JP2007011046A - Photosensitive composition, image recording material and image recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition excellent in storage stability, work efficiency and economical efficiency, adaptable to a CTP system, usable as an image recording material of a lithographic printing plate for scanning exposure having high sensitivity to an oscillation wavelength of an inexpensive short-wavelength semiconductor laser, and using a new photopolymerization initiation system having high sensitivity to various wavelengths of 350-850 nm. <P>SOLUTION: The photosensitive composition contains (A) a biimidazole type compound of a specific structure, (B) a sensitizing dye having an absorption maximum λ<SB>max</SB>at 350-850 nm and (C) an addition polymerizable compound which reacts with at least one of a radical and an acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a photosensitive composition that can be used for image forming materials such as three-dimensional stereolithography, holography, planographic printing plates, color proofs, photoresists and color filters, and photocurable resin materials such as inks, paints, and adhesives. And an image recording material and an image recording method using the same. In particular, the present invention relates to a photosensitive composition that can be directly made from a digital signal of a computer or the like using various lasers, and is preferably used as a so-called lithographic printing plate material capable of direct plate making, and an image recording material and an image recording method using the same.

  Solid-state lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm are easily available as high-power and small-sized lasers. It is very useful as a recording light source when making a plate directly from data. Various researches have been made on recording materials that are sensitive to these various laser beams. As typical examples, as materials that can be recorded with an infrared laser having a photosensitive wavelength of 760 nm or more, a positive recording material described in Patent Document 1 is used. In addition, there are acid-catalyst-crosslinked negative recording materials described in Patent Document 2, and the recording materials for 300 nm to 700 nm ultraviolet light or visible light laser are described in Patent Document 3 and Patent Document 4. There are many known radical polymerization type negative recording materials.

  The problem common to all these image forming materials is how to enlarge the ON / OFF of the image in the above-mentioned various energy irradiated portions and unexposed portions, that is, the high sensitivity and storage stability of the image forming materials. It is compatible. Usually, the radical photopolymerization system is highly sensitive, but the sensitivity is greatly lowered due to polymerization inhibition by oxygen in the air. Therefore, means for providing an oxygen barrier layer on the image forming layer is taken. However, when an oxygen-blocking layer is provided, fogging due to dark polymerization or the like occurs, and storage stability deteriorates. Accordingly, it is difficult to achieve both high sensitivity and storage stability. The conventional technique has not obtained a satisfactory result, and a new technique that has not been conventionally required has been demanded.

On the other hand, high-sensitivity photoinitiators are described in Non-Patent Document 1 and Non-Patent Document 2, and are known.
U.S. Pat. No. 4,708,925 JP-A-8-276558 U.S. Pat. No. 2,850,445 Japanese Patent Publication No. 44-20189 Bruce M. By Monroe et al., Chemical Rev. , 93, 435 (1993) R. S. By Davidson et al., Journal of Photochemistry and biology, 73, 81 (1993).

Accordingly, an object of the present invention is to provide a photosensitive composition that is excellent in sensitivity, plate making property, storage stability, workability, and economy, and is used as an image recording material for scanning exposure that is compatible with a CTP system. Specifically, it can be used as an image recording material that is highly sensitive to the oscillation wavelength of an inexpensive short-wave semiconductor laser, and particularly by recording using solid-state laser and semiconductor laser light emitting ultraviolet light, visible light, and infrared light. Another object of the present invention is to provide a photosensitive composition suitable as a plate material for lithographic printing that can be directly made from digital data such as a computer. Another object of the present invention is to provide a photosensitive composition that uses a novel photopolymerization initiation system that is highly sensitive to a wide wavelength range from 350 nm to 850 nm and has high workability. Still another object of the present invention is to provide an image recording material and an image recording method using the photosensitive composition.

  As a result of intensive studies to achieve the above object, the present inventors have achieved extremely high sensitivity, plate making, storage stability, and workability when a sensitizing dye and a biimidazole compound having a specific structure are combined. It has been found that an excellent photopolymerization initiation system can be obtained, and a photopolymerization initiation system suitable for exposure at 350 nm to 850 nm, particularly 350 nm to 450 nm can be obtained. Furthermore, an image recording material using a photosensitive composition comprising this photopolymerization initiation system and an addition polymerizable compound that reacts with a radical or an acid, specifically, an addition polymerizable compound having an ethylenically unsaturated double bond. Thus, the inventors have found that a lithographic printing plate precursor having sufficient sensitivity to the oscillation wavelength of a short-wave semiconductor laser and that can be handled even under a bright safelight is obtained, and the present invention has been achieved.

That is, the present invention is as follows.
(1) (A) at least one of the compounds represented by the following general formulas (I), (II) and (III),
(B) a sensitizing dye having an absorption maximum λ _max at 350 nm to 850 nm, and (C) an addition polymerizable compound that reacts with at least one of a radical and an acid,
Containing the photosensitive composition.

(In the general formula (I), R _{1 to} R ₆ each independently represent a monovalent nonmetallic atomic group, and R ₇ and R ₈ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.
In general formula (II), one group in (R ₉ , R ₁₂ ) or (R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ ) is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a cyclo An alkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkyl ketone group is represented, and the other group represents a substituted or unsubstituted aryl group or heteroaryl group.
In the general formula (III), R _{16 to} R ₁₉ and R _{21 to} R ₂₄ are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkyl ketone group. R ₁₅ and R _{20 each} represents a substituted or unsubstituted aryl group or heteroaryl group. )

(2) An image recording material having a photosensitive layer containing the photosensitive composition according to (1) above on a support.
(3) An image recording method of performing scanning exposure on an image recording material having a photosensitive layer containing the photosensitive composition described in (1) above on a support using a laser light source having a wavelength of 450 nm or less.

The photosensitive composition of the present invention is a hexaarylbiimidazole compound (initiator) having a nonmetallic atomic group that is not a hydrogen atom as a substituent at the ortho position on all aromatic rings represented by the general formula (I). Or a biimidazole compound (initiator) having a specific structure selected from general formula (II) or (III), a sensitizing dye, and an addition polymerizable compound that reacts with at least one of a radical and an acid. Contained as.
The photosensitive composition of the present invention is characterized by having high film forming properties, high storage stability, and workability while having high sensitivity. Specific features of the present invention are shown below.

  As a general hexaarylimidazole compound currently on the market, there is LD-5 (the following compound abbreviated as o-Cl HABI)). This compound is a highly sensitive initiator that generates an active radical by acting as an electron acceptor from a sensitizing dye. However, because of insufficient thermal stability, a small amount of active radicals may be generated due to homogenous C—N bond cleavage in the drying process at the time of making the photosensitive layer, and development failure may occur gradually. In order to impart storage stability to the light-sensitive material, this improvement is required.

  In the photosensitive composition of the present invention, a hexaarylbiimidazole compound represented by the above general formula (I) having a nonmetallic atomic group that is not a hydrogen atom as a substituent at the ortho position on all aromatic rings, A biimidazole compound having a specific structure selected from general formula (II) or general formula (III) is used. Here, in the compound represented by the general formula (I), a steric twist occurs in the structure of the lophyl radical that can be generated by introducing a substituent into each ortho position of the aromatic ring, and the π-conjugated stabilization effect of the radical It is considered that the dimer is cleaved homolytically to generate radicals. In addition, the compounds represented by the general formulas (II) and (III) are also considered to suppress the thermal cleavage process because the π-conjugate stabilization effect of the lofil radicals that can be generated is small (there are few aromatic rings). It is done. For this reason, in the photosensitive composition of the present invention containing the biimidazole compound having the specific structure, it is considered that thermal CN bond cleavage is suppressed and development failure is suppressed in the plate-making heat-drying step. It is done. Further, even after the plate making, since generation of active radicals due to a small amount of bond cleavage is suppressed, it is considered to have high storage stability.

  The photosensitive composition of the present invention has sufficient sensitivity suitable for scanning exposure with a short-wavelength semiconductor laser such as InGaN, and is excellent in plate making, storage stability, workability, and economy. When used as a printing plate material, a lithographic printing plate satisfying these characteristics can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
First, the photosensitive composition of this invention is demonstrated.
The photosensitive composition of the present invention contains a photopolymerization initiating system having a specific hexaarylbiimidazole compound or a specific biimidazole compound and a sensitizing dye having an absorption maximum λ _{max in} a specific range and an addition polymerizable compound.

[Photopolymerization initiation system]
The photopolymerization initiation system used in the photosensitive composition of the present invention includes a sensitizing dye having an absorption maximum λ _max at 350 to 850 nm or less, and a hexaarylbiimidazole type compound represented by the general formula (I) described later. (Initiator) or a biimidazole type compound (initiator) having a specific structure selected from general formula (II) or (III).

<(A) Imidazole compound (initiator)>
The biimidazole compound constituting the photopolymerization initiation system used in the photosensitive composition of the present invention contains a nonmetallic atomic group that is not a hydrogen atom at the ortho position on all aromatic rings represented by the general formula (I). Hexaarylbiimidazole compound (initiator) having a substituent, biimidazole type compound (initiator) having a specific structure represented by general formula (II), biimidazole type having a specific structure represented by general formula (III) It is at least one of the compounds (initiators).

(In the general formula (I), R _{1 to} R ₆ each independently represent a monovalent nonmetallic atomic group, and R ₇ and R ₈ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.
In general formula (II), one group in (R ₉ , R ₁₂ ) or (R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ ) is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a cyclo An alkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkyl ketone group is represented, and the other group represents a substituted or unsubstituted aryl group or heteroaryl group.
In the general formula (III), R _{16 to} R ₁₉ and R _{21 to} R ₂₄ are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkyl ketone group. R ₁₅ and R _{20 each} represents a substituted or unsubstituted aryl group or heteroaryl group. )
The “non-metallic atomic group” here does not include a hydrogen atom.

Next, the hexaarylbiimidazole type compound represented by the general formula (I) will be described in detail.
R _{1 to} R ₆ are preferably halogen atoms, cyano groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkoxycarbonyl groups, substituted Or it is an unsubstituted alkyl ketone group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group.

Next, preferred examples of R _{1 to} R ₆ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, 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.

  Specific examples of preferred cycloalkyl groups include those in which 3 to 8 carbon atoms form a ring structure, and more preferred are cyclopentane and cyclohexane structures having 5 or 6 carbon atoms.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino 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-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id 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-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), di Rukiruhosuhono group _{(-PO 3 (alkyl) 2)} , 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 referred to as arylphosphonato group) ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO _3). (aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups, which may further have a substituent.

  Preferred examples of the alkoxy group include a methoxy group and an ethoxy group, and the halogen is preferably a fluoro group, a chloro group or a bromo group. More preferred is a chloro group. The alkoxycarbonyl group is preferably methoxycarbonyl or ethoxycarbonyl, more preferably methoxycarbonyl.

Specific examples of preferred aryl groups as R _{1 to} R ₆ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Examples of the alkyl part of the preferred alkyl ketone group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group and an ethyl group. Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s Examples include -butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group. Of these, 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.

Specific examples of preferred substituted aryl groups as R _{1 to} R ₆ include those having a monovalent non-metallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. Used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphoro Phenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl Group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom is used, and a heteroaryl ring in a particularly preferred heteroaryl group is used. Examples of thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoir , Indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cynoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalzazine, pheno Spoon, furazan, phenoxazine and the like, and these are further may be benzo-fused or may have a substituent.

R ₁ and R ₄ in the general formula (I) are preferably an alkyl group and a halogen atom, and more preferably a chloro group and a bromo group. R ₂ , R ₃ , R ₅ and R ₆ are preferably an alkoxy group, an alkyl group and a halogen atom, more preferably a methoxy group and an ethoxy group.

In the general formula (II), one of the groups in (R ₉ , R ₁₂ ) or (R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ ) is preferably an alkyl group, a cycloalkyl group, or a cyano group. More preferred is a substituted alkyl group, and specific examples include a trifluoromethyl group and a trichloromethyl group. The remaining group is preferably an aryl group having a substituent, and more preferably an aryl group having an alkoxy group, a halogen atom or a cyano group as a substituent at the ortho position. Among them, as shown below, when the aryl group is at the 2-position of the imidazole structure, an aryl group having a chloro group or a bromo group at the ortho-position is preferable, and the aryl group is at the 4- or 5-position of the imidazole structure. In some cases, an aryl group having a methoxy group or an ethoxy group in the ortho position is preferred.

R _{16 to} R ₁₉ and R _{21 to} R ₂₄ in the general formula (III) are preferably an alkyl group, a cycloalkyl group, and a cyano group, more preferably a substituted alkyl group, specifically a trifluoromethyl group. And a trichloromethyl group.
R ₁₅ and R ₂₀ are preferably an aryl group having a substituent, and more preferably an aryl group having an alkoxy group, a halogen atom or a cyano group as a substituent at the ortho position. Among them, an aryl group having a chloro group or a bromo group at the ortho position is particularly preferable.

The monovalent nonmetallic atomic group in R ₇ and R ₈ in the general formula (I) is the same as R _{1 to} R _6, and the substitution for R _{9 to} R ₂₄ in the general formula (II) or (III) The group is the same as described above.
The following exemplary compounds (T-1) to (T-42) are shown as biimidazole type compounds having a preferred structure, but the present invention is not limited to these. T-1 to T-12 are examples of the compound represented by the general formula (I), T-13 to T-30 are examples of the compound represented by the general formula (II), and T- 31-T-42 is an example of a compound represented by general formula (III).

  Here, the typical synthesis example of the biimidazole type compound mentioned above is shown.

Synthesis of [Exemplary Compound (T-7)] <Working Step>
(The following compound is designated as T′-7)

After mixing 4.0 g of potassium ferricyanide, 3.3 g of potassium hydroxide, 70 ml of water and 40 ml of toluene, the mixture was stirred at room temperature until there was no solid. Thereafter, 2.0 g of T′-7 was added, and the oil bath was heated to 80 ° C. and stirred for 4 hours under reflux.
The reaction solution stirred for 4 hours under reflux was allowed to cool, 100 ml of water was added, and the mixture was extracted with toluene. The organic tank made of toluene was washed with an aqueous sodium chloride solution and then with water. After washing, the organic phase was concentrated to give a red light oil. The obtained viscous liquid was recrystallized with 2-propanol to obtain 1.6 g of the intended T-7.

Synthesis of [Exemplary Compound (T-31)] <Working Step>
(The following compound is T'-31)

0.1 mol of hydrazine and 0.22 mol of T′-31 were dissolved in 300 ml of tetrahydrofuran, and the mixture was stirred at 0 ° C. for 1 hour. Thereafter, the reaction solution was extracted with ethyl acetate and washed with an aqueous sodium chloride solution and then with water. After washing, the organic phase was concentrated to give a pale yellow oil. The obtained viscous liquid was subjected to column chromatography to obtain 0.08 mol of the intended T-31.
Other biimidazole type compounds can be synthesized in the same manner by appropriately selecting starting materials, compounds to be added, and the like.

  In the photosensitive composition of the present invention, at least one of the biimidazole type compounds represented by the above general formulas (I) to (III) is added in an amount of 0.5 to 20 in the total solid content constituting the composition. It is preferable to contain by mass. More preferably, it is 1-10 mass%.

In the present invention, in addition to the specific biimidazole type compound, other known photopolymerization initiators, thermal polymerization initiators and the like can be selected and used in combination as long as the effects of the present invention are not impaired. Examples of these polymerization initiators that can be used in combination include known onium salts having no carboxylic acid structure in the counter cation moiety, triazine compounds having a trihalomethyl group, peroxides, azo polymerization initiators, azide compounds, and quinonediazides. Etc.

  Specific examples of the onium salt that can be suitably used as a radical generator that can be used in combination include those described in paragraphs [0030] to [0033] of JP-A No. 2001-133969.

When other polymerization initiators are used in combination, these contents are preferably 50 parts by mass or less when the content of the biimidazole compound as the specific radical generator is 100 parts by mass.
The radical generator (the biimidazole compound and other polymerization initiator) used in the present invention preferably has a maximum absorption wavelength of 500 nm or less, and more preferably 400 nm or less.

<(B) Sensitizing dye>
The sensitizing dye used in the photosensitive composition of the present invention is a sensitizing dye having an absorption peak (absorption maximum) at 350 to 850 nm. When the absorption peak is less than 350 nm, a sufficient sensitizing effect cannot be obtained because it is a short wave in view of the wavelength of a laser currently used for plate making. The same applies to the wavelength region exceeding 850 nm, and a sensitizing dye having a wavelength of 350 nm or more and 850 nm or less is selected from the viewpoint of practicality.
Examples of such sensitizing dyes include spectral sensitizing dyes and the following dyes or pigments that absorb light from a light source and interact with a photopolymerization initiator.
Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thianes). Carbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines ( For example, phthalocyanine, metal phthalocyanine), porphyrins (for example, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (for example, chlorophyll, chlorophyllin, central gold) Substituted chlorophyll), metal complexes, anthraquinones, such as (anthraquinone), squaryliums, include, for example, (squarylium), and the like.

  More preferred examples of spectral sensitizing dyes or dyes include styryl dyes described in JP-B-37-13034, cationic dyes described in JP-A-62-143044, and quinoxalinium salts described in JP-B-59-24147. New methylene blue compounds described in JP-A No. 64-33104, anthraquinones described in JP-A No. 64-56767, benzoxanthene dyes described in JP-A No. 2-1714, JP-A No. 2-226148 and JP-A No. Hei. Acridines described in JP-A-2-226149, pyrylium salts described in JP-B-40-28499, cyanines described in JP-B-46-42363, benzofuran dyes described in JP-A-2-63053, and JP-A-2 Conjugated ketone dyes described in JP-A-85858 and JP-A-2-216154 7-10605 described in JP-dye. Azocinnamylidene derivatives described in JP-B-2-30321, cyanine dyes described in JP-A-1-287105, JP-A-62-31844, JP-A-62-31848, JP-A-62-143043 Xanthene dyes described in Japanese Patent Publication No. JP-A-59-28325, aminostyryl ketones described in JP-B-59-28325, merocyanine dyes described in JP-B-61-9621, and dyes described in JP-A-2-17943. A merocyanine dye described in JP-A-2-244050, a merocyanine dye described in JP-B-59-28326, a merocyanine dye described in JP-A-59-89303, a merocyanine dye described in JP-A-8-129257, and Examples thereof include benzopyran dyes described in JP-A-8-334897.

In addition, the following infrared absorbers (dyes or pigments) are also preferably used as sensitizing dyes.
Preferred examples of the dye include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. And cyanine dyes described in British Patent 434,875.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and further substituted aryl benzoates described in US Pat. No. 3,881,924 are also used. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, JP-A-58-220143, 59-41363, 59-84248, 59-84249, 59-146063, 59-146061, pyrylium compounds described in JP-A-59-216146, and cyanine described in JP-A-59-216146 Dyes, pentamethine thiopyrylium salts described in US Pat. No. 4,283,475, etc., and Japanese Patent Publication Nos. 5-13514 and 5-19702. Pyrylium compounds as mounting is also preferably used.

  Also preferred are near-infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513 A2. It can be mentioned as a dye.

Furthermore, an anionic infrared absorber can also be used suitably.
Here, the anionic infrared absorbing agent refers to those having an anionic structure without a cation structure in the mother nucleus of a dye that substantially absorbs infrared rays. For example, (b1) an anionic metal complex, (b2) anionic carbon black, (b3) anionic phthalocyanine, and (b4) a compound represented by the following general formula A can be used. The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

Formula ^{_{A [G a - -M-G}} b] m X m +

  Here, the (b1) anionic metal complex refers to a substance that becomes an anion in the central metal and the entire ligand of the complex part that substantially absorbs light.

  Examples of (b2) anionic carbon black include carbon black to which anionic groups such as sulfonic acid, carboxylic acid, and phosphonic acid groups are bonded as a substituent. In order to introduce these groups into carbon black, as described in Carbon Black Handbook 3rd Edition (Edited by Carbon Black Association, April 5, 1995, published by Carbon Black Association), page 12, What is necessary is just to take means, such as oxidizing carbon black.

  (B3) Anionic phthalocyanine refers to a phthalocyanine skeleton bonded with the anionic group previously mentioned in the description of (b2) as a substituent to form an anion as a whole.

Next, the compound (b4) represented by formula A will be described in detail. In Formula _A, G _a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a 1 to m-valent cation containing a proton, and m represents an integer of 1 to 6. M represents a conjugated chain, and this conjugated chain M may have a substituent or a ring structure.
The conjugated chain M can be represented by the following formula.
-(C (-R < ¹ >) = C (-R _< ² _> )) _n- C (-R _< ³ >) =

In the above formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, It represents an oxy group or an amino group, and these may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

  Cationic infrared absorbers and nonionic infrared absorbers can also be preferably used.

  As other dyes, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, diimmonium dyes, aminium dyes, squarylium dyes, metal thiolate complexes, etc. Is mentioned.

  Examples of pigments that can be used as sensitizing dyes include commercially available pigments and the Color Index (CI) manual, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology”. (CMC Publishing, published in 1986) and “Printing Ink Technology” published by CMC Publishing, published in 1984) can be used. For example, types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

These pigments may be used without surface treatment, or may be used after surface treatment.
The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Sachibo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 1 μm, and particularly preferably 0.1 μm to 1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

Still more preferred examples of the sensitizing dye in the present invention include the merocyanine dye described in JP-B-61-9621, the merocyanine dye described in JP-A-2-17943, and the merocyanine described in JP-A-2-244050. Dye, merocyanine dye described in JP-B-59-28326, merocyanine dye described in JP-A-59-89303, merocyanine dye described in JP-A-6-269047, and benzopyran described in JP-A-8-334897 System dyes. And infrared absorbers described in JP-A No. 11-209001 described above.
The sensitizing dye in the present invention is also preferably used alone or in combination of two or more. Furthermore, the photopolymerizable composition of the present invention may contain a known compound having a function of further improving sensitivity or suppressing inhibition of polymerization by oxygen as a co-sensitizer.

Details of the method of use, such as which structure of these sensitizing dyes are used, whether they are used alone or in combination of two or more, and how much is added, can be appropriately set according to the performance design of the final photosensitive material .
For example, the compatibility with the photosensitive composition layer can be enhanced by using two or more sensitizing dyes in combination. In selecting the sensitizing dye, in addition to the photosensitivity, the molar extinction coefficient at the emission wavelength of the light source used is an important factor. By using a dye having a large molar extinction coefficient, the amount of the dye added can be made relatively small, which is economical and advantageous from the viewpoint of film properties of the photosensitive layer when used in a lithographic printing plate precursor. is there. Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposure film are greatly affected by the absorbance at the light source wavelength, the addition amount of the sensitizing dye is appropriately set in consideration of these factors.
However, for example, for the purpose of curing a thick film having a thickness of 5 μm or more, the degree of curing may be increased by lower absorbance.
When the photosensitive composition is used as a lithographic printing plate having a relatively thin film thickness, the absorbance of the photosensitive layer is preferably in the range of 0.1 to 1.5, more preferably 0. It is preferably set to be in the range of 25 to 1. Specifically, usually in the range of 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of all components of the photosensitive composition. It is.

  Regarding the sensitizing dye in the present invention, when a lithographic printing plate precursor is used, various chemical modifications for improving the characteristics of the photosensitive layer can be performed. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, the exposure film can be increased in strength or exposed. Unnecessary precipitation suppression of the dye from the subsequent film can be performed.

  Furthermore, when a lithographic printing plate precursor is prepared using the photosensitive composition of the present invention, it is hydrophilic for the purpose of increasing the suitability for processing to an (alkali) aqueous developer, which is a preferred mode of use of the photosensitive layer. Introduction of a site (carboxyl group and its ester, sulfonic acid group and its ester, ethylene oxide group or other acid group or polar group) is effective. In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer, so that they have excellent compatibility, and in the developer, acid groups are generated by hydrolysis to increase hydrophilicity. Have In addition, for example, a substituent can be appropriately introduced in order to improve the compatibility in the photosensitive layer and to suppress crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be remarkably suppressed. In addition, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, adhesion to an inorganic substance such as a metal or a metal oxide can be improved. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

<(C) Addition polymerizable compound that reacts with at least one of radical and acid>
The photosensitive composition of the present invention contains, in addition to the above-described photopolymerization initiation system, a compound that reacts with at least one of a radical and an acid to change and maintain its physical or chemical properties. Such a compound is specifically an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and more specifically, at least one, preferably two, terminal ethylenically unsaturated bonds. It is selected from the compounds having the above. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention.
These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.

In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, amide and monofunctional or polyfunctional isocyanate, addition reaction product of epoxy, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
In addition, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanato group or an epoxy group, an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine or a thiol, a halogen atom, Also suitable are substitution reaction products of unsaturated carboxylic acid esters and amides with monofunctional or polyfunctional alcohols, amines and thiols having a leaving substituent such as a tosyloxy group.
As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.
Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (IV) to a polyisocyanate compound having two or more isocyanate groups. Etc.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (IV)
(However, R and R ′ each independently represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable.

  Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are listed. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  For these addition-polymerizable compounds, details on how to use them, such as what type of structure is used, whether they are used alone or in combination, and how much is added, according to the performance design of the final photosensitive material, Can be set arbitrarily. For example, it is selected from the following viewpoints. From the viewpoint of the speed of photosensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, when used in a photosensitive layer for a lithographic printing plate, in order to increase the strength of the image area, that is, the cured film, those having three or more functional groups are preferable. A method of adjusting both photosensitivity and strength is also effective by using a combination of an ester, a methacrylic ester, a styrene compound, or a vinyl ether compound. A compound having a large molecular weight or a compound having a high hydrophobicity is not preferable in terms of development speed and precipitation in a developing solution, although it is excellent in photosensitive speed and film strength. In addition, the selection of the addition polymerization compound is also required for compatibility and dispersibility with other components in the photosensitive layer (for example, the binder polymer described later, the photopolymerization initiator (system) described above, the colorant described later, etc.). -The usage method is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, overcoat layer and the like.

The addition amount of the addition polymerizable compound in the photosensitive composition is more advantageous in terms of sensitivity, but if it is too much, undesirable phase separation occurs or the production process due to the adhesiveness of the photosensitive layer occurs. (For example, defective transfer due to transfer of photosensitive material components and adhesion) and precipitation from the developer may occur. From these viewpoints, the preferred blending amount is often 5 to 80% by mass, preferably 25 to 75% by mass, based on the total components of the composition. These may be used alone or in combination of two or more.
In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

<(D) Binder polymer>
When the photosensitive composition of the present invention is applied to the photosensitive layer of a lithographic printing plate precursor as a preferred embodiment thereof, a binder polymer may be used in addition to the above-mentioned photopolymerization initiation system and addition polymerizable compound. preferable. The binder preferably contains a linear organic high molecular polymer. Any such “linear organic polymer” may be used. Preferably, a linear organic high molecular weight polymer that is soluble in water or weakly alkaline water or swellable that enables water development or weak alkaline water development is selected.
The linear organic high molecular polymer is selected and used not only as a film-forming agent for the composition but also according to its use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12777, and JP-B. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer , Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer and [allyl (meth) acrylate /
(Meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer is preferable because of its excellent balance of film strength, sensitivity and developability.

  In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. The urethane-based binder polymer containing an acid group described in each publication of JP 271741 and JP-A No. 13-312062 is very excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure. is there. A binder having an amide group described in JP-A No. 11-171907 is suitable because it has both excellent developability and film strength.

In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
These binder polymers can be mixed in an arbitrary amount in the entire composition. However, when it exceeds 90% by mass, a preferable result is not given in terms of the strength of the formed image. Preferably it is 30-85 mass%. The photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic polymer are preferably in the range of 1/9 to 7/3 by mass ratio. In a preferred embodiment, a binder polymer that does not require water and is soluble in alkali is used. By doing so, an organic solvent that is not environmentally preferable is not used as the developer, or the amount can be limited to a very small amount. In such a method of use, the acid value of the binder polymer (the acid content per gram of the polymer expressed as a chemical equivalent number) and the molecular weight are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 0.4 to 3.0 meq / g, the preferred molecular weight is in the range of 3000 to 500,000, more preferably the acid value is 0.6 to 2.0 and the molecular weight is in the range of 10,000 to 300,000. It is.

<(E) Other ingredients>
In order to use the photosensitive composition of the present invention as a photosensitive layer of an image recording material such as a lithographic printing plate precursor, other components suitable for its application and production method can be added as appropriate.
Hereinafter, preferred additives will be exemplified.

(E1) Co-sensitizer The sensitivity of the photosensitive layer can be further improved by using a certain additive (hereinafter referred to as a co-sensitizer). These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, a photoreaction initiated by light absorption of the above-described photopolymerization initiation system, and various intermediate active species (radicals, peroxides, oxidizing agents, reducing agents, etc.) generated in the course of the subsequent addition polymerization reaction, It is presumed that the co-sensitizer reacts to generate a new active radical. These can be broadly divided into (a) those that can be reduced to generate active radicals, (b) those that can be oxidized to generate active radicals, and (c) radicals that are more active by reacting with less active radicals. Can be classified into those that act as chain transfer agents, but there is often no generality as to which of these individual compounds belong.

(A) Compound that is reduced to produce an active radical Compound having a carbon-halogen bond: It is considered that the carbon-halogen bond is reductively cleaved to generate an active radical. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be preferably used.
Compound having nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used.
Compound having oxygen-oxygen bond: It is considered that the oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides are preferably used.
Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active radicals. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used.
Ferrocene and iron arene complexes: An active radical can be reductively generated.

(B) Compound which is oxidized to generate an active radical Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, for example, triarylalkyl borates are preferably used.
Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.
Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.
α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and these and a hydroxylamine were reacted, and then N—OH was etherified. Oxime ethers can be listed.
Sulfinic acid salts: An active radical can be reductively generated. Specific examples include sodium arylsulfinate.

(C) Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents include, for example, SH, PH in the molecule , SiH, and GeH are used. These can generate hydrogen by donating hydrogen to a low-activity radical species to generate radicals, or after being oxidized and deprotonated. Specifically, 2-mercaptobenzimidazoles etc. are mentioned, for example.

  Many more specific examples of these co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity. Some examples are shown below, but the present invention is not limited thereto.

  These co-sensitizers can also be subjected to various chemical modifications for improving the characteristics of the photosensitive layer of the lithographic printing plate precursor as in the case of the sensitizing dye. For example, bonds with sensitizing dyes, titanocene, addition polymerizable unsaturated compounds and other radical generating parts, introduction of hydrophilic sites, improved compatibility, introduction of substituents for suppressing crystal precipitation, substituents for improving adhesion Methods such as introduction and polymerization can be used. These co-sensitizers can be used alone or in combination of two or more. The amount used is preferably 0.05 to 100 parts by weight, more preferably 1 to 80 parts by weight, and still more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the addition polymerizable compound.

(E2) Thermal polymerization inhibitor In addition to the above basic components, the photosensitive composition of the present invention does not require a compound having an ethylenically unsaturated double bond that can be polymerized during its production or storage. In order to prevent thermal polymerization, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01 parts by mass to about 5 parts by mass with respect to 100 parts by mass of the total composition. In addition, when applied as a photosensitive layer such as a lithographic printing plate precursor, a higher fatty acid derivative such as behenic acid or behenic acid amide is added as necessary to prevent polymerization inhibition by oxygen, and drying after coating is performed. In this process, it may be unevenly distributed on the surface of the photosensitive layer. The amount of the higher fatty acid derivative added is preferably about 0.5 parts by mass to about 10 parts by mass with respect to 100 parts by mass of the total composition.

(E3) Colorant When the photosensitive composition of the present invention is used as a photosensitive layer of an image recording material such as a lithographic printing plate precursor,
Further, a dye or pigment colorant may be added for the purpose of coloring the photosensitive layer. As a result, it is possible to improve so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a lithographic printing plate precursor.
As a colorant, since many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer, it is particularly preferable to use a pigment. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5 parts by mass to about 5 parts by mass with respect to 100 parts by mass of the total composition.

(E4) Other additives When the photosensitive composition of the present invention is used in a photosensitive layer such as a lithographic printing plate precursor, an inorganic filler, other plasticizer, and the photosensitive agent are used to further improve the physical properties of the cured film. You may add well-known additives, such as a fat-sensitizing agent which can improve the ink inking property of a layer surface.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder polymer.

Addition of UV initiators, thermal cross-linking agents, etc. to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) of the photosensitive layer of the lithographic printing plate precursor described later You can also.
In addition, it is possible to provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support and for improving the development removability of the unexposed photosensitive layer. For example, by adding or undercoating a compound having a relatively strong interaction with a substrate described later, such as a compound having a diazonium structure or a phosphone compound, adhesion can be improved and printing durability can be increased. By adding or undercoating with a hydrophilic polymer such as acrylic acid or polysulfonic acid, the developability of the non-image area is improved, and the stain resistance can be improved.

  When the photosensitive composition of the present invention is applied on a support as a photosensitive layer of an image recording material such as a lithographic printing plate precursor, it is used after being dissolved in various organic solvents. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

Next, the image recording material of the present invention will be described.
The image recording material of the present invention has a photosensitive layer containing the above-described photosensitive composition of the present invention on a support.
The support coating amount of the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, the strength and printing durability of the exposed film, and is preferably selected as appropriate according to the application. When the coating amount is too small, the printing durability is not sufficient. On the other hand, if the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. For the lithographic printing plate for scanning exposure which is the main purpose of use of the photosensitive composition of the present invention, the coating amount is suitably in the range of about 0.1 g / m ² to about 10 g / m ² in terms of the mass after drying. is there. More preferably from 0.5 to 5 g / m ^2.
The thickness of the photosensitive layer is not particularly limited, but is usually about 0.1 to 3.0 μm.

<(F) Support>
In order to obtain a lithographic printing plate precursor, which is one of the main purposes of use of the photosensitive composition of the present invention, it is desirable to provide a photosensitive layer comprising the photosensitive composition on a support having a hydrophilic surface. . As the hydrophilic support, any conventionally known hydrophilic support used in a lithographic printing plate precursor can be used without limitation.
The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.) Paper or plastic film, etc., laminated or vapor-deposited with such metals is included, and appropriate physical and chemical treatments are applied to these surfaces for the purpose of imparting hydrophilicity and improving strength as necessary. You may give it.

  In particular, preferred supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface with excellent hydrophilicity and strength is provided by surface treatment as required. An aluminum plate which can be used is particularly preferred. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

  A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is usually about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

In the case of a support having a surface of metal, particularly aluminum, roughening (graining) treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate, etc., or anodic oxidation treatment, etc. It is preferable that surface treatment is performed.
The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. Further, prior to roughening the aluminum plate, for example, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed in order to remove the rolling oil on the surface, if desired.

Furthermore, an aluminum plate that has been roughened and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Patent Publication No. 47-5125, an aluminum plate is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is carried out in an electrolytic solution in which an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt solution thereof, or a combination of two or more thereof, is used. This is carried out by passing an electric current using the aluminum plate as an anode.
Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

Further, a support body provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, JP-A-52-30503, and the above-described anodizing treatment and sodium silicate treatment. A surface treatment in combination with is also useful.
Further, those obtained by performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment in this order as disclosed in JP-A-56-28893 are also suitable.

Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Those having a primer such as a yellow dye or an amine salt are also suitable.
Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-7-159983 is covalently used.

Other preferred examples include those in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. Examples of such a surface layer include a layer composed of an inorganic pigment and a binder described in US Pat. No. 3,055,295 and JP-A-56-13168, and a hydrophilic swelling described in JP-A-9-80744. A layer, a sol-gel film made of titanium oxide, polyvinyl alcohol, silicic acid or the like described in JP-A-8-507727 can be raised.
These hydrophilic treatments are performed to make the surface of the support hydrophilic, in order to prevent harmful reactions of the photosensitive composition provided thereon, and to improve the adhesion of the photosensitive layer, etc. It is given for.

<(G) Protective layer>
In the lithographic printing plate for scanning exposure, which is a desirable use mode of the photosensitive composition of the present invention, since exposure is usually performed in the air, a protective layer is further formed on the layer made of the photosensitive composition. It is preferable to provide it.
The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer, and enables exposure in the atmosphere. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure. Such a device relating to the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729.

As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, the use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400.

  Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

  Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic polymer layer, film peeling due to insufficient adhesion tends to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization.

  On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, sufficient adhesiveness can be obtained by mixing 20 to 60% by mass of an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer in a hydrophilic polymer composed of polyvinyl alcohol and laminating the polymer layer. can get. Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method for the protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that is excellent in the transmission of light from 350 nm to 450 nm and that can absorb light of 500 nm or more, which is used for exposure, it does not cause a decrease in sensitivity and is suitable for safelight. Can be further enhanced.

Next, the image recording method of the present invention will be described.
The image recording method of the present invention is an image recording method in which scanning exposure is performed using a laser light source having a wavelength of 450 nm or less on the image recording material of the present invention having the photosensitive layer containing the photosensitive composition of the present invention. is there.
In the image recording method of the present invention, similarly to the normal image recording method, after image exposure, an unexposed portion of the photosensitive layer is removed with a developer to obtain an image.

  When the photosensitive material using the photosensitive composition of the present invention is used as an image recording material such as a lithographic printing plate precursor, usually, after image exposure, the unexposed portion of the photosensitive layer is removed with a developer, Get. When these photosensitive compositions are used for lithographic printing plate precursors, preferred developers include those described in JP-B-57-7427, such as sodium silicate and potassium silicate. , Sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. A suitable inorganic alkaline agent or an aqueous solution of an organic alkaline agent such as monoethanolamine or diethanolamine is suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.

  Such an alkaline aqueous solution may contain a small amount of a surfactant, an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480. Further, the developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, and 56-42860 are also excellent.

As a particularly preferred developer, a nonionic compound represented by the following formula described in JP-A No. 2002-202616 is contained, the pH is 11.5 to 12.8, and 3 to 30 mS / cm. And a developer having the following conductivity.
A-W
(In the formula, A represents a hydrophobic organic group having LogP of AH of 1.5 or more, and W represents a nonionic hydrophilic organic group having LogP of less than 1.0.)

  In the present invention, the log P value is C.I. Hansch, A.M. Leo, “Substituent Constants for Correlation Analysis in Chemistry and Biology”, J. Am. It is generally used as the hydrophobicity parameter described in Wille & Sons, 1979. Specifically, for each compound, A. K. Gose et. al. , "J. Comput. Chem." 9, 80 (1988).

  In addition, as a plate-making process of a lithographic printing plate from a lithographic printing plate precursor using the photosensitive composition of the present invention for a photosensitive layer, the entire surface is exposed before exposure, during exposure, and from exposure to development as necessary. You may heat. By such heating, the image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to subject the developed image to full post heating or full exposure. Usually, the heating before development is preferably performed under a mild condition of 150 ° C. or less. If the temperature is too high, problems such as covering up to the non-image area occur. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC. If the temperature is low, sufficient image strengthening action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

  As a method for exposing a lithographic printing plate precursor using the photosensitive composition of the present invention for a photosensitive layer, a known method can be used without limitation. Desirably, the wavelength of the light source is 350 nm to 450 nm, and specifically, an InGaN-based semiconductor laser is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. In addition, the photosensitive layer component can be made soluble in neutral water or weak alkaline water by using a highly water-soluble component, but the lithographic printing plate precursor having such a constitution is used on a printing press. After loading, the method of exposure-development can be performed on the machine.

Further, as other exposure light rays for the photopolymerizable composition according to the present invention, ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet lasers. A lamp, a fluorescent lamp, a tungsten lamp, sunlight, etc. can also be used.
As available laser light sources of 350 nm to 450 nm, the following can be used.
As a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW), and solid laser as Nd: YAG (YVO ₄ ) and SHG crystals × 2 combinations (355 nm, 5 mW to 1 W), Cr: LiSAF and SHG crystals (430 nm, 10 mW),

As a semiconductor laser system, a KNbO ₃ ring resonator (430 nm, 30 mW), a combination of a waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a waveguide type wavelength conversion element, AlGaInP, and an AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 450 nm, 5 mW to 30 mW), etc., N ₂ laser (337 nm, pulse 0.1 to 10 mJ) as pulse laser, XeF (351 nm, pulse 10 to 250 mJ) . Among these, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

Further, as the lithographic printing plate exposure apparatus of the scanning exposure method, there are an inner drum method, an outer drum method, and a flat bed method as an exposure mechanism, and a light source that can continuously oscillate among the light sources can be preferably used. . Practically, the following exposure apparatus is particularly preferable in terms of the relationship between the photosensitive material sensitivity and the plate making time.
・ Single-beam to triple-beam exposure equipment that uses one or more gas lasers or solid-state laser light sources so that it becomes a semiconductor laser with a total output of 20 mW or more with an internal drum system. ・ A total output of 20 mW or more with a flatbed system. Multi-beam (1 to 10) exposure equipment that uses one or more semiconductor lasers, gas lasers, or solid-state lasers ・ Use one or more semiconductor lasers, gas lasers, or solid-state lasers to achieve a total output of 20 mW or more with the external drum system Multi-beam (1 to 9) exposure devices ・ More than multi-beam (10 or more) exposure devices that use one or more semiconductor lasers or solid-state lasers so that the total output is 20 mW or more in the external drum system in the lithographic printing plate of such a laser direct drawing type, generally the photosensitive material sensitivity X (J / cm ^2), the exposure of the photosensitive material Product S (cm ^2), the laser light source 1 power q (W), Formula (eq1) is established between the laser number n, the total exposure time t (s).

  X · S = n · q · t (eq 1)

i) In the case of the internal drum (single beam) system, the laser rotation speed f (radians / s), the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dots / cm), and the total exposure time t (s) In general, equation (eq 2) holds.

f · Z · t = Lx (eq 2)

ii) External drum (multi-beam) system Drum rotation speed F (radians / s), photosensitive material sub-scanning length Lx (cm), resolution Z (dots / cm), total exposure time t (s), number of beams In general, formula (eq 3) is established during (n).

  F.Z.n.t = Lx (eq 3)

iii) Flat head (multi-beam) system Polygon mirror rotation speed H (radians / s), photosensitive material sub-scanning length Lx (cm), resolution Z (dots / cm), total exposure time t (s), Equation (eq 4) is generally established between the number of beams (n).

  F.Z.n.t = Lx (eq 4)

Resolution (2560 dpi) required for an actual printing plate, plate size (A1 / B1, sub-scanning length 42 inch), exposure conditions of about 20 sheets / hour and photosensitive characteristics of the photosensitive composition of the present invention (photosensitive wavelength, By substituting (sensitivity: about 0.1 mJ / cm ² ) into the above formula, the photosensitive material using the photosensitive composition of the present invention can be combined with a multi-beam exposure method using a laser having a total output of 20 mW or more. It can be seen that it is particularly preferable. Further, by combining operability, cost, etc., a combination with an external drum type semiconductor laser multi-beam (10 or more) exposure apparatus is most preferable.

As mentioned above, although this invention was demonstrated in detail, this invention is not restrict | limited to the above-mentioned description, A various change is possible in the range which does not deviate from the meaning of this invention.
For example, the application of the photosensitive composition according to the present invention can be applied without limitation to what is widely known as an application of a photo-curing resin in addition to a lithographic printing plate for scanning exposure. For example, a highly sensitive optical modeling material can be obtained by applying to a liquid photopolymerizable composition used in combination with a cationic polymerizable compound as necessary. Further, a hologram material can be obtained by utilizing a change in refractive index accompanying photopolymerization. It can be applied to various transfer materials (peeling sensitive material, toner developing sensitive material, etc.) by utilizing the change in surface adhesiveness accompanying photopolymerization. It can also be applied to photocuring of microcapsules. It can also be applied to the production of electronic materials such as photoresists, and photocurable resin materials such as inks, paints, and adhesives.

  Furthermore, the photopolymerization initiation system comprising the compound represented by the general formula (I) or (II) and the sensitizing dye contained in the photosensitive composition of the present invention has excellent photosensitivity and excellent stability. In addition to the photosensitive composition described in detail above, various utilization methods can be used. For example, radical generation with high efficiency by light can cause, for example, oxidative color development of a triphenylmethane leuco dye with high sensitivity. In addition, a decoloring reaction due to radical addition can be caused for certain polymethine dyes. In addition, since the photopolymerization initiation system generates an acid component simultaneously with radicals by light, it can be decomposed by an acid, a compound that changes absorption by an acid, a resin composition that undergoes a crosslinking reaction by an acid, and can improve solubility. By combining with a resin composition, a highly sensitive image forming material can be produced.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Examples 1 to 12 and Comparative Examples 1 to 6]
(Preparation of support)
An aluminum plate having a thickness of 0.3 mm was etched by being immersed in 10% by mass sodium hydroxide at 60 ° C. for 25 seconds, washed with running water, neutralized with 20% by mass nitric acid, and then washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% by mass nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode time electricity of 300 coulomb / dm ² . Subsequently, after dipping in a 1% by mass aqueous sodium hydroxide solution at 40 ° C. for 5 seconds and then in a 30% by mass sulfuric acid aqueous solution and desmutting at 60 ° C. for 40 seconds, the current density in a 20% by mass sulfuric acid aqueous solution was 2A / current density. At dm ² , the anodization treatment was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μm (Ra display according to JIS B0601).

The following sol-gel reaction solution was applied to the back surface of the substrate thus treated with a bar coater.
The substrate was dried at 00 ° C. for 1 minute, and a support provided with a backcoat layer having a coating amount after drying of 70 mg / m ² was prepared.

Sol-gel reaction solution Tetraethyl silicate 55 parts by weight Water 25 parts by weight Methanol 10 parts by weight Phosphoric acid 0.05 parts by weight

  When the above components were mixed and stirred, heat generation started in about 5 minutes. After reacting for 60 minutes, a backcoat coating solution was prepared by adding the following raw material solutions.

Raw material liquid Pyrogallol formaldehyde condensation resin (molecular weight 2000) 6 parts by mass Dimethyl phthalate 6 parts by mass Fluorosurfactant 0.7 parts by mass (N-butylperfluorooctanesulfonamidoethyl acrylate /
Polyoxyethylene polyoxyethylene acrylate copolymer: molecular weight 20,000)
Methanol silica sol 50 parts by mass (manufactured by Nissan Chemical Industries, Ltd., methanol 30% by mass)
800 parts by mass of methanol

(Preparation of photosensitive layer)
A photosensitive composition having the following composition was coated on a support made of the aluminum plate thus treated and having a back coat layer formed thereon so that the dry coating amount was 1.0 g / m ² . Next, it was dried at 80 ° C. for 2 minutes to form a photosensitive layer.

1.54 g of the above addition polymerizable compound
Binder polymer 2.1 g
Allyl methacrylate / methacrylic acid / N-isopropylacrylamide copolymer (copolymerization molar ratio 67/13/20)
Photopolymerization initiation system (described in Tables 1 and 2)
Sensitizing dye Xg
Initiator compound Yg
Co-sensitizer Zg
Fluorine-based nonionic surfactant (F-177P) 0.015 g
Thermal polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt 0.02 g
Pigment dispersion 1.9 g
Methyl ethyl ketone 20.0 g
Propylene glycol monomethyl ether 20.0 g
(Composition of pigment dispersion)
Composition: Pigment Blue 15: 6 15 parts by mass Allyl methacrylate / methacrylic acid copolymer 10 parts by mass (copolymerization molar ratio 83/17)
Cyclohexanone 15 parts by mass Methoxypropyl acetate 22 parts by mass Propylene glycol monomethyl ether 40 parts by mass

(Preparation of protective layer)
On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating weight was 2 g / m ² , dried at 100 ° C. for 2 minutes, and protected. A layer was formed to obtain a lithographic printing plate precursor.

<Sensitivity evaluation method by exposure wavelength>
(Evaluation of sensitivity 1: 830 nm exposure)
Among the obtained negative lithographic printing plate precursors using A-1 as a sensitizing dye, a Trend setter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser, output 9 W, outer drum rotation speed 210 rpm, The exposure was performed under the conditions of a plate surface energy of 100 mJ / cm ² and a resolution of 2400 dpi.
After the exposure, the film was developed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water dilution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenisher. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.
The amount of energy necessary for recording was calculated based on the line width and laser output of the image obtained by the above exposure (with an infrared laser having a wavelength of about 830 to 850 nm) and development, the loss in the optical system, and the scanning speed. The smaller the value, the higher the sensitivity. The results are shown in Table 1.
(Evaluation of sensitivity 2: 532, 405 nm exposure)
Among the obtained lithographic printing plate precursors, those using A-2 and A-3 as sensitizing dyes, Fuji Step Guide (ΔD = 0.15) manufactured by Fuji Photo Film Co., Ltd. was placed on the lithographic printing plate precursor. With a xenon lamp that is passed through an optical filter (Kenko BP-53 (for 532 nm), BP-40 (for 405 nm)). It exposed so that it might become. As an optical filter, for the purpose of estimating the suitability for exposure to a short-wave semiconductor laser, monochromatic light of 532 nm for those using A-2 as a sensitizing dye or 405 nm for those using A-3 as a sensitizing dye Kenko BP-53 and 40, which can be exposed to light, were used. Thereafter, the film was immersed in a developer having the following composition at 25 ° C. for 10 seconds, developed, and the sensitivity (clear sensitivity) was calculated from the maximum number of steps at which the image was completely removed (Table 1). Here, the clear sensitivity represents the minimum energy required for image formation, and the lower this value, the higher the sensitivity.

(Developer composition)
1K potassium silicate 2.4g
Potassium hydroxide 0.2g
The following compound 5.0g
91.3g of water
Ethylenediaminetetraacetic acid, 4Na salt 0.1g

Measured acid value obtained by NaOH titration 1.08 meq / g
Mass average molecular weight determined by GPC measurement 52,000

<Sensitivity at different exposure wavelengths>
Points to note about the above sensitivity. The smaller the sensitivity value, the higher the sensitivity, but the ones with different exposure wavelengths cannot be compared. This is because the amount of energy per photon differs when the light source wavelength is different, so even if it is simply considered, it is possible to sensitize even if the exposure amount is small as the short wave usually becomes short. Sensitivity. Therefore, in Table 1, the sensitivity comparison between different exposure conditions is meaningless, and it is necessary to see the difference between the example and the comparative example under the same exposure condition.

(Evaluation of storage stability)
The lithographic printing plate prepared with the configuration described in the Examples was evaluated for storage stability by comparing the clear sensitivity and the sensitivity after aging under forced conditions under the following two conditions.
(I) Immediately after coating, exposure and development (ii) Storage under forced storage conditions at 60 ° C. for 10 days, exposure and development The clear sensitivity here is the same as described above. The difference between the sensitivity of (i) and the sensitivity of (ii) ((ii) / (i)) was defined as the clear sensitivity ratio. The closer this value is to 1, the smaller the change in image forming sensitivity between the time-sensitive material and the time-sensitive material, and it can be said that the storage stability is high.

(Evaluation of radical generation start temperature of biimidazole compound)
A composition based on the following photosensitive layer preparation method was applied to an aluminum support plate, dried under the following conditions, and cut into 3 cm squares to prepare samples. Measurement and analysis were performed according to the following analysis method using the obtained sample, and evaluation was performed according to the following evaluation method.
<Method for preparing photosensitive layer for evaluation>
Composition for photosensitive layer allyl methacrylate / methacrylic acid / N-isopropylacrylamide copolymer (copolymerization molar ratio 67/13/20) 5.3 g
Biimidazole compound 0.7g
LCV (leuco crystal violet) 0.4g
Methyl ethyl ketone 40.0g
Propylene glycol monomethyl ether 40.0g
Drying temperature: 80 degrees, drying time: 1 minute

The plate used here is different from the plate used for sensitivity evaluation and the like, and is prepared for evaluating the radical generation temperature.
(analysis method)
<Measurement device> Shimadzu UV-2100PC, integrating sphere ISR-260
Mini Heater and LakeShore330 Autonomous Temperature Controller
<Measurement method> Measure the reflection absorption of the AL coated sample before and after heating with a mini-heater and examine the difference spectrum <Measurement method>
(1) Unheated sample absorption measurement → (2) Heated for 5 min. → (3) Heated sample absorption measurement → (4) Unheated sample absorption measurement without LD-5 → (5) Heated for 5 min. → (6) Absorption measurement of heated sample without LD-5 → (7) Calculate only the color developed by heating LD-5 in ((3)-(1))-((6)-(4)). This was performed at 120, 100, 80, 70, 60 ° C.
<Analysis>
Using the color absorbance at 100 ° C. as the Y axis (reference value 1.0), a graph is created in which the relative color development amount at each temperature (X axis) is plotted. The relative value of the Y axis in the approximate curve is 0. A temperature exceeding 05 is defined as a radical generation start temperature.

(Evaluation methods)
The higher this temperature, the lower the radical generation rate due to heat, the better the platemaking property, and the higher the storage stability of the biimidazole compound.
(Evaluation of fogging)
Further, for the plate subjected to 405 nm exposure, in order to evaluate the safety light suitability as an index of workability, the obtained photosensitive material was exposed to yellow light (cut below 500 nm) for 30 minutes before exposure, and the same Then, exposure and development were performed. Visual observation was performed, and the fogging evaluation was carried out, assuming that the photosensitive material in which fogging occurred (no safelight suitability) was evaluated as “x”, and the photosensitive material in which fogging did not occur (safelight suitability) was given as “◯”. The results are shown in Table 1.

  According to the results in Table 1 above, it can be seen that the hexaarylimidazole compounds of Examples 1 and 2 are initiators excellent in thermal stability compared to Comparative Examples 1 and 2. As structural specificity, T-13,16 (compound of general formula II) and T31,32 (compound of general formula III) are more sensitive than the hexaarylbiimidazole compound represented by general formula (I). Although it is inferior, it turns out that thermal stability is very high. In addition, the present initiator can be applied to a photosensitive layer for any wavelength range, and provides a photosensitive layer having high sensitivity and high thermal stability. It was confirmed that the practicality was very high.

  In addition, the structure of the biimidazole compound in a present Example is what was illustrated in this specification, and the structure of another compound is as follows.

Claims (3)

(A) at least one of the compounds represented by the following general formulas (I), (II) and (III),
(B) a sensitizing dye having an absorption maximum λ _max at 350 nm to 850 nm, and (C) an addition polymerizable compound that reacts with at least one of a radical and an acid,
Containing the photosensitive composition.

(In the general formula (I), R _{1 to} R ₆ each independently represent a monovalent nonmetallic atomic group, and R ₇ and R ₈ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.
In general formula (II), one group in (R ₉ , R ₁₂ ) or (R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ ) is a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a cyclo An alkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkyl ketone group is represented, and the other group represents a substituted or unsubstituted aryl group or heteroaryl group.
In the general formula (III), R _{16 to} R ₁₉ and R _{21 to} R ₂₄ are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkyl ketone group. R ₁₅ and R _{20 each} represents a substituted or unsubstituted aryl group or heteroaryl group. )   An image recording material having a photosensitive layer containing the photosensitive composition according to claim 1 on a support.   An image recording method of performing scanning exposure on an image recording material having a photosensitive layer containing the photosensitive composition according to claim 1 on a support using a laser light source having a wavelength of 450 nm or less.