JPH11338128A - Photosensitive resinous composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resinous compsn. and a preparation method thereof which can form a rib having good transparency to visible light, improved curing property at the lower part of the rib, good adhesiveness to a profile and a rib forming base, high density and an aspect ratio of >3. SOLUTION: A photosensitive resinous compsn. is characterized in that it comprises at least a photoresist contg. at least an ethylenic unsatd. compd., a sensitizing pigment and a radical polymerization initiator and at least inorg. particles having an average particle diameter of 0.01-10 μm. A method for forming a rib is characterized in that the photosensitive resinous compsn. is provided as a layer on a base for a plasma display and that exposing from the back side of the base and exposing from the front side of the base are carried out at least once respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive resin composition, and more particularly to a photosensitive resin composition comprising inorganic particles for forming a rib of a plasma display and a photoresist, and a method for forming the rib.

[0002]

2. Description of the Related Art Heretofore, there has been known a method of forming ribs and the like for a plasma display by pattern-printing a composition containing glass for forming a rib and then firing the composition. However, a rib having a narrower line width and a higher height and a high aspect ratio in order to realize a pixel having a higher density in recent years is highly desired.

Therefore, a photo process using a photosensitive resin composition has been studied, but in order to achieve a high aspect ratio, each step of coating, exposing, and developing is performed several times to secure the height. It must be performed, or in one process, the degree of cure at the bottom of the rib is insufficient, the cross section of the rib becomes an inverted trapezoidal shape, or the adhesion to the base supporting the rib is reduced. And so on.

[0004] Such a problem is due to the fact that the inorganic particles, which are rib-forming substances mixed with the photoresist, are present at a high filling, so that the light scattering intensity from the inorganic particles during exposure increases. In the case where visible light, for example, green is used for the exposure by direct drawing with a laser or the like, a photosensitive resin composition that improves light transmittance has been desired.

[0005] Therefore, even if the inorganic particles are highly filled, they have a high density and a high aspect ratio, for example, a height of 100 to 150 μm.
There has been a demand for a photosensitive resin composition containing a photoresist capable of obtaining a rib having an m and an aspect ratio of 3 or more, and a method for forming such a rib.

[0006]

DISCLOSURE OF THE INVENTION The present invention has good transparency to visible light, improved curability at the lower part of a rib, good profile and good adhesion to a rib forming base, high density and high density. An object of the present invention is to provide a photosensitive resin composition capable of forming a rib having an aspect ratio of 3 or more, and a rib forming method using the same.

[0007]

The present invention has the following arrangement. 1. A photosensitive resin composition comprising at least a photoresist containing at least an ethylenically unsaturated compound, a sensitizing dye and a radical polymerization initiator, and inorganic particles having an average particle size of 0.01 to 10 μm.

[0008] 2. 2. The photosensitive resin composition according to the above item 1, wherein the sensitizing dye is at least one selected from the following group A. Group A: a compound represented by the following general formula (I)

[0009]

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(Wherein R ^{1 to} R ⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted amino group. the R ¹ to R ⁴ are ring may be the other to form .R ⁵ consisting of nonmetallic atoms together with the carbon atoms to which it is attached, R ⁶
Each independently represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaromatic group, an acyl group, a cyano group, an alkoxycarbonyl group, a carboxyl group, or a substituted alkenyl group. R ⁵ and R ⁶ may together form a ring composed of a nonmetallic atom.

X represents O, S, NH or a nitrogen atom having a substituent. G ¹ and G ² may be the same or different, and each represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, or an aryl group. Represents a carbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G ¹ and G ² may form a ring composed of a non-metallic atom together with the carbon atom to which they are bonded. ) A compound represented by the following general formula (II)

[0012]

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(Wherein R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group, A represents an alkynyl group or a substituted alkynyl group, wherein A represents a carbon atom substituted by an oxygen atom, a sulfur atom, an alkyl group or an aryl group, or a carbon atom substituted by two alkyl groups;

J represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring. Y represents a phenyl group, a substituted phenyl group, an unsubstituted or substituted heteroaromatic ring.
Z ¹ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group, and Z ¹ and Y are mutually bonded To form a ring. ) A compound represented by the following general formula (III)

[0015]

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(Wherein R ^{10 to} R ¹³ are each independently a hydrogen atom, an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, an unsubstituted or substituted alkenyloxy group having 1 to 6 carbon atoms, 1-6 unsubstituted or substituted alkylthio group, a dialkylamino group having a carbon number of 1 to 4 each alkyl group, a hydroxyl group, an acyloxy group, a halogen atom, a nitro group or .R represents multiple ring ¹⁰ to R ^13, And a ring-constituting carbon atom to which the substituent of R ^{10 to} R ¹³ is bonded to form a condensed ring or a condensed ring system in which each condensed ring is a 5- or 6-membered ring. You may.

R⁹Represents a hydrogen atom or a C 1-4 unsubstituted
Or an unsubstituted or substituted alkyl group having 6 to 12 carbon atoms
Is a substituted aryl group, or R¹⁴Represents -CO-. here
And R ¹⁴Is an alkoxy group, cycloalkoxy group, hydroxyl
Group, aryloxy group, alkenyloxy group, aralkyl
Ruoxy group, alkoxycarbonylalkoxy group, al
A killed carbonyl alkoxy group, or the following (III-a):
Represents a substituent represented by (III-c).

[0018]

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R ^{15 to} R ¹⁸ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group,
Represents an alkoxyalkyl group or a cycloalkyl group, m is 1 to 5, and n is 0 to 10. Q ¹ is a cyano group,
A heterocyclic or -Z ² -R ^19,. Here, R ¹⁹ is an unsubstituted or substituted alkyl group, alkenyl group, or alkoxy group having 1 to 10 carbon atoms, an unsubstituted or substituted aryl group having 6 to 12 carbon atoms, an unsubstituted or substituted aryloxy group having 6 to 12 carbon atoms. An unsubstituted or substituted heterocyclic group having 5 to 15 carbon atoms and hetero atoms constituting the group or the ring,
Or a hydroxyl group or an acyl group. Z ² is a carbonyl group,
Represents a sulfonyl group, a sulfinyl group or an arylenedicarbonyl group,-(CH = CH) _k (k is 1 or 2). ) 3. 3. The photosensitive resin composition according to the above item 1 or 2, wherein the ethylenically unsaturated compound is an acrylic compound.

4. 4. The photosensitive resin composition according to any one of the above items 1 to 3, wherein the photoresist contains a polymer binder and / or a crosslinking agent. 5. The photosensitive resin composition according to any one of the above items 1 to 4, wherein the inorganic particles include at least one selected from low-melting glass particles, metal powders, metal oxides, and phosphors.

6. The photosensitive resin composition according to any one of the above items 1 to 5, which is used for forming ribs of a plasma display. 7. 7. A plasma, wherein the photosensitive resin composition according to 6 is provided as a layer on a base for a plasma display, and exposure processing from the back of the base and exposure processing from the front of the base are performed at least once each. Display rib forming method.

Hereinafter, the present invention will be described in detail. The photosensitive resin composition of the present invention comprises a photoresist having a specific composition and inorganic particles having a specific size. The photoresist used in the present invention is preferably a negative type. The photoresist comprises at least an ethylenically unsaturated compound, at least one sensitizing dye selected from the above group A, and a radical polymerization initiator.

The ethylenically unsaturated compound used in the present invention is not particularly limited, but a preferred ethylenically unsaturated compound has at least two terminal unsaturated groups, It is a compound that can be photopolymerized by irradiation (hereinafter abbreviated as polyfunctional monomer). As the polyfunctional monomer, an acrylic compound is particularly preferable. Here, the acrylic type includes an acrylic acid derivative and a methacrylic acid derivative.

Specifically, JP-B-35-5,093, JP-B-35-14,719, and JP-B-44-2.
The following compounds described in JP-A-8,727 and the like.
First, acrylic compounds include acrylic esters and methacrylic esters, and polyacrylates and polymethacrylates of polyhydric alcohols (here, “poly” refers to di (meth) acrylate or higher). is there. Examples of the polyhydric alcohol include polyethylene glycol, polypropylene glycol, polybutylene glycol, polycyclohexene oxide, polystyrene oxide, polyoxetane, polytetrahydrofuran, cyclohexanediol, xylylene diol, di- (β-hydroxyethoxy) benzene, glycerin and diglycol. Glycerin, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, butanediol, butanetriol, 2-
Butene-1,4-diol, 2-n-butyl-2-ethyl-propanediol, 2-butene-1,4-diol, 3-chloro-1,2-propanediol, 1,4-
Cyclohexanedimethanol, 3-cyclohexene-
1,1-dimethanol, decalindiol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-dihydroxy-1,2,3 , 4-tetrahydronaphthalene, 2,5
-Dimethyl-2,5-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol, dodecanediol, mesoerythritol, 2-ethyl-1,3- Hexanediol, 2-ethyl-2- (hydroxymethyl) -1,3-
Propanediol, 2-ethyl-2-methyl-1,3-
Propanediol, heptanediol, hexanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 2
-Methyl-1,4-butanediol, 2-methyl-2,
4-pentanediol, nonanediol, octanediol, pentanediol, 1-phenyl-1,2-ethanediol, propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,3
5,6-tetramethyl-p-xylene-α, α'-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne -1,4-diol, 1,2,6-trihydroxyhexane, 1,1'-bi-2-naphthol, dihydroxynaphthalene, 1,1'-methylenedi-2-naphthol, 1,2,4-benzenetriol , Biphenol,
2,2'-bis (4-hydroxyphenyl) butane,
1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol,
4-chlororesorcinol, 3,4-dihydroxyhydrocinnamic acid, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methyl-2,4,6-trihydroxybenzoate, phloroglucinol, pyrogallol, resorcinol, glucose, α- (1 -Aminoethyl) -p-hydroxybenzyl alcohol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propane Diol, N- (3-aminopropyl) -diethanolamine, N, N'-bis- (2-hydroxyethyl) piperazine, 2,2-bis (hydroxymethyl) -2,2 ',
2 ″ -nitrilotriethanol, 2,2-bis (hydroxymethyl) propionic acid, 1,3-bis (hydroxymethyl) urea, 1,2-bis (4-pyridyl) -1,2-ethanediol, N -N-butyldiethanolamine, diethanolamine, N-ethylenediethanolamine, 3-mercapto-1,2-propanediol, 3-piperidino-1,2-propanediol,
2- (2-pyridyl) -1,3-propanediol, triethanolamine, α- (1-aminoethyl) -p-
Examples include hydroxybenzyl alcohol and 3-amino-4-hydroxyphenyl sulfone. Of these acrylates and methacrylates, the most preferred are ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetrapropylene glycol diacrylate, dodecapropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, penta Erythritol tetraacrylate, Pentaery Lithol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, diglycerin dimethacrylate, 1,3-propanediol diacrylate, 1,
2,4-butanetriol trimethacrylate, 1,4
-Cyclohexanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate to which ethylene oxide is added, and the like.

Among the acrylic compounds, acrylamides and methacrylamides include methylenebisacrylamide, methylenebismethacrylamide,
Ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene, bis (2-aminopropyl) amine, diethylenetriaminediamine, heptamethylenediamine, octamethylenediamine, polyamines interrupted by hetero atoms, polyamines having rings (eg, phenylene Polyacrylamides and polymethacrylamides of diamine, xylylenediamine, β- (4-aminophenyl) ethylamine, diaminobenzoic acid, diaminotoluene, diaminoanthraxine, diaminofluorene and the like.

N-β-hydroxyethyl-β- (methacrylamido) ethyl acrylate, N, N-bis (β-
Compounds having two or more different addition-polymerizable unsaturated bonds, such as methacryloxyethyl) acrylamide and allyl methacrylate, are also suitably used as the acrylic compound.

The following are examples of other ethylenically unsaturated compounds. For example, as an allyl compound,
For example, diallyl esters of dicarboxylic acids such as phthalic acid, terephthalic acid, sebacic acid, adipic acid, glutaric acid, malonic acid, oxalic acid, for example, anthraquinone disulfonic acid, benzenedisulfonic acid, 2,5-dihydroxy-p
-Diallyl esters and diallylamides of disulfonic acids such as benzenedisulfonic acid, dihydroxynaphthalenedisulfonic acid and naphthalenedisulfonic acid.

Examples of the vinyl ether compound include polyvinyl ethers of the above-mentioned polyhydric alcohols, for example, ethylene glycol divinyl ether, 1,3,5-tri-β
-Vinyloxyethoxybenzene, 1,3-di-β-vinyloxyethoxybenzene, glycerol trivinyl ether and the like.

As vinyl esters, divinyl succinate, divinyl adipate, divinyl phthalate,
Divinyl terephthalate, divinylbenzene-1,3-
Disulfonate and divinylbutane-1,4-disulfonate.

Examples of the styrene compound include divinylbenzene, p-allylstyrene, p-isopropenestyrene and the like.

Furthermore, a reaction product obtained by reacting a polyol compound having at least two hydroxyl groups with a slightly excessive polyisocyanate compound having at least two isocyanate groups is added to a reaction product obtained by reacting at least one hydroxyl group and at least one ethylenically unsaturated compound. A polyfunctional urethane compound having at least two ethylenically unsaturated groups obtained by reacting a compound having a group is also suitably used in the present invention.

These polyfunctional monomers can be used alone or in combination of two or more, and are used in the range of 5 to 90% by weight, preferably 15 to 60% by weight of the photoresist solids. Further, the photoresist used in the present invention is not particularly limited as a polymer binder which preferably further uses a polymer binder, a crosslinking agent, and the like as a binder component. Among the synthetic, semi-synthetic and natural polymer substances, those satisfying the following conditions are preferably used. That is, the affinity with the inorganic particles, and the compatibility with the ethylenically unsaturated compound, the radical polymerization initiator, and other components, for example, a crosslinking agent, etc. are demixed during the preparation of the photosensitive resin composition and during storage. That the binder itself has appropriate strength, stretchability, abrasion resistance, chemical resistance, etc., and furthermore, the molecular weight, intermolecular force, hardness, and softening temperature of the polymer binder. , Crystallinity, elongation at break, etc. are appropriate.

Specific examples of the polymer binder include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, and poly (meth) acrylic acid alkyl esters (alkyl groups include methyl, ethyl and butyl). Copolymer of (meth) acrylic acid and alkyl (meth) acrylate (alkyl group is the same as above), poly (meth) acrylic acid, alkyl (meth) acrylate (alkyl group is the same as above) and acrylonitrile, chloride Copolymers with at least one monomer such as vinyl, vinylidene chloride, styrene, butadiene, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, acetic acid Copolymer of vinyl and vinyl chloride, polyacrylonitrile, A copolymer of lonitrile and styrene, a copolymer of acrylonitrile and butadiene and styrene, a copolymer of styrene and an unsaturated dibasic anhydride such as maleic anhydride, polyvinyl butyral, styrene butadiene rubber, chlorinated rubber, Examples include cyclized rubber and homopolymers or copolymers such as acetylcellulose. Here, (meth) acrylic acid means acrylic acid or methacrylic acid.

When the polymer binder is a copolymer, the content ratio of the component monomers can take a wide range of values, but in general, a specific monomer which is a main component of the copolymer and another copolymer monomer are used. Is preferably contained in a molar ratio of 5% or more. Further, polymers other than these can be used as the photoresist polymer binder of the present invention as long as they satisfy the above conditions.

Of the above-mentioned polymer binders, particularly preferably used are chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, methyl methacrylate-acrylonitrile copolymer (molar content of methyl methacrylate: 20 to 80%). , Vinyl chloride-acrylonitrile copolymer (vinyl chloride molar content 20-80%),
Vinylidene chloride-acrylonitrile copolymer (molar content of vinylidene chloride 20-80%), styrene-maleic anhydride copolymer, Japanese Patent Application No. 59-114736 (The polymer binder is methyl methacrylate / methacrylic acid / 2 -Ethylhexyl methacrylate / benzyl methacrylate quaternary copolymer) and JP-B-54-34327 (the polymer binder is, for example, a terpolymer of methyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid). JP-B-55-38961 (polymer binder is, for example, styrene / maleic acid mono-n-butyl ester copolymer) and JP-B-54-25957 (polymer binder is, for example, ethylene / methyl methacrylate / A quaternary copolymer of ethyl acrylate / methacrylic acid), and JP-A-52-99810. (Polymeric binder is, for example, benzyl methacrylate / methacrylic acid copolymer), JP-B-5
No. 8-12577 (the polymer binder is, for example, a terpolymer of acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid) and JP-B-55-6210 (the polymer binder is, for example, methyl methacrylate / acrylic acid). And styrene / maleic anhydride copolymers partially esterified with isopropanol, and the like.

These polymer binders may be used alone or in combination. However, during the steps from the preparation of two or more photoresists to the formation of a layer of the photosensitive resin composition and the resulting photosensitive resin, Polymers compatible with each other so as not to cause demixing during storage of the composition can be used by mixing them in an appropriate ratio. The molecular weight of such a polymer binder can take a wide range depending on the type of the polymer, but is generally 5,000 to 2,000,000, more preferably 50,000 to 1,000,000. Those in the range are preferably used in the present invention.

The amount of the polymer binder is from 5 to 95 wt%, preferably from 40 to 80 wt%, based on the solid content of the photoresist.
%.

The crosslinking agent that can be used in the present invention is preferably a crosslinking agent capable of performing a crosslinking reaction with the above-mentioned ethylenically unsaturated compound and / or polymer binder, and is not particularly limited. And a silane-based crosslinking agent are preferred. Examples of the silane-based crosslinking agent include, for example,

[0039]

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And the like.

[0041]

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Is preferred. The crosslinking agent can be used in a range of usually 5 to 95% by weight, preferably 10 to 90% by weight based on the solid content of the photoresist. When the amount of the crosslinking agent decreases from the appropriate amount, the sensitivity decreases,
The film loss tends to increase and the profile tends to deteriorate.
Further, when the amount of the crosslinking agent is increased from an appropriate amount, the developability tends to deteriorate, and the development residue tends to be easily generated.

The sensitizing dye used in the present invention is not particularly limited. For example, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, 2,4 -Diethylthioxanthone, isoproprithioxanthone, 2,3-bis (4-
Diethylaminobenzal) cyclopentanone, 2,6-
Bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4
-Methylhexanone, Michler's ketone, 4,4-bis (diethylamino) -benzophenone, p-dimethylaminobenzylideneindanone, N-phenyl-N-ethylethanolamine, N-phenylethanolamine,
N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3
-Phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole, 2
-(P-dimethylaminophenylpinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, and the like, Preferably, the above general formula (I), general formula (II) or general formula (II
It is selected from the compounds represented by I).

In the general formula (I), as the alkyl group for R ^{1 to} R ⁴ , those having 1 to 20 carbon atoms such as methyl, ethyl and t-butyl can be used. Further, as the aryl group, those having 1 to 10 carbon atoms such as phenyl can be used. Further, as the alkoxy group for R ^{1 to} R ⁴ , those having 1 to 6 carbon atoms such as methoxy, ethoxy, butoxy and the like can be used. In addition, as the substituted amino group for R ^{1 to} R ⁴ , methylamino,
Dimethylamino, diethylamino, diphenylamino,
An alkylamino group having 1 to 20 carbon atoms and an arylamino group such as piperidino and morpholino can be used.

These alkyl group, aryl group, alkoxy group, alkylamino group and arylamino group may have a substituent. Examples of the substituent include a halogen atom such as fluorine, chlorine and bromine, an alkoxycarbonyl group such as an ethoxycarbonyl group, an alkoxy group such as methoxy and ethoxy, an aryl group such as phenyl, and a cyano group. When R ^{1 to} R ⁴ form a ring composed of a nonmetallic atom together with a carbon atom bonded thereto, examples of the structure containing a ring include those shown in the following (A), (B) and (C).

[0046]

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When R ⁵ and R ⁶ are acyl groups, an alkyl group having 1 to 10 carbon atoms such as acetyl and benzoyl;
Examples thereof include those having an aryl group and those having an alkyl group having 1 to 6 carbon atoms such as ethoxycarbonyl in the case of an alkoxycarbonyl group. Further, in the case of a substituted alkenyl group, those having 2 to 10 carbon atoms such as a styryl group can be used, and in the case of a heteroaromatic group, those shown in the following (D) to (F) can be used.

[0048]

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Further, both R ⁵ and R ⁶ may form a ring together with the carbon atom bonded thereto. Examples include the structure shown in (G) below.

[0050]

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When X is a nitrogen having a substituent, the substituent may be the same as the alkyl and aryl groups described for R ^{1 to} R ⁶ . G ¹ and G ² may be the same or different, and each represents a hydrogen atom, a cyano group,
An alkoxycarbonyl group having an alkyl group having 1 to 10 carbon atoms such as an ethoxycarbonyl group, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms such as a phenoxycarbonyl group, an acetyl group, a propionyl group having 1 to 1 carbon atoms. 7 to 7 carbon atoms such as acyl group and benzoyl group
C1-C6 arylthio groups such as 11-arylcarbonyl group, methylthio group, ethylthio group, etc. C1-C6 alkylthio group, C6-C10 arylthio group such as phenylthio group, and C6-C10 arylsulfonyl such as phenylsulfonyl group Represents an alkylsulfonyl group having 1 to 6 carbon atoms such as a group, a methylsulfonyl group, an ethylsulfonyl group, or a fluorosulfonyl group.

These alkoxycarbonyl group, aryloxycarbonyl group, acyl group, arylcarbonyl group, alkylthio group, arylthio group, arylsulfonyl group and alkylsulfonyl group may have a substituent, and the substituent may be chlorine. Halogen atom, etc., carbon number 1
An alkoxycarbonyl group having from 6 to 6 alkyl groups,
Examples thereof include a carboxyl group, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group. In the case of an aryloxycarbonyl group, an arylcarbonyl group, an arylthio group, or an arylsulfonyl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group can be used in addition to the above substituents.

When G ¹ and G ² form a ring consisting of a nonmetal atom together with the carbon atom to which they are bonded, the ring is usually a merocyanine dye used as an acidic nucleus. . (A) 1,3-dicarbonyl nucleus, for example, 1,3-indandione, 1,3-cyclohexanedione, 5,5-
Dimethyl-1,3-cyclohexanedione and 1,3-dioxane-4,6-dione.

(B) pyrazolinone nucleus, for example, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3- Methyl-2-pyrazolin-5-one. (C) isoxazolinone nucleus, for example 3-phenyl-
2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.

(D) Oxindole nucleus, for example, 1-
Alkyl-2,3-dihydro-2-oxindole. (E) 2,4,6-triketohexahydropyrimidine nucleus, for example barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of such derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl; 1,3-dialkyl compounds such as 1,3-diethyl and 1,3-dibutyl;
3-diphenyl, 1,3-di (p-chlorophenyl),
Examples thereof include 1,3-diaryl compounds such as 1,3-di (p-ethoxycarbonylphenyl) and 1-alkyl-3-aryl compounds such as 1-ethyl-3-phenyl.

(F) 2-thio-2,4-thiazolidinedione nucleus, for example, rhodanine and its derivatives. Such derivatives include 3-alkyl rhodanines such as 3-ethyl rhodanine and 3-allyl rhodanine, and 3-aryl rhodanines such as 3-phenyl rhodanine. (G) 2-thio-2,4-oxazolidinedione (2
-Thio-2,4- (3H, 5H) -oxazoledione) nucleus, for example 2-ethyl-2-thio-2,4-oxazolidinedione.

(H) Thianaphthenone nucleus, for example, 3 (2
H) -thianaphthenone and 3 (2H) -thianaphthenone-1,1-dioxide. (I) 2-thio-2,5-thiazolidinedione nucleus, for example, 3-ethyl-2-thio-2,5-thiazolidinedione. (J) 2,4-thiazolidinedione nucleus, for example, 2,4
-Thiazolidinedione, 3-ethyl-2,4-thiazolidinedione and 3-phenyl-2,4-thiazolidinedione.

(K) Thiazolidione nucleus, for example, 4-thiazolidinone, 3-ethyl-4-thiazolidinone. (L) 4-thiazozolinone nucleus, for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one.

(M) 2-imino-2-oxozoline-
It is a 4-one (coagulation hydantoin) nucleus. (N) 2,4-imidazolidinedione (hydantoin) nucleus, for example, 2,4-imidazolidinedione, 3-
Ethyl-2,4-imidazolidinedione. (O) 2-thio-2,4-imidazolidinedione (2
-Thiohydantoin) nuclei such as 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-
It is imidazolidinedione.

(P) 2-imidazolin-5-one nucleus,
An example is 2-n-propyl-mercapto-2-imidazolin-5-one. (Q) Furan-5-one.

The compound represented by the general formula (I) used in the present invention includes a compound represented by the general formula (Ia) or (Ib) and a compound represented by the formula (Ic) Can be synthesized from

[0062]

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[0063] (L _1, L ₂ in the above formula is an alkyl group, Za ^-
Represents an anion) Specific examples of the compound represented by formula (I) used in the present invention are shown below.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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Next, the sensitizing dye represented by formula (II) will be described. In the formula (II), R ⁷ and R ⁸ are a hydrogen atom,
Alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkoxycarbonyl group, aryl group, substituted aryl group, alkynyl group, represents a substituted alkynyl group,
They may be the same or different. Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group,
Isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2
-Methylhexyl, cyclohexyl, cyclopentyl, and 2-norbornyl groups. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent for the substituted alkyl group, a monovalent nonmetallic atomic group other than hydrogen is used. Preferred examples thereof include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, Alkoxy, aryloxy, mercapto, alkylthio, allyl-thio, alkyldithio, aryldithio, amino, N-alkylamino, N, N-dialkylamino, N-arylamino, N, N- Diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N An arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group,
N'-alkylureido groups, N ', N'-dialkylureido groups, N'-arylureido groups, N', N'-diarylureido groups, N'-alkyl-N'-arylureido groups,

N-alkylureido, N-arylureido, N'-alkyl-N-alkylureido,
N'-alkyl-N-alkylureido groups, N ', N'
-Dialkyl-N-alkylureido group, N ', N'-
Dialkyl-N-arylureido, N'-aryl-N-alkylureido, N'-aryl-N-arylureido, N ', N'-diaryl-N-alkylureido, N', N'- Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-
N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-
N-alkoxycarbonylamino group, N-alkyl-N
-Aryloxycarbonylamino group, N-aryl-N
-Alkoxycarbonylamino group, N-aryl-N-
Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N
- arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfo group (-SO ₃ H) and its conjugate Base group (hereinafter,
Sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N
-Diarylsulfinamoyl group, N-alkyl-N-
Arylsulfinamoyl group,

Sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-
Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, referred to as phosphonate group) , dialkyl phosphono group ₍₂ -PO ₃ (alkyl)), diaryl phosphono group (-PO ₃ (aryl) _2), alkyl aryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono Group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter, arylphosphonate) Phonooxy group (-OPO ₃ H ₂ ) and its conjugated base group (hereinafter, referred to as “onato group”).
Phosphodiesterase referred to isocyanatomethyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), diaryl phosphonooxy group (-OPO ₃ (aryl) _2), alkylaryl phosphonooxy group (-OPO ₃ (alkyl ) (Aryl)), monoalkylphosphonooxy group (—OPO ₃ H
(Alkyl)) and its conjugate base group (hereinafter, referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter, arylphosphonatooxy group) ), A cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group and the like.

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group,
Examples include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butynyl group, a cinnamyl group and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. As R in the acyl group (RCO-),
Examples include hydrogen, and the above-described alkyl and aryl groups. Of these substituents, an even more preferred one is a halogen atom (-F, -Br, -Cl,-
I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N-
Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group , N, N-dialkylcarbamoyl, N-arylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulfo, sulfonato, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl A group, an N-arylsulfamoyl group,
An N-alkyl-N-arylsulfamoyl group, a phosphono group, a phosphonate group, a dialkylphosphono group, a diarylphosphono group, a monoalkylphosphono group, an alkylphosphonato group, a monoarylphosphono group, an arylphosphonate group, Examples include a phosphonooxy group, a phosphonatoxy group, an aryl group, and an alkenyl group.

Specific examples include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, and tolylthiomethyl. Group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group,
N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonyl Methyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl Group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- ( Phosphono Enyl) sulfamoyl, octyl, phosphonobutyl, phosphonatohexyl, diethylphosphonobutyl, diphenylphosphonopropyl, methylphosphonobutyl, methylphosphonatobutyl, tolylphosphonohexyl, tolylphospho Onatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group,
Allyl group, 1-propenylmethyl group, 2-butenyl group,
2-methylallyl group, 2-methylpropenylmethyl group,
Examples thereof include a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include those in which one to three benzene rings form a condensed ring and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Examples of the substituent of the substituted aryl group include the substituents of the above-mentioned substituted alkyl group. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acetonaphthenyl group, and a fluorenyl group.

The alkenyl group may have 1 to 2 carbon atoms.
Up to 0 straight, branched and cyclic alkenyl groups can be mentioned. Examples of the substituent of the substituted alkenyl group include the substituents described for the substituted alkyl group. Specific examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, and a 1-methyl-1 group. -Propenyl, styryl, 2-pentenyl, 2-cyclohexynyl and the like.

Examples of the alkynyl group include linear and branched alkynyl groups having 1 to 20 carbon atoms.

The substituent of the substituted alkynyl group includes
The substituents described for the substituted alkyl group can be mentioned, and specific examples thereof include ethynyl, 2-phenylethynyl, 1-butynyl group and the like. Examples of the alkoxycarbonyl group include a residue in which a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxycarbonyl group. Specific examples thereof include a methoxycarbonyl group, Ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group,
Examples thereof include a sec-butoxycarbonyl group and a tert-butoxycarbonyl group.

Although R ⁷ and R ⁸ have been described above, in the present invention, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group are preferred.

A in the general formula (II) represents an oxygen atom, a sulfur atom,
A carbon atom substituted by an alkyl or aryl group,
Or a carbon atom substituted by two alkyl groups. A
Examples of the aryl group and the alkyl group therein include those described for R ⁷ and R ⁸ . Examples of the nitrogen-containing five-membered ring completed by J in cooperation with A, C and N in the general formula (II) include the following.

[0085]

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The substituent E in the formulas (a-1) to (a-4)
Means that the Hammett ρ value is in the range of -0.9 to +0.5
There is something. Examples include hydrogen, methyl
Group, isopropyl group, tert-butyl group, phenyl
Group, trifluoromethyl group, acetyl group, ethoxycal
Bonyl group, carboxyl group, carboxylate group (-CO
O ^-), Amino group, methylamino group, dimethylamino
Group, ethylamino group, diethylamino group, acetylamino
No group, -PO_ThreeH group, methoxy group, ethoxy group, propo
Xy, isopropoxy, butoxy, benzyloxy
Groups, phenoxy groups, hydroxy groups, acetoxy groups,
Tylthio, ethylthio, isopropylthio, mel
Capto group, acetylthio group, thiocyano group (-SC
N), a methylsulfinyl group, an ethylsulfinyl group,
Methylsulfonyl group, ethylsulfonyl group, aminosulfon
Honyl group, dimethylsulfonyl group, (-S⁺(C
H_Three)_Two), A sulfonato group, (—SO_Two ^-), A fluorine atom,
Chlorine, bromine, iodine, iodyl, trimethyl
Lucyl group (-Si (CH_Three)_Three), Triethylsilyl
Group, trimethylstannyl group (-Sn (CH_Three)_Three)
be able to. Preferred among these substituents
Represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group,
Xyl group, dimethylamino group, diethylamino group, chlorine atom
Child, bromine atom.

Examples of Y in the general formula (II) are shown below. Examples of the substituent of the substituted phenyl group include the same as those described above for E. Examples of the polynuclear aromatic ring include a naphthyl group, an anthryl group, and a phenanthryl group, and these may be substituted with the substituent E described above. Examples of the heteroaromatic ring include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyrrolyl group, and a 3-pyrrolyl group, which are substituted by the substituent E described above. May be.

An example of Z ¹ in the general formula (II) will be described below. Examples of the alkyl group, substituted alkyl group, aryl group and substituted aryl group include R ⁷ and R
^The same ones as mentioned in the example ⁸ can be mentioned. Examples of the alkylthio group and the arylthio group include a linear, branched, and cyclic alkyl group having 1 to 10 carbon atoms and a residue in which an aryl group having 1 to 20 carbon atoms is bonded to a thio group (sulfur atom). Specific examples thereof include methylthio, ethylthio, propylthio, butylthio, sec-butylthio, and te.
Examples thereof include an rt-butylthio group, a phenylthio group, and a naphthylthio group.

Examples of the alkoxyl group include a residue in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxy group (oxygen atom). Group, ethoxyl group,
Examples include a propoxyl group, a butoxyl group, a sec-butoxyl group, and a tert-butoxyl group. As the substituted amino group, a linear group having 1 to 10 carbon atoms,
An amino group substituted by a branched or cyclic alkyl group can be mentioned, and specific examples thereof include a dimethylamino group, a diethylamino group, and a dipropylamino group.

The acyl group includes a hydrogen atom and a carbon atom of 1
To 10, preferably 1 to 6 also include a residue in which a linear, branched or cyclic alkyl group, phenyl group or naphthyl group is bonded to carbonyl, and specific examples thereof include a formyl group, Acetyl group,
Examples include a propionyl group, a butyryl group, a valeryl group, a benzoyl group, and a naphthoyl group.

Examples of the alkoxycarbonyl group include a residue in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxycarbonyl group. Group, ethoxycarbonyl group, propoxycarbonyl group,
Butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group.

Examples of the ring formed by combining Y and Z ¹ with each other are shown below.

[0093]

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[0094]

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The group of compounds represented by the general formula (II) is “Ru
ll. Soc. Chimie Belges, Vol. 57, 364-372
Page (1948) Abstract: Chemical Abstracts, No. 4
The compound can be synthesized according to the method described in Vol. 4, columns 60e to 61d (1950). Specific examples of the compound represented by the general formula (II) are shown below.

[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

[Table 1]

[0103]

[Table 2]

Next, the sensitizing dye represented by formula (III) used in the present invention will be described. In the formula, R ^{10 to} R ¹³ independently represent a hydrogen atom, an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, an unsubstituted or substituted alkenyloxy group having 1 to 6 carbon atoms, an unsubstituted having 1 to 6 carbon atoms. Or a substituted alkylthio group, a dialkylamino group having 1 to 4 carbon atoms in each alkyl group, a hydroxyl group, an acyloxy group, a halogen atom, a nitro group, or a multiple ring group. 2 of R ¹⁰ to R ¹³
Or three and the ring-constituting carbon atoms to which the substituents of R ^{10 to} R ¹³ are bonded to form a condensed ring of 5 or 6
A fused ring or fused ring system that is a membered ring may be formed.

R⁹Represents a hydrogen atom or a C 1-4 unsubstituted
Or an unsubstituted or substituted alkyl group having 6 to 12 carbon atoms
Is a substituted aryl group, or R¹⁴Represents -CO-. here
And R ¹⁴Is an alkoxy group, cycloalkoxy group, hydroxyl
Group, aryloxy group, alkenyloxy group, aralkyl
Ruoxy group, alkoxycarbonylalkoxy group, al
A killed carbonyl alkoxy group, or (III-a) to (II
The substituent represented by I-c) (R ^Fifteen~ R¹⁸Is a hydrogen atom,
Group, hydroxyalkyl group, hydroxyalkoxyl
Alkyl, alkoxyalkyl and cycloalkyl groups
Represent. ).

Q ¹ represents -CN, a heterocyclic ring, -Z ² -R ¹⁹ , wherein R ¹⁹ is methyl, ethyl, propyl, isopropyl,
t-butyl, isobutyl, butyl, amyl, hexyl,
C1-C10 alkyl, including heptyl, octyl, nonyl, decyl and cycloalkyl such as cyclopentyl, cyclohexyl, etc .; substituted alkyl; aryl such as phenyl; nitro, alkoxy, halogen, carboalkoxy, alkyl, aryl, carboxy A substituted aryl substituted with a substituted amino or the like such as hydroxy, amino, dialkylamino or trialkylammonium; an alkoxy such as methoxy, ethoxy, butoxy; an aryloxy such as phenoxy; 15 heterocyclic groups, for example of the formula

[0107]

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(Wherein R ⁴¹ is methyl, ethyl, propyl, isopropyl, butyl, n-butyl, isobutyl,
alkyl having 1 to 4 carbon atoms including s-butyl and the like;
^- the FSO ₃ ^-, Br ₄ ^-, p-toluenesulfonate, halogen (e.g., Cl, Br, I) is an anion, and the like) of pyridinium; nicotinyl; Nikochiniumu; furyl; 2- benzofuranyl; 2-thiazolyl; 2-thienyl or the like; or a formula

[0109]

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(Wherein R ^{42 to} R ⁴⁶ are selected from the same groups as the above-mentioned substituents), and is an acyl group such as 3-substituted coumarinyl, acetyl, etc., and Z ² is carbonyl, sulfonyl, sulfinyl or aryl. A bonding group selected from range carbonyl. As the aryl group for R ¹⁹ ,
Examples include a phenyl group, a naphthyl group and an indenyl group.

Examples of the heterocyclic ring include those having the following structure.

[0112]

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Here, M is -CH or a nitrogen atom, and T is-
CH ₂ —, NH, and S are represented, and W represents a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear or dinuclear aromatic heterocyclic group. In particular,

[0114]

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And the like. Examples of the sensitizing dye of the formula (III) include the following. 3-benzoyl-5,7-dimethoxycoumarin 3-benzoyl-7-methoxycoumarin 3-benzoyl-6-methoxycoumarin 3-benzoyl-8-ethoxycoumarin 7-methoxy-3- (p-nitrobenzoyl) coumarin 3-benzoyl Coumarin 3- (p-nitrobenzoyl) coumarin 3-benzoylbenzo [f] coumarin 3,3'-carbonylbis (7-methoxycoumarin) 3-acetyl-7-methoxycoumarin 3-benzoyl-6-bromocoumarin 3,3 '-Carbonylbiscoumarin 3-benzoyl-7-dimethylaminocoumarin 3,3'-carbonylbis (7-diethylaminocoumarin) 3-carboxycoumarin 3-carboxy-7-methoxycoumarin 3-ethoxycarbonyl-6-methoxycoumarin3- Ethoxycal Nyl-7-methoxycoumarin 3-acetylbenzo [f] coumarin 3-acetyl-7-methoxycoumarin 3- (1-adamantoyl) -7-methoxycoumarin 3-benzoyl-7-hydroxycoumarin 3-benzoyl-6-nitro Coumarin 3-benzoyl-7-acetocoumarin 3-benzoyl-7-diethylaminocoumarin 7-dimethylamino-3- (4-iodobenzoyl) coumarin 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin 7-methoxy-3- (4-methoxybenzoyl) coumarin 3- (4-nitrobenzoyl) benzo [f] coumarin 3- (4-ethoxycinnamoyl) -7-methoxycoumarin 3- (4-dimethylaminocinnamoyl) coumarin 3- (4- Diphenylaminocinnamoyl) coumarin 3-[(3-methylbenzothiazole-2-ylidene)
Acetyl] coumarin 3-[(1-methylnaphtho [1,2-d] thiazole-
2-ylidene) acetyl] coumarin 3,3'-carbonylbis (6-methoxycoumarin) 3,3'-carbonylbis (7-acetoxycoumarin) 3,3'-carbonylbis (7-dimethylaminocoumarin) 3,3 '-Carbonylbis- (5,7-diisopropoxy) coumarin 3,3'-carbonylbis- (5,7-di-n-propoxy) coumarin 3,3'-carbonylbis- (5,7-di- n-butoxy) coumarin 3-cyano-6-methoxycoumarin 3-cyano-7-methoxycoumarin 7-methoxy-3-phenylsulfonylcoumarin 7-methoxy-3-phenylsulfinylcoumarin 1,4-bis (7-diethylamino-3 -Coumarylcarbonyl) benzene 7-diethylamino-5 ', 7'-dimethoxy-3,
3'-carbonylbiscoumarin 7-dimethylamino-3-thenoylcoumarin 7-diethylamino-3-furoylcoumarin 7-diethylamino-3-thenoylcoumarin 3-benzoyl-7- (1-pyrrolidinyl) coumarin 5,7, 6'-trimethoxy-3,3'-carbonylbiscoumarin 5,5,7'-trimethoxy-3,3'-carbonylbiscoumarin 7-diethylamino-6'-methoxy-3,3'-carbonylbiscoumarin 3-nicotinoyl -7-methoxycoumarin 3- (2-benzofuranylcarbonyl) -7-methoxycoumarin 3- (7-methoxy-3-coumarinoyl) -1-methylpyrimidium fluorosulfate 3- (5,7-diethoxy-3 -Coumarinoyl-1-methylpyrimidium fluoroborate N- (7-methoxy 3 Kumari hexanoyl methyl) pyridinium bromide 9- (7-diethylamino-3-Kumarinoiru) -1,
2,4,5-tetrahydro-3H, 6H, 10H [1]
Benzopyrano [a, 9a.l-gh] quinolazine-10
And compounds represented by the following chemical formulas (III-1) to (III-15).

[0116]

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[0117]

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The sensitizing dyes represented by formulas (I) to (III) may be used alone or in combination of two or more.
These sensitizing dyes are used in an amount of 0.05 to 30 parts by weight per 100 parts by weight of the compound having an ethylenically unsaturated double bond.
Parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight.

Next, the radical polymerization initiator used in the present invention will be described. The radical polymerization initiator is not particularly limited, but the compounds shown in the following (a) to (nu) are preferable. (A) Compound having a carbon-halogen bond (b) Ketone compound represented by the following general formula (IV)

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(Where Ar is the following (VI-a) or (VI-a)
b) an aromatic group represented by ²⁰, R^{twenty one}Is hydrogen
Represents an atom or an alkyl group;²⁰, R^{twenty one}Are each other
It may be linked to represent an alkylene group.

[0122]

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In the above formula, R ^{22 to} R ²⁶ may be the same or different, and each represents a hydrogen atom, alkyl group, substituted alkyl group, alkenyl group, aryl group, substituted aryl group,
Hydroxyl group, alkoxy group, -SR ²⁸ group, -SO-R
²⁸ groups represent a -SO ₂ -R ²⁸ group, at least one -S-R ²⁸ group of ^{R 22 ~R 26, -SO-R} 28 group, -SO ₂ -
A R ^{2 8} group, R ²⁸ represents an alkyl group, an alkenyl group. R ²⁷ represents a hydrogen atom, an alkyl group or an acyl group, and Y ¹ represents a hydrogen atom or

[0124]

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Represents the following. R ²⁹ has the same meaning as R ^20, and R ³⁰ has the same meaning as R ²¹ . (C) a ketoxime compound represented by (V) in the following general formula

[0126]

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(Wherein, R ³¹ and R ³² may be the same or different and each represents a substituent or a hydrocarbon group or a heterocyclic group which may contain an unsaturated bond. R ³³ and R ³⁴ are the same. Or may be different, a substituent, a hydrocarbon group which may contain an unsaturated bond, a heterocyclic group, a hydroxy group,
Represents a substituted oxy group, a mercapto group, or a substituted thio group. R ³³ and R ³⁴ are bonded to each other to form a ring, and —O— and —N
R ³⁷ —, —O—CO—, —NH—CO—, —S— and / or —SO ₂ — represent an alkylene group having 2 to 8 carbon atoms which may be contained in the ring main chain. R ³⁷ represents a hydrogen atom, a substituent, a hydrocarbon group optionally having an unsaturated bond, or a substituted carbonyl group. R ³⁵ , R ³⁶
Represents a hydrogen atom, a substituent, a hydrocarbon group which may contain an unsaturated bond, or a substituted carbonyl group. (D) Organic peroxide (e) Thio compound represented by the following general formula (VI)

[0128]

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(Wherein R ³⁸ represents an alkyl group, an aryl group or a substituted aryl group, R ³⁹ represents a hydrogen atom or an alkyl group. R ³⁸ and R ³⁹ are bonded to each other to form an oxygen, sulfur, nitrogen atom Represents a group of nonmetallic atoms necessary for forming a 5- to 7-membered ring which may contain a heteroatom selected from the group consisting of: (f) hexaarylbiimidazole (g) aromatic onium salt (h) ketoxime Ester (li) N-phenylglycine (nu) titanocene compound

As the compound (a) having a carbon-halogen bond, compounds represented by the following formulas (VII) to (XIII) are preferable. General formula (VII)

[0131]

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(Wherein X represents a halogen atom; Y ²
Is ^{_{-CX 3, -NH 2, -NHR 47}} , -NR 47, -OR 47
Represents Here, R ⁴⁷ is an alkyl group, a substituted alkyl group,
Represents an aryl group or a substituted aryl group. R ⁴⁸ is -C
X _{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ). General formula (VIII)

[0133]

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(Where R ⁴⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxy group, a nitro group or a cyano group; Is a halogen atom, and n is an integer of 1 to 3.).

Formula (IX) R⁵⁰-Z^Three-CH_2-mX_m-R⁵¹ (IX) (However, R⁵⁰Is an aryl group or a substituted aryl group
R⁵¹Is -CO-NR ⁵²R⁵³Or

[0136]

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Or Z ³ is -CO-,-
CS- or -SO ₂ - and is, R ^52, R ⁵³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, R ⁵⁴ is R in the general formula (VII) Same as ⁴⁷ , m is 1 or 2. ). General formula (X)

[0138]

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Wherein R ⁵⁵ is an optionally substituted aryl group or a heterocyclic group, and R ⁵⁶ is
A trihaloalkyl or trihaloalkenyl group having three, and p is 1, 2 or 3.

Formula (XI)

[0141]

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(Where L is a hydrogen atom or a compound of the formula: CO—
^{_{(R 57) n (CX 3}} ) substituents represented by _m (n is 0 to 2, m is 1 to 3) and, D is a substituted or unsubstituted alkylene group, Q ² Is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or an NR ⁵⁸ group;
+ Q ² together form a 3 or 4 heterocycle, R ⁵⁸ is an alkyl, aralkyl or alkoxyalkyl group, R ⁵⁷ is a carbocyclic or heterocyclic aromatic group, X
Is a chlorine, bromine or iodine atom, q = 0 and r = 1
Or q = 1 and r = 1 or 2. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group;

Formula (XII)

[0144]

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(Where X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁵⁹ is a hydrogen atom or a CH _{3-t Xt} group, ⁶⁰ is an s-valent optionally substituted unsaturated organic group). Represented by
4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivatives.

Formula (XIII)

[0147]

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(Where X is a halogen atom, v is an integer of 1-3, u is an integer of 1-4, R ⁶¹ is a hydrogen atom or a CH _{3-v Xv} group, ⁶² is a u-valent unsaturated organic group which may be substituted). Represented by
2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivatives.

Compounds having such a carbon-halogen bond are described, for example, in Wakabayashi et al., Bull. Chem. Soc.
Japan, 42 , 2924 (1969).
-Phenyl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
Tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2-
(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6- Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (triclomethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis ( Trichloromethyl) -S-triazine and the like. In addition, British Patent No. 1388
No. 492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine , 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-
Compounds described in JP-A-53-133428, such as triazine and 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine;
-(4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S -Triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
The compounds described in German Patent No. 3337024, for example, the following compounds can be mentioned.

[0150]

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[0151]

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Also, J. Org. Che by FC Schaefer et al.
m .; 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S
-Triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like.

Further, there may be mentioned the compounds described in JP-A-62-58241, for example, the following compounds.

[0154]

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[0155]

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Further, there may be mentioned the compounds described in JP-A-5-281728, such as the following compounds.

[0157]

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Alternatively, MPHutt, EFElslager
And LMWerbel, Journal of Heterocyclic Chemist
The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis method described in ry Vol. 7 (No. 3), pp. 511 et seq. (1970) can be mentioned.

[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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Alternatively, compounds such as those described in DE-A-2641100, for example 4-
(4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5
-Trimethoxy-styryl) -6-trichloromethyl-
2-pyrone or the compounds described in DE 33 33 450, for example,

[0169]

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Alternatively, a group of compounds described in German Patent No. 3021590,

[0171]

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Alternatively, a group of compounds described in German Patent No. 3021599, for example,

[0173]

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The following can be mentioned.

Next, the ketone compound represented by the above general formula (IV) (II) will be described. In the formula, R ²⁰ and R ²¹ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ²⁰ and R ²¹ may combine to represent an alkylene group. R ^{22 to} R in (IV-a) and (VI-b) which are Ar
²⁶ independently of one another are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group,- SR- ²⁸ group, -SO-R- ²⁸ group, -S
Represents an O ₂ —R ²⁸ group, wherein R ²⁷ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an acyl group having 2 to 13 carbon atoms. These alkyl group, aryl group, alkenyl group, and acyl group may be further substituted with a substituent having 1 to 6 carbon atoms.

R ^{29 in} Y ^{1 has the same} meaning as R ^20, and R ³⁰ has the same meaning as R ²¹ . A specific example is disclosed in U.S. Pat.
The following compounds described in JP-A-8,791 and European Patent 0284561A can be exemplified.

[0177]

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[0178]

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Next, the ketoxime compound represented by the above formula (C) and represented by the general formula (V) will be described. Wherein R ³¹ ,
R ³² is the same or different and represents a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group. R ³³ and R ³⁴ are the same or different and are a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted Represents a thio group. Also, R
³³ and R ³⁴ are bonded to each other to form a ring, -O-, -NR
^{37 -, - O-CO -} , - S-, and -SO ₂ - represents an alkylene group having from 2 carbon atoms which may contain a linking backbone of the ring 8. R ³⁷ represents a hydrogen atom, a substituent, a hydrocarbon group optionally having an unsaturated bond, or a substituted carbonyl group.

R ³⁵ and R ³⁶ represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. As specific compounds,
The following can be mentioned, but not limited thereto.

[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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Examples of the organic peroxide (d) include compounds having an oxygen-oxygen bond in the molecule. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane,
2,2-bis (tert-butylperoxy) butane, tertiarybutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-di Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide,
Dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide,

2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, dimethoxyisopropylperoxy Carbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxypivalate, tertiary butyl peroxypivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxyoctano Eat,
Tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy laurate, tertiary butyl peroxy benzoate,
Ditertiary butyl peroxyisophthalate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary butyl peroxide maleic acid, tertiary butyl peroxyisopropyl carbonate,
3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ', 4 , 4'-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,
4'-tetra- (t-octylperoxycarbonyl)
Benzophenone, 3,3 ', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Of these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) Benzophenone, 3,3 ', 4,4'
-Tetra- (t-xylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone,
Peroxide esters such as di-t-butyldiperoxyisophthalate are preferred.

The above (e) thio compound has the general formula (VI)
Indicated by The alkyl group of R ³⁸ and R ³⁹ in the general formula (VI) is preferably one having 1 to 4 carbon atoms. The aryl group of R ³⁸ is preferably a group having 6 to 10 carbon atoms such as phenyl and naphthyl. As the substituted aryl group, a halogen atom such as a chlorine atom and a methyl group And those substituted with an alkoxy group such as an alkyl group, a methoxy group or an ethoxy group.

Specific examples of the thio compound represented by the general formula (VI) include the compounds shown in the following table.

[0191]

[Table 3]

[0192]

[Table 4]

[0193]

[Table 5]

The hexaarylbiimidazole of the component (f) used in the present invention includes 2,2'-bis (o-
(Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Bis (o, p-dichlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and the like.
Examples of the ketoxime ester include 3-benzoyloximinobtan-2-one and 3-acetoxyiminobutan-
2-one, 3-propionyloxy iminobutan-2-
On, 2-acetoxyiminopentan-3-one, 2-
Acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropane-1
-One, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-
1-phenylpropan-1-one and the like.

The (g) aromatic onium salts include elements of Groups V, VI and VII of the Periodic Table, specifically N, P, As, Sb, Bi, O, S, Se, Te or I aromatic onium salts are included. Examples of such aromatic onium salts include JP-B-52-14277 and JP-B-52-1.
No. 4278 and JP-B No. 52-14279 can be mentioned, and specifically, the following compounds can be mentioned.

[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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Of these, preferred are BF ₄ salts,
Or a compound of a PF ₄ salt, more preferably a BF ₄ salt or a PF ₄ salt of an aromatic iodonium salt.

Examples of the above (t) ketoxime esters include 3-benzoyloximinobtan-2-one,
Acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-
1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-
ON and the like.

The (nu) titanocene compound is a titanocene compound capable of generating an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye, and is, for example, disclosed in JP-A-59-152396 and JP-A-59-152396. Known compounds described in JP-A-61-151197 can be appropriately selected and used. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,
6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1
-Yl, di-cyclopentadienyl-Ti-bis-2,
4-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis -2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl,
Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium and the like can be mentioned.

These radical polymerization initiators (a) to (nu) can be used alone or in combination of two or more. The use amount is suitably from 0.05 to 100 parts by weight, preferably from 1 to 80 parts by weight, more preferably from 3 to 50 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound. When the amount of the radical polymerization initiator is inappropriately large, undesired results such as blocking of effective light tend to occur. The amount of the radical polymerization initiator used in the present invention is in the range of 0.01% by weight to 60% by weight based on the total amount of the ethylenically unsaturated compound and the polymer binder optionally added. preferable. More preferably, from 1% by weight to 30%
Good results are obtained with% by weight.

Further, the photosensitive resin composition of the present invention may contain an organic halogen compound and a leuco dye for the purpose of distinguishing the color of the exposed portion and the unexposed portion.
As the organic halide, the above-mentioned radical polymerization initiator (a) a compound having a carbon-halogen bond is generally used. The amount of the organic halogen compound used in the present invention as such a printing-out agent ranges from 0.001% by weight to 5% by weight based on the solid content of the photoresist. More preferably, it is 0.005% by weight to 1% by weight.

Typical leuco dyes usable in the present invention include the following. Tris (p-dimethylaminophenyl) methane, leuco crystal violet, tris (p-diethylaminophenyl) methane, tris (p-dimethylamino-o-methylphenyl) methane, tris (p-diethylamino-o-methylphenyl) methane, Bis (p-dibutylaminophenyl)-[p- (2-cyanoethyl) methylaminophenyl] methane, bis (p-dimethylaminophenyl) -2
Aminotriarylmethanes such as quinolylmethane and tris (p-dipropylaminophenyl) methane;
-Bis (diethylamino) -9-phenylxanthene,
3-amino-6-dimethylamino-2-methyl-9-
Aminoxanthenes such as (o-chlorophenyl) xanthene, 3,6-bis (diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene, 3,6-
Aminothioxanthenes such as bis (dimethylamino) thioxanthene, 3,6-bis (diethylamino) -9,
Amino-9,10-dihydroacridines such as 10-dihydro-9-phenylacridine, 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine, and 3,7-bis (diethylamino) phenoxy Aminophenoxazines such as sagin; aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine;
3,7-bis (diethylamino) -5-hexyl-5,
Aminodihydrophenazines such as 10-dihydrophenazine; aminophenylmethanes such as bis (p-dimethylaminophenyl) anilinomethane; 4-amino-4'-
Dimethylaminodiphenylamine, 4-amino-α, β
-Aminohydrocinnamic acids such as methyl-dicyanohydrocinnamate, hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine, 1,4-bis (ethylamino) -2,3-dihydroanthraquinone and the like Amino-
Phenethylanilines such as 2,3-dihydroanthraquinones and N, N-diethyl-p-phenethylaniline;
It has no oxidizable hydrogen such as an acyl derivative of a leuco dye containing a basic NH group such as 10-acetyl-3,7-bis (dimethylamino) phenothiazine and tris (4-diethylamino-o-tolyl) ethoxycarbonylmethane. , A leuco-like compound which can be oxidized to a color-forming compound, a leucoin digoid dye, which can be oxidized to a color-forming form as described in U.S. Pat. Nos. 3,042,515 and 3,042,517. Such organic amines. The following may be mentioned as typical compounds of this type. 4,4'-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4'-methylenediaminetriphenylamine, N-vinylcarbazole.
Of these, particularly preferred is leuco crystal violet.

The amount of the leuco dye is in the range of 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the solid content of the photoresist.

In the present invention, a dye can be used for the purpose of coloring a photoresist or imparting storage stability. Examples of suitable dyes include brilliant green sulfate, eosin, ethyl violet, erythrosin B, methyl green, crystal violet,
Basic fuchsin, phenolphthalein, 1,3-
Diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange N, diphenylthiocarbazone, 2,7-
Dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl-red, nile blue A, phenacetaline, methyl violet, malachite green oxalate, parafuchsin,
Oil Blue # 603 [Orient Chemical Industry Co., Ltd.
Manufactured), rhodamine B, rhodamine 6G and the like.

A particularly preferred dye is malachite green oxalate.

It is preferable to add a thermal polymerization inhibitor to the photoresist of the present invention. Specific examples of the thermal polymerization inhibitor include, for example, p-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone,
t-butylcatechol, pyrogallol, cuprous chloride, chloranil, naphthylamine, β-naphthol, 2,6
-Di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, organic copper, methyl salicylate and the like. These thermal polymerization inhibitors are used in an amount of 0.00
It is preferably contained in the range of 1 to 5% by weight.

In the present invention, a plasticizer may be added to control the physical properties of the film. Representative examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, Phthalates such as dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diaryl phthalate, dimethyl glycolose phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene Glycol esters such as glycol dicaprylate, and phosphate esters such as tricresyl phosphate and triphenyl phosphate. , Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, fatty acid dibasic acid esters such as dibutyl malate, benzenesulfonamide, p-toluenesulfonamide, N-n-butylacetamide and the like Examples include amides, triethyl citrate, glycerin triacetyl ester, and butyl laurate.

In the present invention, a known so-called adhesion promoter can be used to improve the adhesion to the base. For example, JP-B-50-9177, JP-B-54-5,292, JP-B-55-22,481, JP-A-51-64,919, and JP-A-51-64,920.
JP-A-50-63,087, JP-A-52-2,7
No. 24, JP-A-53-702, JP-A-53-124,
No. 541, JP-A-53-124594, JP-A-54
-133,585, JP-A-54-133,586,
JP-A-55-65,947 and JP-B-57-46,05.
No. 3, JP-B-57-46,054, JP-A-56-1
No. 1,904, JP-B-57-21,697, JP-A-5
6-75,642, JP-A-56-67,844, JP-B-57-40,500, JP-A-56-99,202.
JP-A-56-100,803, JP-A-57-66-1
0,327, JP-A-57-62,047, DAS
No. 2,448,850, US Pat. No. 4,629,679, JP-B-57-49,894, JP-A-57-148,39.
No. 2, JP-A-57-192,946, JP-A-58-1
00,844, JP-A-59-113,432, JP-A-59-125,725, JP-A-59-125,72.
6, JP-A-59-125,727, JP-A-59-1
25,728, JP-A-59-152,439, JP-A-59-154,440, JP-A-59-154,44
No. 1, JP-A-59-165,051, JP-A-60-1
2,543, JP-A-60-12,544 and JP-A-6
0-135,931, JP-A-60-138,540
JP-A-60-146,233, JP-A-61-4,
No. 038, JP-A-61-6,644, JP-A-61-644
No. 6,646, JP-A-61-166,541, JP-A-61-172,139, JP-A-61-186,952
No., JP-A-61-190,330, JP-A-61-19
8,146, JP-A-61-223,836, JP-A-61-282,835, JP-A-61-360,237
JP-A-62-91,935, JP-A-62-96,
939, JP-A-62-180,354, JP-A-62
-180,355, JP-A-62-180,356,
JP-A-62-180,357, JP-A-62-181,
No. 303, JP-A-62-208,042, JP-A-62
-240,950, JP-A-62-277,405,
JP-A-62-286,035, JP-A-62-290,
No. 702, JP-B-63-13,526 and JP-A-63-63.
There are compounds described in JP-A-24-243, JP-A-63-57,622, JP-A-63-61,241 and the specification.

Specifically, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole,
2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2
-Thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole and the like.

A particularly preferred compound is 3-morpholinomethyl-1-phenyltriazole-2-thione. Next, the inorganic particles used in the present invention will be described. The inorganic particles of the present invention have an average particle size of 0.01 to 1
The thickness is 0 μm, preferably 0.05 to 5 μm, and the material is not particularly limited. The shape of the inorganic particles is not particularly limited, but is preferably spherical, elliptical, or the like. In addition, the average particle diameter referred to in the present invention refers to an average of the maximum major diameter of the particles.

As the material of the inorganic particles, glass particles, metal powders, metal oxides, phosphors and the like are preferable. As the glass, a low melting point glass having a low melting point (Tm) is preferable. In the present invention, Tm is selected depending on the material of the substrate on which the photosensitive resin composition is provided or the material to be insulated, or the material of the inorganic structure to be patterned on the substrate. ~ 650 ° C.

The glass composition is not particularly limited, but is appropriately adjusted so as to have an affinity for the photoresist and the inorganic compound or the metal compound used in the present invention, and to be able to be uniformly dispersed in the photoresist. Are preferred. Further, it is preferable that other inorganic particles also have such characteristics. For example, as the glass composition, SiO ₂ , Al ₂ O ₃ , B ₂ O ₂ , CaO, Mg
O, BaO, ZnO, Na ₂ O, K ₂ O, Li ₂ O, F
e ₂ O ₃ , PbO, CeO ₂ , ZrO ₂ , TiO ₂ , S
b ₂ O ₃ , BiO, Bi ₂ O ₃ , P ₂ O ₅ , As
₂ O ₃ , CoO, Cr ₂ O ₃ , Ag, Au, F, Cl,
At least one kind may be appropriately selected from Br and the like.

Usually, when the inorganic structure is formed on a glass substrate, the glass composition may be such that silicon oxide is blended in the range of 3 to 80% by weight. If the content is less than 3% by weight, the denseness, strength and stability of the glass layer are reduced, and the coefficient of thermal expansion deviates from desired values, so that a mismatch with the glass substrate is likely to occur.

Glass particles containing at least one of bismuth oxide and lead oxide and having a total content of 5 to 60% by weight, or boron oxide, bismuth oxide or lead oxide having a total content of 8 to 60% by weight. Those containing at least one of lithium oxide, sodium oxide and potassium oxide in an amount of 3 to 15% by weight,
Usually, the melting point is low.

Examples of the metal powder include silver, platinum,
Examples include gold, nickel, palladium, tungsten, ruthenium, and alloys thereof (which may include silicon, carbon, phosphorus, and the like). Examples of the metal oxide include oxides such as boron, aluminum, barium, calcium, magnesium, titanium, zinc, iron, copper, tin, and zirconium, with alumina being preferred. One or more metal atoms of these metal oxides may be used. these,
The metal oxide can have a ceramic structure.

In the present invention, the inorganic structure after firing can be colored by adding various metal oxides. For example, when the photosensitive resin composition contains 1 to 10% by weight of a black metal oxide, an inorganic structure having a black pattern can be formed. Blackening can be achieved by including at least one, and preferably three or more, of oxides of Cr, Fe, Co, Mn, and Cu as the black metal oxide used at this time. In particular, Fe and M
By containing 0.5% by weight or more of each oxide of n, a blacker pattern can be formed.

Further, by using a paste to which an inorganic pigment that develops a color such as red, blue, or green in addition to black is added, an inorganic structure having a pattern of each color can be formed. These coloring patterns can be suitably used for a color filter of a plasma display and the like. The phosphor used in the present invention is not particularly limited, but includes an ultraviolet-excited phosphor, for example, red = Y ₂ O ₃ : Eu, Y ₂ SiO ₅ : Eu, Y ₂ Al
_{5 O 12: Eu, YVO 4} : Eu, (Y, Gd) BO 3: E
u, YBO ₃ : Eu, Zn ₃ (PO ₄ ) ₂ : Eu, GdB
O ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu Green = Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, B
aMgAl ₁₄ O ₂₃ : Mn, SrAl ₁₂ O ₁₉ : Mn, Z
nAl ₁₂ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn Blue = B
aMgAl ₁₄ O ₂₃ : Eu, BaMgAl ₁₆ O ₂₇ : Eu,
Y ₂ SiO ₅ : Ce and the like can be exemplified.

In the present invention, it is preferable that other inorganic particles, for example, alumina particles are contained as the inorganic particles together with the low melting point glass particles. When low-melting glass particles and alumina particles are used as the inorganic particles, the low-melting glass particles generally have a composition in the range of 20 to 90% by weight, preferably 35 to 85% by weight based on the entire inorganic particles. It is.

As for the inorganic particles, the lower the firing temperature, the lower the heat energy and the wider the range of selection of the substrate, filter and other materials. In order not to let
The coefficient of linear thermal expansion is 50 to 90 × 10 ⁻⁷ ,
It is desirable to use glass particles of 90 × 10 ⁻⁷ .

The shrinkage rate during firing can be suppressed by using a combination of fine particles having different components as the inorganic particles used in the present invention, particularly, by using glass fine particles or ceramic fine particles having different melting points. . Since the photosensitive resin composition of the present invention can form an inorganic body formed by baking the contained inorganic particles corresponding to an arbitrary exposed region, the shape or pattern of the inorganic body and its use are There is no particular limitation. For example, an inorganic substance is used for a circuit or a conductor, a resistor, a phosphor, a rib of a partition wall, and the like, and the photosensitive resin composition of the present invention is suitable for forming a rib of a plasma display.

The method for forming the ribs of the plasma display is not particularly limited. However, the photosensitive resin composition of the present invention is provided as a layer on a base for a plasma display, and the backside of the base is exposed to light. It is preferable to carry out the treatment and the exposure treatment from the table of the base at least once each. Here, the exposure from the back of the base is performed by irradiating more light to the vicinity of the lower portion of the photosensitive resin composition layer on the base (that is, an area closer to the base) through the base to thereby expose the lower photosensitive resin composition. It is intended to further improve the photocurability and can be expected to further improve the profile. Therefore, the base material needs to be at least light transmissive. The exposure process from the base table is to directly expose the layer which is usually performed.

The method for forming the layer of the photosensitive resin composition is as follows.
Known coating methods include, for example, screen printing, curtain flow coating, spray coating, roll coating, blade coating, bar coating and the like. The viscosity of the photosensitive resin composition is usually 100 to 100,000 cps.
(Centipoise), depending on the application method. For example, in a screen printing method, preferably 15,000 to 7
It is in the range of 000 cps.

The viscosity can be appropriately adjusted by the type of the photoresist, the size of the inorganic particles, the proportion thereof, the solvent added as required, other plasticizers, thickeners and the like. The photosensitive resin composition of the present invention is at least composed of a photoresist and inorganic particles, but the inorganic particles need to be uniformly dispersed in the photoresist, and the dispersion method is particularly limited. Although not to be performed, a method of kneading and dispersing a mixture of photoresist, inorganic particles and a solvent, a method of adding and kneading inorganic particles in a photoresist, and a method of dispersing, and kneading and dispersing both solvent dispersions And the like. Note that a solvent is not necessarily required as long as the inorganic particles are uniformly dispersed in the photoresist.

In the photosensitive resin composition of the present invention, the mixing ratio of the photoresist (solid content) and the inorganic particles is 1/99 to 99/99 of the photoresist (solid content) and the inorganic particles.
1, preferably in the range of 5/95 to 80/20. Examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol and sec.
Alcohols such as butanol and n-hexanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone, ethyl acetate, butyl acetate, n-amyl acetate, methyl formate, methyl propionate and ethyl phthalate , Esters such as ethyl benzoate, toluene, xylene,
Aromatic hydrocarbons such as benzene and ethylbenzene, carbon tetrachloride, trichloroethylene, chloroform,
Halogenated hydrocarbons such as 1,1-trichloroethane, methylene chloride, monochlorobenzene, etc., ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, dimethylformamide , Dimethyl sulfoxide and the like.

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates, alkyldi (aminoethyl) Good amphoteric surfactants such as glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type, For example, a surfactant such as a fluorine-based surfactant described in JP-A-62-170950 can be added.

These surfactants may be added alone or in some combination. The proportion of the surfactant in the photosensitive resin composition is usually 5% by weight or less, preferably 1% by weight or less. Examples of the base material include glass, ceramics, and a polymer film.

In the exposure treatment, exposure can be performed directly by a known means, for example, through a photomask or with visible light laser light, Ar ion laser light, or the like, and an inorganic substance profile corresponding to the exposed region can be formed. . Examples of the exposure apparatus include a stepper type and a proximity type. Further, the exposure processing may be performed while transporting the base.

The light for the exposure treatment is not particularly limited, but includes visible light, ultraviolet light, electron beam, X-ray, laser light and the like. In the present invention, since the exposure processing is performed from behind, the exposure conditions can be relaxed as compared with the conventional case, and an energy saving effect can be expected. For example, when ultraviolet rays are used, the exposure conditions are as follows:
000 mJ / cm ² , exposure amount 5 to 800 mJ / c from the table
The processing of m ² is exemplified as a suitable processing.

If desired, after exposure, the temperature is 80 to 130 ° C.
A step of heating at about the temperature may be added. Examples of the developing method after exposure include an immersion method, a spray method, and a brush method. Examples of the developing solution include an aqueous solution of an alkali or a solution to which an organic solvent such as an alcohol or a surfactant is added.

Examples of the alkalis include inorganic alkalis such as potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; ethylamine;
Primary amines such as -propylamine, diethylamine,
Secondary amines such as di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; and quaternary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Examples thereof include ammonium salts, cyclic amines such as pyrrole and piperidine.

The temperature during development is usually from 15 to 30.
C., but preferably at 18 to 28C. Next, the desired pattern obtained by the development can be baked to obtain a patterned inorganic substance. Conditions such as the firing atmosphere and the temperature are selected according to the components of the photosensitive resin composition and the type of the substrate. Examples of the firing atmosphere include an atmosphere in which the partial pressure of nitrogen, hydrogen, or the like is appropriately adjusted in the air. Examples of the furnace include a batch type and a continuous type.

The firing temperature is usually from 350 to 800 ° C.
Done in When patterning on a glass substrate,
Holding at 400 to 650 ° C. for 10 to 180 minutes is common. In addition, during the above-described steps of forming a coating layer, exposing, developing, and firing, usually 50 to 12 for drying or preliminary reaction.
A 0 ° C. heating step may be provided.

[0239]

Hereinafter, specific examples of the present invention will be described.
The present invention is not limited to this. In addition, "part"
Means "parts by weight". Example 1 A uniform photosensitive resin composition was prepared by mixing the following components. Ethylenically unsaturated compound Polypropylene glycol diacrylate (average molecular weight: 822) 6.5 parts Tetraethylene glycol dimethacrylate 1.5 parts Sensitizing dye I-5 0.05 parts Radical polymerization initiator VII-1 0.1 parts Polymer Binder 42.9 parts 35% by weight of methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / benzyl methacrylate copolymer (molar ratio 55 / 28.8 / 11.7 / 4.5, weight average molecular weight 90,000) Solution (solvent: methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (weight ratio) Crosslinking agent 15 parts of the following compound

[0240]

Embedded image

P-toluenesulfonamide 0.5 part malachite green oxalate (1% methanol solution) 1.625 parts 3-morpholinomethyl-1-phenyltriazole-2-thione 0.01 part phenyltribromomethylsulfone 0 .05 parts Leuco Crystal Violet 0.20 parts Lead-containing low-melting glass 70 parts (average particle diameter 1 μm, melting point 560 ° C)

Next, a layer of a photosensitive resin composition having a dry thickness of 200 μm was provided on a glass base for a plasma display. Then, using an argon laser, each pattern of a pitch of 300 μm, a line width of 60 μm (hereinafter referred to as pattern 1), a bitch of 100 μm, and a line width of 30 μm (hereinafter referred to as pattern 2) was formed by laser scanning with a layer of 100 mJ / cm ^2.
And then immersed in a 0.5% aqueous solution of NaOH for development. In addition, the dry thickness is 150
Except for changing to μm, a sample exposed and developed using the same laser as in pattern 1 (pattern 3) and a sample exposed and developed using the same laser as in pattern 2 (pattern 4) were prepared.

The glass base having the developed patterns 1 to 4 was dried and baked at 590 ° C. for 120 minutes to form ribs. Example 2 Baking was performed in the same manner as in Example 1 except that the exposure conditions were changed from the back exposure of the base and the exposure from the front of the base to exposure once each at the following exposure amount. ,
Ribs were formed.

Exposure conditions per exposure: Exposure from the back of the base: Exposure amount: 20 mJ / cm ² Exposure from the base table: Exposure amount: 100 mJ / cm ² The adhesion to the glass base was all good. The obtained profile was evaluated as follows, and the results are shown in Table 6.

Evaluation ◎: In a cross section perpendicular to the base, the portion of the rib near the base has a foot shape of a mountain, and the upper portion has a rectangular shape. ：: In a cross section perpendicular to the base, the rib has a rectangular shape as a whole without any missing portion near the base.

[0246]

[Table 6]

From the above table, it can be seen that the ribs obtained from the photosensitive resin composition of the present invention have excellent adhesion to the base and excellent profile despite high density. In addition, it can be seen that the profile can be improved by using the method of the present invention that uses exposure from behind.

[0248]

According to the present invention, by combining a negative photoresist having high sensitivity and high resolution with inorganic particles having an average particle diameter in a specific range, good adhesion to a profile and a base and high density can be obtained. Further, a rib for a plasma display having a high aspect ratio can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01J 9/02 H01J 9/02 F 17/49 17/49 Z

Claims (7)

[Claims] 1. A photosensitive resin composition comprising at least a photoresist containing at least an ethylenically unsaturated compound, a sensitizing dye and a radical polymerization initiator, and inorganic particles having an average particle diameter of 0.01 to 10 μm. Stuff. 2. The sensitizing dye is selected from the following group A:
2. The method according to claim 1, wherein the at least one kind is selected from the group consisting of:
Photosensitive resin composition. Group A: a compound represented by the following general formula (I):(However, R in the formula¹~ R^FourAre independently a hydrogen atom,
Halogen atom, alkyl group, substituted alkyl group, aryl
Group, substituted aryl group, hydroxyl group, alkoxy group, substituted
Represents a xy group, an amino group, or a substituted amino group. Also R¹~
R^FourIs a non-metallic atom together with the carbon atom to which it is attached.
May form a ring. R^Five, R⁶Are independent of each other
Hydrogen, halogen, alkyl, substituted alkyl
Group, aryl group, substituted aryl group, heteroaromatic group,
Sil group, cyano group, alkoxycarbonyl group, carboxy
Represents a sil group or a substituted alkenyl group. Also R^FiveAnd R⁶Is
May form a ring composed of a non-metallic atom. X is
O, S, NH, or a nitrogen atom having a substituent.
G¹, G^TwoMay be the same or different from each other.
Hydrogen atom, cyano group, alkoxycarbonyl group,
Alkoxycarbonyl group, aryloxycarbonyl group,
Substituted aryloxycarbonyl group, acyl group, substituted acyl
Group, arylcarbonyl group, substituted arylcarbonyl
Group, alkylthio group, arylthio group, alkylsulfo
Nil group, arylsulfonyl group, fluorosulfonyl group
Represents Where G¹And G^TwoIs the carbon atom to which it is attached
May form a ring composed of a non-metallic atom together. ) A compound represented by the following general formula (II):(However, R in the formula⁷, R⁸May be the same or different
Hydrogen, alkyl, substituted alkyl, alkenyl
Group, substituted alkenyl group, alkoxycarbonyl group,
Reel, substituted aryl, alkynyl or substituted
Represents a rukinyl group. A is an oxygen atom, a sulfur atom, an alkyl
A carbon atom substituted by a group or an aryl group, or
Represents a carbon atom substituted by two alkyl groups. J is nitrogen-containing
Non-metallic atoms necessary to form a 5-membered heterocyclic ring
You. Y is a phenyl group, a substituted phenyl group, unsubstituted or substituted
Represents a substituted heteroaromatic ring. Z¹Is a hydrogen atom, al
Kill group, substituted alkyl group, aryl group, substituted aryl
Group, alkoxy group, alkylthio group, arylthio group,
Substituted amino group, acyl group, or alkoxycarbonyl
Z represents a group¹And Y may combine with each other to form a ring
No. ) A compound represented by the following general formula (III):(However, R in the formula^Ten~ R¹³Are independently a hydrogen atom,
An unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, carbon number
1-6 unsubstituted or substituted alkenyloxy groups, carbon number
1-6 unsubstituted or substituted alkylthio groups, each alkyl
Dialkylamino group having 1 to 4 carbon atoms, hydroxyl
Group, acyloxy group, halogen atom, nitro group, or
Represents a multiple ring group. R^Ten~ R¹³Two or three of the above and R
^Ten~ R¹³And the ring-constituting carbon atom to which the substituent of
A fused ring wherein each fused ring is a 5- or 6-membered ring
May form a fused ring system. R⁹Is hydrogen atom, carbon number
1-4 unsubstituted or substituted alkyl groups or 6-carbon atoms
12 unsubstituted or substituted aryl groups, or R¹⁴-CO
Represents-. Where R ¹⁴Is an alkoxy group, cycloalkoxy
Xy, hydroxyl, aryloxy, alkenyloxy
Group, aralkyloxy group, alkoxycarbonyl alcohol
A xy group, an alkylcarbonylalkoxy group, or
Represents a substituent represented by any of the following (III-a) to (III-c). Embedded imageR^Fifteen~ R¹⁸Is a hydrogen atom, an alkyl group, a hydroxyalkyl
Group, hydroxyalkoxyalkyl group, alkoxyl
Represents an alkyl group or a cycloalkyl group, and m is 1 to 5.
And n is 0 to 10. Q¹Is a cyano group, a heterocyclic ring,
Or -Z^Two-R¹⁹Represents Where R¹⁹Has 1 to 10 carbon atoms
An unsubstituted or substituted alkyl group, alkenyl group, or
Alkoxy group, unsubstituted or substituted ant having 6 to 12 carbon atoms
Unsubstituted or substituted aryloxy having 6 to 12 carbon atoms
5 carbon atoms and hetero atoms constituting the xy group or the ring
Up to 15 unsubstituted or substituted heterocyclic groups, or hydroxyl
Represents an acyl group. Z^TwoIs carbonyl group, sulfonyl
Group, sulfinyl group or arylenedicarbonyl group,
-(CH = CH)_k(K is 1 or 2). ) 3. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated compound is an acrylic compound. 4. The photosensitive resin composition according to claim 1, wherein the photoresist contains a polymer binder and / or a crosslinking agent. 5. The inorganic particles include at least one selected from low-melting glass particles, metal powders, metal oxides and phosphors.
The photosensitive resin composition according to any one of claims 1 to 4, comprising a seed. 6. The photosensitive resin composition according to claim 1, which is used for forming ribs of a plasma display. 7. The photosensitive resin composition according to claim 6 is provided as a layer on a base for a plasma display, and exposure processing from the back of the base and exposure processing from the front of the base are performed at least once each. A method of forming a rib for a plasma display.