JP2000187322A - Photosensitive composition, image forming material and image forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition and an image forming material high in sensitivity to infrared rays and good in adhesiveness and an image forming method. SOLUTION: The photoresist composition is characterized by containing (a) an alkali-soluble resin, (b) an infrared absorbing dye, (c) a polymerization initiator, and (d) a compound having an ethylenically unsaturated double bond. At that time, the alkali-soluble resin (a) of the photosensitive composition may have a side chain having a double bond. The image forming material is provided with a photosensitive layer comprising the above photosensitive composition on a substrate and an image is formed by using this image forming material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, an image-forming material and an image-forming method capable of forming an image by photocrosslinking by irradiation with actinic rays and developing with an alkali developing solution or the like. More specifically, the present invention relates to a photosensitive composition, an image forming material, and an image forming method that can use infrared rays as actinic rays and can be directly drawn by a semiconductor laser, a solid laser, or the like. The photosensitive composition of the present invention is useful for a printing plate, a plasma display, a printed board, a plating resist for semiconductors, an etching resist, and a color resist for a color filter.

[0002]

2. Description of the Related Art A vinyl resin having a carboxyl group and a double bond in a side chain is useful as a binder resin of a photosensitive resin for forming an image because of its high developability and curability. In particular, it has been found that a method of introducing a double bond into a resin side chain using an unsaturated compound having an alicyclic epoxy group exhibits excellent effects in terms of synthesis and physical properties (Japanese Patent Application Laid-Open No. -325400). These methods use ultraviolet rays as actinic rays and require a mask as an original image for imagewise exposure.

[0003] On the other hand, a technique of directly drawing with a laser beam based on image data of a computer is being studied earnestly. In particular, semiconductor lasers and solid-state lasers having an output in the infrared are characterized by stability, cost, output, and compactness, so that compositions having photosensitive characteristics in such a wavelength region are required. Examples of such a composition include a composition utilizing a phase change of a novolak resin (Japanese Patent Application Laid-Open No. 9-43847) and a composition utilizing a thermal reaction by a light-to-heat conversion material (Japanese Patent Application Laid-Open Nos. JP-A-43845, JP-A-8-276558, JP-A-9-13
No. 4009). Since these compositions lack sensitivity and stability, there is a strong demand for improved photosensitive compositions .

[0004]

An object of the present invention is to provide a highly stable photosensitive composition having high photosensitivity to a laser emitting infrared light, an image forming material and an image forming method. is there. In addition, photosensitive compositions, image forming materials, and the like, which are excellent in adhesion, durability, and the like, can be suitably used for etching resists, plating resists, and the like used for processing printed boards, plasma displays, liquid crystal display elements, semiconductors, and the like. An image forming method is provided.

[0005]

Means for Solving the Problems As a result of diligent studies, the present inventor has found that an alkali-soluble resin having a side chain double bond, particularly a resin having a side chain double bond introduced by an alicyclic epoxy unsaturated compound, is used. It has been found that a photosensitive composition containing an infrared absorbing dye, a polymerization initiator, and an unsaturated compound has high sensitivity to infrared laser light and also has excellent stability of a photosensitive solution. That is, the gist of the present invention is (a) an alkali-soluble resin, (b) an infrared absorbing dye, (c) a polymerization initiator,
And (d) a photosensitive composition containing an ethylenically unsaturated double bond-containing compound, wherein (a) the alkali-soluble resin has a side chain double bond. Also, the present invention relates to an image forming material and an image forming method having a photosensitive layer comprising the above photosensitive composition on a substrate.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described in detail. (A) Alkali-soluble resin The alkali-soluble resin of the present invention has a double bond (ethylenically unsaturated bond) in the resin side chain. The side chain double bond can be obtained, for example, by adding an ethylenically unsaturated group-containing epoxy compound to a carboxyl group of an alkali-soluble resin having a carboxyl group.

As a resin having a carboxyl group, 1)
Resin obtained by radical or ionic polymerization of a monomer having a carboxyl group; 2) Resin obtained by subjecting a monomer having an acid anhydride to radical or ionic polymerization to hydrolyze or half-esterify an acid anhydride unit; 3)
Epoxy acrylates obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride are exemplified.

Specific examples of vinyl resins having a carboxyl group include (meth) acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-maleinoloyloxyethyl methacrylate as monomers having a carboxyl group. Resins obtained by homopolymerizing unsaturated carboxylic acids such as 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, maleic acid, fumaric acid, itaconic acid and crotonic acid, and unsaturated carboxylic acids thereof. The acid is styrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, ( (Meth) acrylamide, glycidyl (meth) a Lylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonate, (meth) acrylic chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N-dimethylacrylamide, N- Resins copolymerized with a vinyl monomer having no carboxyl group, such as methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethylacrylamide.

Further, maleic anhydride is copolymerized with styrene, α-methylstyrene and the like, and the maleic anhydride unit is half-esterified with a monohydric alcohol such as methanol, ethanol, propanol, butanol and hydroxyethyl (meth) acrylate. Alternatively, a resin hydrolyzed with water may be used.

In addition, (meth) acrylic acid, 2-succinoloyloxyethyl methacrylate, novolak epoxy acrylate resin, bisphenol epoxy resin, etc.
2-malenoloyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-methacrylic acid
After adding an unsaturated carboxylic acid such as hexahydrophthaloyloxyethyl, maleic acid, fumaric acid, itaconic acid, crotonic acid or a saturated carboxylic acid such as acetic acid, propionic acid or stearic acid, maleic anhydride, itaconic anhydride Resins modified with acid anhydrides such as acids, tetrahydrophthalic anhydride and phthalic anhydride are also included.

Among the above, from the viewpoint of developability, a resin having a carboxyl group, particularly a (meth) acrylic acid (co) polymer resin containing (meth) acrylic acid is preferable. Specifically, for example, methyl methacrylate described in JP-A-60-208748 /
Methacrylic acid copolymer, methyl methacrylate / methyl acrylate / methacrylic acid copolymer described in JP-A-60-214354, benzyl methacrylate / methyl methacrylate / methacrylic acid / JP-A-5-36581 2-ethylhexyl acrylate copolymer, methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer described in JP-A-5-333542, styrene described in JP-A-7-261407 / Methyl methacrylate / methyl acrylate / methacrylic acid copolymer, JP-A-10-11000
No. 8, Methyl methacrylate / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer described in JP-A-8-108, and methyl methacrylate / n-butyl acrylate / 2-acrylate acrylate described in JP-A-10-198031.
Examples include an ethylhexyl / styrene / methacrylic acid copolymer.

As the epoxy unsaturated compound, a compound having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether can be used, but an unsaturated compound having an alicyclic epoxy group is preferable. . Examples of such a compound include the following compounds.

[0013]

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The reaction for introduction into the resin side chain includes, for example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride, pyridine, triphenylphosphine. The reaction can be carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using the above as a catalyst. If the amount of the alicyclic epoxy unsaturated compound to be introduced is controlled so that the acid value of the obtained resin satisfies the range of 5 to 200 KOH.mg/g, it is preferable in terms of alkali developability. The molecular weight is 500-500 by weight average.
0000, more preferably 1000 to 500,000.

(B) Infrared absorbing dye The infrared absorbing dye is a compound having strong absorption in the infrared region, more specifically, in the infrared region of 780 nm or more. Examples of such compounds include phthalocyanine dyes, cyanine dyes, polymethine dyes, anthraquinone dyes, aminium dyes, iminium dyes, diimmonium dyes, thiol nickel complex dyes, naphthoquinone dyes, and fulgide dyes. Among them, phthalocyanine dyes, cyanine dyes and polymethine dyes are preferred.

The phthalocyanine dye is represented by the following formula (I) or (II)
Having a phthalocyanine basic skeleton.

[0017]

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[0018]

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[In the formula (II), M represents a metal element forming a phthalocyanine complex salt, the aromatic ring may have a substituent, and the substituents are connected to each other to form a condensed ring. And the condensed ring may have a substituent. ]

As the central metal M, an alkali metal (I
a), Alikari earth metal (IIa), IIIb group, IVb group, Vb group,
VIb, VIIb, VIIIb, Ib, IIb, IIIa, IV
Examples include various metals of group a, group Va, lanthanides and actinides, and those having no central metal can also be preferably used.

Examples of the substituent for the aromatic ring and the condensed ring include an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, a halogen atom, a nitro group, a cyano group, an amino group, an alkoxycarbonyl group, a vinyl group, a carboxyl group and an acryloyl group. Thioether group, silyl group and the like, and a plurality of substituents may be the same or different.

Examples of such compounds include, for example, JP-A-64-60660, JP-A-1-110171, JP-A-3-31247, and JP-A-4-152.
No. 63, JP-A-4-15264, JP-A-4-15264
Phthalocyanine compounds described in JP-A-15265 and JP-A-4-15266; alkylphthalocyanine compounds described in JP-A-2-138382;
JP-A-77840 and JP-A-3-100066, and acyloxyphthalocyanine compounds described in JP-A-4-34.
No. 8168, alkoxy phthalocyanine compounds, JP-A-60-23451, JP-A-61-21
5662, JP-A-61-215663, JP-A-63-270765, JP-A-1-28717
No. 5, JP-A-2-43269, JP-A-2-2-2
No. 96885, JP-A-3-43461, JP-A-3-265664, and naphthalocyanine compounds described in JP-A-3-265665.
No. 8264, and dinaphthalocyanine compounds described in JP-A-1-108265.

Specific examples include the following compounds. In the following examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and P represents a butyl group.
h represents a phenyl group, respectively.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The cyanine dye and the polymethine dye have a structure in which a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is bonded by a polymethine (—CH ＝) _n chain, and are so-called cyanine dyes in a broad sense. Has a structure in which a hetero atom forms a heterocyclic ring and the heterocyclic ring is bonded via a polymethine chain. Specifically, for example, quinoline (so-called cyanine in a narrow sense), indole ( So-called indocyanine-based, benzothiazole-based (so-called thiocyanine-based), pyrylium-based, thiapyrylium-based, squarylium-based, croconium-based, azurenium-based, and the like. The polymethine dye is acyclic through a polymethine chain. It has a structure in which a heteroatom is bonded, and among these, cyanine dyes such as quinoline, indole, and benzothiazole And polymethine dyes are preferable.

If the specific chemical structure is exemplified, the following can be exemplified. In the following examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As quinoline dyes,

[0037]

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The indole dyes include

[0039]

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[0040]

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The benzothiazole dyes include

[0042]

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The polymethine dyes include

[0044]

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(C) Polymerization initiator The polymerization initiator is not particularly limited as long as it is a compound capable of generating an active radical capable of polymerizing an ethylenically unsaturated double bond-containing compound by actinic rays.
For example, an organic boron complex described later in detail, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (4-methoxynaphthyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl)-
halomethylated triazine compounds such as s-triazine, 2
-Trichloromethyl-5- (2'-benzofuryl)-
1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,
3,4-oxadiazole, 2-trichloromethyl-5
-[Β- (2 ′-(6 ″ -benzofuryl) vinyl)]
Halomethylated oxadiazole compounds such as -1,3,4-oxadiazole and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2- (2′-chlorophenyl) -4,5 -Diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2-
(2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2- (4′-
Methoxyphenyl) -4,5-diphenylimidazole dimer and other imidazole compounds, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin compounds, 2-methylanthraquinone, 2-ethylanthraquinone, 2- t-butylanthraquinone, 1
Benzophenone compounds such as anthraquinone compounds such as -chloroanthraquinone, benzanthrone compounds, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-
Isopropylphenyl) ketone, 1-hydroxy-1-
(P-dodecylphenyl) ketone, 2-methyl- (4 ′
Acetophenone compounds such as-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2- Chlorothioxanthone, 2,4
Thioxanthone compounds such as -dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzoic acid esters such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- ( acridine compounds such as p-methoxyphenyl) acridine, 9,10
Phenazine compounds such as dimethylbenzphenazine, 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-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti
-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophenyl
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Yl, di-methylcyclopentadienyl-Ti-bis-
Titanocene compounds such as 2,6-di-fluorophenyl-1-yl and di-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-yl) -phenyl-1-yl; Can be mentioned. Among them, the organic boron complex is preferable because it is excellent in sensitivity and stability.

The organoboron complex used in the present invention is a compound having a basic structure represented by the following formula (III).

[0047]

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[In the formula (III), R ¹ , R ² , R ³ and R
⁴ each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, Alkenyl group which may have a substituent, alkynyl group which may have a substituent, alicyclic group which may have a substituent, or And a heterocyclic group which may be linked to each other to form a cyclic structure, and X ⁺ represents a counter cation. ]

The alkyl groups and alicyclic groups represented by R ¹ , R ² , R ³ and R ⁴ have 1 to 10 carbon atoms, and the alkenyl groups and alkynyl groups have carbon atoms. Those having a number of 1 to 15, and those of the aryl group, aralkyl group and alkaryl group each having 6 to 20 carbon atoms are preferable, and the aryl group is particularly preferably a phenyl group. Examples of the substituent include an alkyl group, an alkoxy group, a carboxy group, an acyloxy group, an alkoxycarbonyl group, a hydroxy group, an amino group, an alkylamino group, a halogenated alkyl group, and a halogen atom. Particularly preferred.

From the viewpoints of stability and high polymerization activity, R ¹ to
A triarylalkyl boron complex in which three of R ⁴ are an aryl group which may have a substituent and one is an alkyl group which may have a substituent are preferred. Further, those in which the aryl groups bonded to boron have a chemical bond as described below are also preferable. Here, R is an alkyl group.

[0051]

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Specific examples of preferred anions in these organic boron complexes include, for example, n-butyl-triphenylboron anion, n-butyl-tris (p-methylphenyl) boron anion, n-butyl-tris (2, 4,6-trimethylphenyl) boron anion,
n-butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (p-fluoro Phenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n-
Butyl-tris (2,4,6-trifluorophenyl)
Boron anion, n-butyl-tris (2,3,4,
5,6-pentafluorophenyl) boron anion, n
-Butyl-tris (m-trifluoromethylphenyl)
Boron anion, n-butyl-tris (3,5-di-trifluoromethylphenyl) boron anion, n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) boron anion, n-hexyl-tris ( (m-fluorophenyl) boron anion.

As the counter cation, JP-A-62-1430
No. 44, JP-A No. 62-150242, and cationic dyes having absorption in the visible light region are inferior in stability, and therefore, those having as little absorption as possible in the visible light region are preferable. Examples include onium cation groups such as ammonium, phosphonium, arsonium, stibonium, oxonium, sulfonium, selenonium, stannonium, and iodonium, and transition metal coordination cation complexes. Among them, an ammonium cation is preferable, and a tetraalkyl (C 1-10) ammonium cation is particularly preferable.

Examples of the organoboron complex satisfying the above conditions include, for example, JP-A-9-188686,
-18885, JP-A-9-188710, JP-A-9-106242, JP-A-8-217
No. 813, an organic boron ammonium complex described in JP-A-6-157623 and JP-A-6-175564.
JP-A-6-175554, JP-A-6-175561, and organic boron-sulfonium complex or organoboron oxosulfonium complex described in JP-A-6-175561.
JP-A-175553, the organic boron iodonium complex described in JP-A-9-188710, the organic boron phosphonium complex described in JP-A-9-188710, JP-A-6-348011,
JP-A-7-128785, JP-A-7-14058
9, JP-A-7-306527, JP-A-7-306527
Specific examples include an organic boron transition metal coordination complex and the like described in Japanese Patent No. 292014 and the like.

Specific examples of such compounds include, for example, the following compounds. In the following examples, Me represents a methyl group, Et represents an ethyl group, and B represents
u represents a butyl group, respectively.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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(D) Ethylenically unsaturated double bond-containing compound (hereinafter referred to as “ethylenically unsaturated compound”) The ethylenically unsaturated compound has at least one polymerizable unsaturated double bond in the molecule. Compounds can be mentioned, and various known unsaturated compounds can be used. Above all, a so-called acrylic monomer is a low molecular weight compound having two or more double bonds in the molecule, particularly, four or more from the viewpoint of sensitivity, from the viewpoints of crosslinking efficiency, change in solubility, and the like. In addition, the molecular weight as a low molecular weight compound is generally 2000 or less, preferably 20 to 1,000. Further, as the acrylic monomer in the present invention,
Contains methacrylic monomer.

As the acrylic monomer, an aliphatic acrylate or an ester acrylate compound obtained by condensing an unsaturated carboxylic acid with an aromatic or heterocyclic hydroxy compound;
Examples thereof include an epoxy acrylate compound obtained by adding an unsaturated carboxylic acid to an aliphatic or aromatic epoxy compound, and a urethane acrylate compound obtained by adding an unsaturated hydroxy compound to an isocyanate compound, but are not necessarily limited thereto. .

Examples of the ester acrylate compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin methacrylate (meth) acrylate, trimethylolpropane di (meth) acrylate Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane ethylene oxide added tri (meth) acrylate, glycerin propylene oxide added Tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) Examples include acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.

Examples of the epoxy acrylate compound include compounds obtained by adding an α, β-unsaturated carboxylic acid to an epoxy compound having an epoxy ring such as a glycidyl group or an alicyclic epoxy group.

As the epoxy compound, the base skeleton to which the epoxy ring is bonded is an aliphatic, aromatic, or heterocyclic ring, or various epoxy compounds having a structure in which these are mixed with each other. Phenol novolak epoxy compound, (o, m,
Examples include p) -cresol novolak epoxy compounds, bisphenol-A epoxy compounds, bisphenol-F epoxy compounds, and halogenated epoxy compounds such as brominated phenol novolak epoxy compounds. These compounds may be low molecular weight compounds or oligomers or high polymers that become resins.

Examples of the aliphatic epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, (poly) glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether,
Hexanediol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) tetramethylene glycol diglycidyl ether, (poly) pentamethylene glycol diglycidyl ether, and the like. Examples of the epoxy compound having a heterocyclic structure include triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

Examples of the alicyclic epoxy compound include Celloxide 2021, 2080, 3000 manufactured by Daicel Chemical Industries, Ltd.
2000, EPOLIDE GT300, GT400 and the like. Α, β-
As the unsaturated carboxylic acid, for example, an epoxy acrylate compound to which (meth) acrylic acid or the like is added as a catalyst with a quaternary ammonium salt or the like can be preferably used, and further, an acid anhydride such as maleic anhydride or tetrahydrophthalic anhydride can be used. A modified epoxy acrylate further modified by the above can also be preferably used.

Examples of urethane acrylate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate;
Aliphatic diisocyanate such as 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω ′
Alicyclic diisocyanate such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α,
aliphatic diisocyanate having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate
4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate and other triisocyanates such as at least two isocyanates in a molecule. Group-containing compounds such as hydroxymethyl (meth) acrylate and hydroxyethyl (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, diisocyanuric acid alkylene oxide-added di (meth) And a) a compound obtained by reacting an acrylic compound having a hydroxyl group such as acrylate, pentaerythritol di (meth) acrylate monostearate, and the like.

The preferred compounding ratio of the components described above is (a) the alkalinized soluble resin 10 having a side chain double bond.
(B) 0.05-30 parts by weight of an infrared absorbing dye, (c) 0.05-30 parts by weight of a polymerization initiator, (d)
The range is from 10 to 500 parts by weight of the ethylenically unsaturated compound. When the ratio is out of the above range, sensitivity, developability and stability may decrease.

The photosensitive composition of the present invention may further comprise, in addition to the above-mentioned essential components, various applicability improvers such as anions, cations, nonions, and fluorine-based surfactants for various uses and purposes.
Additives such as an antifoaming agent, a visible image imparting agent after exposure, a coloring agent, an adhesion improver, a development improver, an ultraviolet absorber, and a polymerization stabilizer can be suitably blended.

The composition of the present invention can be prepared by dissolving the above components in a solvent to form a photosensitive solution, or by coating a support and drying it to form a layer comprising the photosensitive composition of the present invention on the support. It can be used favorably in the form of a lithographic printing plate or dry film.

When used as a photosensitive solution, the above components are dissolved or dispersed in an organic solvent. Examples of such an organic solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether,
Isoprene, ethyl isobutyl ether, butyl stearate, n-octane, diisobutylene, amyl acetate, butyl butyrate, apco thinner, butyl ether, diisobutyl ketone, methyl cyclohexane, methyl nonyl ketone, propyl ether, dodecane, So
cal solvent No. 1 and No. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, se
c, t), hexene, shell TS28 solvent,
Butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, Methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone,
Propyl propionate, propylene glycol-t-
Butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate,
Carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3
-Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, tripropylene Organic solvents such as glycol methyl ether and 3-methyl-3-methoxybutyl acetate can be exemplified. The usage ratio of the solvent is usually in the range of about 1 to 20 times by weight based on the total amount of the photosensitive composition.

Next, the method of using the photosensitive composition of the present invention will be described. When used as a photosensitive solution, the substrate is coated with a blade coater, rod coater, knife coater, rolled coater, roll doctor coater, transfer roll coater, gravure coater, kiss roll coater, cartain coater, spin coater, dip coater, spray coater, etc. Coating, drying by oven or hot plate. In the case of a dry film, a dry film obtained by coating and drying in the same manner is laminated on a substrate by a laminator.

The substrate is not particularly limited, but a substrate usually used for a printing plate, a printed substrate, a plasma display, a color filter and the like is preferable. For example,
Electrolytically treated aluminum plates, resin plates with copper foil laminated epoxy, polyimide, paper phenol, glass epoxy, etc., engineering plastics such as polycarbonate, polyphenylene sulfide, polyether ether ketone, soda glass, quartz glass, lead glass, etc. Various substrates such as glass, ITO, chromium, gold, etc., which are deposited, CVD or sputtered, and ceramic substrates can be used. An image forming material is obtained by forming a layer comprising the photosensitive composition of the present invention on such a substrate.

The coating amount of the photosensitive composition varies depending on the application, but is preferably in the range of 0.5 to 100 μm as a dry film thickness. For example, in the case of a lithographic printing plate, it is 0.5 to 100 μm.
10 μm, preferably 0.5 to 5 μm, more preferably 1 to 3 μm, and 3 to 1 when used for a dry film or the like.
00 μm, more preferably 5 to 70 μm.

When a film having an oxygen-blocking ability, such as poval, polyvinylpyrrolidone, polyethylene, or polypropylene, is further provided on the photosensitive layer, the sensitivity is improved due to the effect of reducing polymerization inhibition by air. In addition, since this layer can provide not only an oxygen blocking function but also a function of suppressing scratches and the like and improving handling properties, it is preferable to provide such a protective film.

When an image is formed using the photosensitive composition or the image forming material of the present invention, a laser exposure machine which emits infrared light from near infrared light is used. The preferred range for the irradiation wavelength is in the range of 780 to 1200 nm. As such a laser exposure machine, a solid-state laser such as a semiconductor laser and YAG can be given as the current state. Drawing is imagewise scanned and exposed based on digital information of a computer, and the exposed portions are cured. Among them, 78
This is advantageous for exposure with an infrared laser in the range of 0 to 880 nm.

The development can be performed by bringing the unexposed portion into contact with a dissolvable liquid. As such a liquid, the same organic solvent as used in the above-described preparation of the photosensitive solution can be used, but an aqueous alkaline solution is preferably used. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, and metasilicate. Inorganic alkalis such as potassium and organic alkalis such as triethanolamine, diethanolamine, monoethanolamine, trimethanolamine, dimethanolamine, monomethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyridine, etc. An aqueous solution of about 10% by weight can be given as an example. A small amount of an additive such as a surfactant, an organic solvent, or an antifoaming agent can be added to the aqueous alkali solution to improve functions such as developability. It is preferable to add a surfactant in many cases to obtain favorable results for improving resolution and background fouling. Examples of such a surfactant include known nonionic, anionic, cationic and betaine-based surfactants. The development method is not particularly limited, and various methods such as spin development, paddle development, dip development, and spray development can be used.

After development, post-baking, post-exposure, and other processing can be added if necessary. By adding such a post-treatment, the crosslink density and adhesion can be improved, and printing durability and etching resistance can be improved.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. Synthesis Example 1 (Synthesis of Alkali-Soluble Resin) 20 g of a styrene / acrylic acid copolymer resin having an acid value of 200 and a weight average molecular weight of 5,000, p-methoxyphenol 0.
2 g, dodecyltrimethylammonium chloride 0.
2 g and propylene glycol monomethyl ether acetate (40 g) were charged into a flask, and 7.6 g of 3,4-epoxycyclohexylmethyl acrylate was added dropwise to the flask.
The reaction was carried out at a temperature of ° C for 30 hours. The reaction solution was re-precipitated in water,
By drying, a styrene / acrylic acid copolymer resin having a double bond in a side chain was obtained. Upon neutralization titration with KOH, the resin acid value was 80 mg · KOH / g. Further, as a result of measuring the molecular weight by GPC, the weight average molecular weight Mw was 8,000, the number average molecular weight Mn was 3000, and the molecular weight distribution Mw / Mn was 2.7.

Synthesis Example 2 (Synthesis of Comparative Resin) Benzyl methacrylate 140 g, methacrylic acid 17
g, ethanol 200 g, azoisobutyronitrile 1.
5 g was added and the temperature was raised by an oil bath, and the reaction was carried out for 8 hours under reflux and nitrogen atmosphere conditions. The reaction solution was reprecipitated in pure water to obtain a benzyl methacrylate / methacrylic acid copolymer resin. Upon neutralization titration with KOH, the resin acid value was 70 mg · KOH / g. The weight average molecular weight Mw is 40000, and the number average molecular weight Mn is 1
0000, and the molecular weight distribution Mw / Mn was 4.

Examples 1 to 3 and Comparative Examples 1 and 2 The components were blended in the following proportions to obtain photosensitive liquid compositions. 1) 100 parts by weight of alkali-soluble resin (described in Table 1) 2) 100 parts by weight of dipentaerythritol hexaacrylate (DPHA) 3) 5 parts by weight of infrared absorbing dye (described in Table 1) 4) Polymerization initiator (described in Table 1) 5 parts by weight 5) Cyclohexanone 1500 parts by weight 6) FC-430 0.1 parts by weight (F-based surfactant manufactured by Sumitomo 3M)

1. Evaluation of Image Characteristics The above-mentioned photosensitive solution was applied to an aluminum substrate having a thickness of 0.2 mm and a size of 400 × 250 mm using a wire bar. It was dried in a convection oven at 70 ° C. for 2 minutes. The thickness of the photosensitive layer after drying was about 1 μm. A 10 wt% aqueous solution of polyvinyl alcohol was applied as a protective film to a thickness of 1 μm on the photosensitive layer film in the same manner. This substrate is 100 × 50m
m and cut to an aluminum roller having a diameter of 100 mm. Output 4 while rotating this aluminum roller at a speed of 100 rpm with a motor.
0mW, irradiation wavelength 830nm, laser spot diameter about 1
It was exposed with a semiconductor laser beam of 0 μm. The substrate is removed from the roller, subjected to dip development at 25 ° C. for 1 minute with an alkali developing solution containing 0.5% by weight of potassium hydroxide and 1% by weight of Emulgen A-60 (a surfactant manufactured by Kao Corporation), and then rinsed with pure water. And dried by pressure. This substrate was observed with a loupe having a magnification of 60 times. The image characteristics were determined based on whether clear images could be formed. The above operation was performed under yellow light. A sample on which a clear image was formed was evaluated as good.

2. Photosensitive solution stability Each photosensitive solution was stored at room temperature for 3 days, and the stability was evaluated by visually observing the presence or absence of a precipitate. Those in which no precipitation occurred were determined to be good.

[0085] 3. The cellophane tape was closely adhered to the pattern in which the adhesion was formed, and whether the pattern was peeled off from the substrate when the cellophane tape was peeled was judged whether or not the adhesion was good. Those which did not show any peeling from the substrate were judged as good, and those which showed even a little peeling were judged as bad.

Table 1 shows the results. In addition, the symbol of Table 1 shows the compound of the said structural formula, or the following compound, respectively.

[0087]

Embedded image

IRG-907; polymerization initiator manufactured by Ciba-Geigy (acetophenone type) IRG-369; same as above (acetophenone type)

[0089]

[Table 1]

[0090]

Since the photosensitive composition of the present invention has high sensitivity to infrared light, an image can be formed without using a mask by scanning exposure with a semiconductor laser or the like. In addition, since it has a photosensitive characteristic selectively in an infrared light region, there is an advantage that these operations can be performed in a bright environment such as a white light such as an ordinary fluorescent light, not in a dark room such as a red light.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) // C08F 8/00 C08F 8/00

Claims (7)

[Claims] 1. A photosensitive composition containing (a) an alkali-soluble resin, (b) an infrared absorbing dye, (c) a polymerization initiator, and (d) a compound containing an ethylenically unsaturated double bond. And (a) the photosensitive composition, wherein the alkali-soluble resin has a side chain double bond. 2. The photosensitive composition according to claim 1, wherein the alkali-soluble resin having a side chain double bond is obtained by adding an alicyclic epoxy unsaturated compound to a vinyl resin having a carboxyl group. . 3. The photosensitive composition according to claim 1, wherein (b) the infrared absorbing dye contains at least one selected from a phthalocyanine dye, a cyanine dye, and a polymethine dye. 4. The photosensitive composition according to claim 1, wherein (c) the polymerization initiator is an organic boron complex. 5. The photosensitive composition according to claim 4, wherein the organic boron complex has a basic skeleton represented by the following general formula (III). Embedded image [In the formula (III), R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group optionally having a substituent, an aryl group optionally having a substituent, Aralkyl group which may have a group, alkaryl group which may have a substituent, alkenyl group which may have a substituent, alkynyl group which may have a substituent, substituent An alicyclic group which may have, or a heterocyclic group which may have a substituent, which may be linked to each other to form a cyclic structure, and X ⁺ represents a counter cation. Show. ] 6. An image forming material having a photosensitive layer comprising the photosensitive composition according to claim 1 on a substrate. 7. An image forming method, comprising exposing a photosensitive layer of the image forming material according to claim 6 to an infrared laser having a wavelength in the range of 780 to 1200 nm, followed by developing with an alkali developing solution.