylammonium chloride, antifoaming agents, dyes, plasticizers, pH adjusting agents, etc. 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 .

  Moreover, as what constitutes a light transmittance adjusting layer, for example, a polymer binder that contains a light-absorbing dye in the visible region such as a coumarin-based dye can be mentioned. Can be made into a protective layer having an oxygen blocking ability and a light transmittance adjusting ability by using polyvinyl alcohol or a derivative thereof or a polyvinyl pyrrolidone polymer mentioned in the oxygen blocking layer.

  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, particularly scanning exposure with laser light, and then development processing. As a result, a resist image is formed.

  Here, the light source including a wavelength range of 350 to 430 nm is not particularly limited, but for example, 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, a low pressure mercury lamp. Lamp light sources such as For example, specific 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, and in particular, a blue-violet laser having a wavelength range of 390 to 430 nm. A light source that generates 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 at 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 to 20 μm, scanning speed is preferably 50 to 500 m / second, more preferably 100 to 400 m / second, scanning density is preferably 2,000 dpi or more, more preferably 4,000 dpi or more, Scan exposure.

  The development processing after 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 of, one or more of these are used at a concentration of about 0.1 to 5 wt%.

  Examples of the surfactant include the same surfactants as those mentioned as the component (F) of the photosensitive composition, and among these, nonionic, anionic, or amphoteric surfactants are preferable. Amphoteric surfactants, especially 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 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.

  The ethylenically unsaturated compounds, sensitizers, photopolymerization initiators, and alkali-soluble resins used in the following examples and comparative examples are as follows.

<Ethylenically unsaturated compound>

<Sensitizer>

<Photopolymerization initiator>

<Alkali-soluble resin>
Methyl methacrylate / 2-ethylhexyl acrylate / n-butyl methacrylate / 2-hydroxyethyl methacrylate / styrene / methacrylic acid copolymer (molar ratio 35/10/10/15/10/20, acid value 144 mg-KOH / g, GPC Weight average molecular weight Mw 62,300 by measurement)

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 the coating liquid 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 20 μm, and dried in an oven at 90 ° C., and a polyethylene film (thickness 20 μm) as a coating film is formed on the formed photosensitive composition layer. Laminated and used as a photosensitive image forming material.

  The absorbance of this photosensitive image forming material was measured by the following method.

<Measurement of absorbance>
The obtained sheet was measured using a UV-Vis spectrophotometer, UV-3100 (manufactured by Shimadzu Corporation), with the above-mentioned polyethylene terephthalate film (thickness 19 μm) not coated with anything as a reference.

  Separately, a copper foil surface of a polyimide resin copper-clad laminate (thickness 1.5 mm, size 250 mm × 200 mm) bonded with a 35 μm-thick copper foil is buffed with “Scotch Bright SF” manufactured by Sumitomo 3M Limited. After washing with water and drying with an air flow, the surface is then preheated to 60 ° C. in an oven, and then the photosensitive image-forming material obtained above is placed on the copper foil of the copper-clad laminate. Using a hand-type roll laminator while peeling the polyethylene film, laminating at a roll temperature of 100 ° C., a roll pressure of 0.3 MPa, and a laminating speed of 1.5 m / min. The composition layer was made.

  About the obtained photosensitive composition layer, the exposure sensitivity was measured by the method shown below.

<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, the sensitivity at the maximum peak of spectral sensitivity was measured by the following method.

<Maximum peak of spectral sensitivity>
A sample obtained by cutting an image forming material into a size of 50 × 60 mm is 350 using a diffraction spectroscopic irradiation device (“RM-23” manufactured by Narumi) and a xenon lamp (“UI-501C” manufactured by USHIO INC.) As a light source. Exposure is performed by irradiating light separated in a wavelength region of ˜650 nm so that the exposure wavelength is linearly changed in the horizontal axis direction and the exposure intensity is logarithmically changed in the vertical axis direction, and irradiated for 10 seconds. An image corresponding to the sensitivity of each exposure wavelength can be obtained by spraying 0.7% by weight sodium carbonate aqueous solution as a developing solution to a pressure of 0.15 MPa and spray developing in 1.5 times the minimum development time. The maximum peak in the spectral sensitivity curve obtained by calculating the exposure energy capable of image formation from the image height, and plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis. It was read.

<[S410], [S410] / [S450], [S450-650] / [S450]>
Further, the minimum exposure amount [S410] (mJ / cm ² ) capable of forming an image at a wavelength of 410 nm was measured by the same method as in the measurement of the maximum peak of the spectral sensitivity.
Further, 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 a wavelength at a wavelength of 450 nm when the exposure is performed while changing the wavelength in the wavelength range of 350 to 650 nm and developing. The minimum exposure amount [S450] (mJ / cm ² ) capable of image formation was determined, 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.
Further, a minimum exposure amount [S450-650] (mJ / cm ² ) capable of forming an image at each wavelength exceeding 450 nm and not more than 650 nm is obtained, and the minimum exposure amount [S450] (mJ / cm ² ) capable of forming an image at a wavelength of 450 nm. ² ) The ratio [S450-650] / [S450] was calculated and evaluated according to the following criteria.
Evaluation criteria of [S450-650] / [S450] A: [S450-650] / [S450] exceeds 10.
B: [S450-650] / [S450] is more than 5 and 10 or less.
C: [S450-650] / [S450] is more than 1 and 5 or less.
D: [S450-650] / [S450] is 1 or less.

  Separately obtained image forming materials were evaluated for safe light properties under a yellow light by the following method.

<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.
Evaluation criteria of safe light property 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.

  These results are shown in Table 2.

Examples 2-16
A photosensitive image forming material was prepared in the same manner as in Example 1 except that the type and blending amount of the sensitizer were changed as shown in Table 2, and various measurements and evaluations were performed in the same manner. The results are shown in Table 2. It was.

Comparative Example 1
A photosensitive image forming material was prepared in the same manner as in Example 1 except that no sensitizer was used, and the exposure sensitivity of the photosensitive composition layer of the obtained image forming material was measured in the same manner as described above. 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 sensitizers shown in Table 2 were used in the blending amounts shown in Table 2, and the resulting photosensitive composition of the image forming material was used. The exposure sensitivity of the layer was measured by the same method as described above, but the sensitivity was very low, and a high-resolution image by a laser was not obtained.

  From Table 2, according to the blue-violet laser photosensitive composition of the present invention using the specific sensitizer represented by the general formulas (I) to (III), a thick photosensitive composition layer is formed. It can be seen that a high-sensitivity photosensitive image forming material can be obtained even when formed.

  The present invention relates to etching for forming conductive circuits, electrode processing substrates, etc. 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. This is useful in the fields of resists, plating resists, storage materials such as DVDs and CD-Rs.

Claims (11)

It contains one or more of the sensitizers represented by the following general formulas (I) to (III), and is subjected to exposure with a light source including a wavelength region of 350 to 430 nm. A photosensitive composition.

(In the above general formulas (I) to (III), the rings A to G each independently have an aromatic hydrocarbon ring or an aromatic heterocyclic ring as a basic skeleton, and the ring A and ring B, the ring D and ring E, Ring F and Ring G may be bonded to each other to form a bonded ring containing N.
In the general formula (II), the linking group L represents a linking group containing an aromatic hydrocarbon ring and / or an aromatic heterocycle, and the linking groups L and N are the aromatic hydrocarbon ring or aromatic heterocycle. And n represents an integer of 2 or more.
In general formula (III), R represents an alkyl group which may have a substituent.
Rings A to G and linking group L may have a substituent, and these substituents may be bonded to each other to form a ring. ) In Claim 1, the rings A to G are each independently an aromatic hydrocarbon ring selected from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an azulene ring, a fluorene ring, an acenaphthylene ring, and an indene ring, or a furan. Ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, thiadizole ring, oxadiazole ring, pyridine ring, pyridazine ring An aromatic heterocycle selected from a pyrimidine ring and a pyrazine ring as a basic skeleton,
When the linking group L includes one or more of the rings selected from the aromatic hydrocarbon ring and aromatic heterocyclic ring, and includes two or more of the rings, these rings are directly connected, or A photosensitive composition, which is bonded through a divalent or higher valent linking group.   The substituent which the rings A to G and the linking group L may have is a halogen atom; a hydroxyl group; a nitro group; a cyano group; a carboxyl group; an alkyl group or a cycloalkyl group which may be substituted. , Alkenyl group, cycloalkenyl group, alkoxy group, alkylthio group, aryl group, aralkyl group, alkenyloxy group, alkenylthio group, acyl group, acyloxy group, amino group, acylamino group, carbamate group, carbamoyl group, carboxylic acid ester group , A sulfamoyl group, a sulfonic acid ester group, a group represented by —C═N, a group represented by —C═N—N, and a saturated or unsaturated heterocyclic group. object.   The photosensitive composition according to any one of claims 1 to 3, wherein the sensitizer represented by the general formulas (I) to (III) has an absorption maximum in a wavelength region of 350 to 430 nm. . In any one of Claims 1 thru | or 4,
An ethylenically unsaturated compound;
A photopolymerizable photosensitive material containing one or more photopolymerization initiators selected from the group consisting of hexaarylbiimidazole compounds, halogenated hydrocarbon derivatives, iodonium salts, organoborates, and titanocene compounds. A photosensitive composition, which is a photosensitive composition.   6. The photosensitive composition according to claim 5, wherein the photopolymerization initiator is a hexaarylbiimidazole compound.   The photosensitive composition according to any one of claims 1 to 4, further comprising a photoacid generator. In Claim 7, the following (N-1) and (N-2) component are contained further, The photosensitive composition characterized by the above-mentioned.
(N-1) Alkali-soluble resin (N-2) Crosslinking agent that acts on alkali-soluble resin under acidic conditions In Claim 7, the following (P-1) component is contained further, The photosensitive composition characterized by the above-mentioned.
(P-1) Acid-decomposable group-containing polymer   The hardened | cured material formed with the photosensitive composition of any one of Claim 1 thru | or 9.   A liquid crystal display device having the cured product according to claim 10.