JP4796890B2 - Planographic printing plate precursor and planographic printing method - Google Patents

Description

The present invention relates to a photosensitive composition, a lithographic printing plate precursor, and a lithographic printing method, and in particular, when used in an image forming layer of a lithographic printing plate precursor, a photosensitive composition having improved developability, sensitivity, and printing durability, and The present invention relates to a lithographic printing plate precursor and a lithographic printing method.

In general, a lithographic printing plate is composed of an oleophilic image portion that receives ink in the printing process and a hydrophilic non-image portion that receives dampening water. Conventional lithographic printing plates are made by exposing a non-image area to a PS plate having a lipophilic photosensitive resin layer on a hydrophilic support through a lith film and then dissolving and removing the non-image area with a developer. It was normal to do.
In recent years, computers electronically process, store, and output images as digital information. Therefore, the image forming process according to the digital image information is to directly form an image on the lithographic printing plate precursor without using a lith film by scanning exposure using a highly directional active radiation such as laser light. Is desirable. In this way, the technology for making a printing plate from digital image information without using a lithographic film is a computer-to-plate (CT).
P).
A conventional plate-making method using a PS plate is a computer-to-plate (CTP).
If the technique is to be implemented, there is a problem that the wavelength region of the laser beam does not match the photosensitive wavelength region of the photosensitive resin.

Further, in the conventional PS plate, a step (development process) for dissolving and removing the non-image portion after exposure is indispensable. Furthermore, a post-processing step of washing the developed printing plate with water, treating it with a rinsing liquid containing a surfactant, or treating with a desensitizing liquid containing gum arabic or starch derivatives is also necessary. The point that these additional wet treatments are indispensable is a big problem for the conventional PS plate. The first half of the plate making process by the above digital processing (image forming process)
However, in the wet process where the latter half (development process) is complicated, the effect of the simplification is insufficient.
Particularly in recent years, consideration for the global environment has become a major concern for the entire industry. In consideration of the environment, processing with a developing solution closer to the neutral range and a small amount of waste liquid are cited as problems.
Furthermore, it is desirable to simplify the wet post-treatment or change to a dry treatment.

Therefore, one way to eliminate the processing process is to remove the non-image area of the printing original plate by mounting the exposed printing original plate on the cylinder of the printing press and supplying dampening water and ink while rotating the cylinder. There is a method called on-press development. That is, after the printing original plate is exposed, it is mounted on a printing machine as it is, and the processing is completed in a normal printing process.
Such a lithographic printing plate precursor suitable for on-press development has an image forming layer soluble in dampening water or an ink solvent, and is suitable for development on a printing press placed in a bright room. It is necessary to have good light room handling.
In the conventional PS plate, it is practically impossible to satisfy such a requirement.

Therefore, in order to satisfy such requirements, a lithographic printing plate precursor in which an image forming layer in which thermoplastic hydrophobic polymer fine particles are dispersed in a hydrophilic binder polymer is provided on a hydrophilic support has been proposed. (For example, refer to Patent Document 1). In making the plate, it is exposed with an infrared laser, and the thermoplastic hydrophobic polymer fine particles are coalesced (fused) with heat generated by photothermal conversion to form an image. On-press development can be performed by supplying at least one of water and ink. This lithographic printing plate precursor also has handleability in a bright room because the photosensitive region is an infrared region.
However, an image formed by coalescence (fusion) of thermoplastic hydrophobic polymer fine particles has insufficient strength and has a problem in printing durability as a printing plate.

In addition, a lithographic printing plate precursor including microcapsules encapsulating a polymerizable compound in place of the thermoplastic fine particles has been proposed (see, for example, Patent Documents 2 to 7). The original plate according to such a proposal has an advantage that the polymer image formed by the reaction of the polymerizable compound is superior in strength to the image formed by fusing fine particles.
In addition, since a polymerizable compound has high reactivity, many methods for isolating it using microcapsules have been proposed (see, for example, Patent Documents 2 to 7). It has been proposed to use a thermally decomposable polymer for the shell of the microcapsule.

Japanese Patent No. 2938397 JP 2000-2111262 A JP 2001-277740 A JP 2002-29162 A JP 2002-46361 A JP 2002-137562 A JP 2002-326470 A

However, in the conventional lithographic printing plate precursors described in Patent Documents 2 to 7, all of the developability, sensitivity and printing durability of the image formed by laser exposure are not sufficient, and development close to the neutral region There were problems such as treatment with liquid and little waste liquid.
The object of the present invention is to overcome the drawbacks of the prior art described above, write with a laser beam, mounted on a cylinder of a printing press, and capable of on-press development with dampening water and / or ink, Photosensitive composition capable of providing a lithographic printing plate precursor that can be developed in an acidic to neutral range and has excellent developability, sensitivity, and printing durability, and lithographic printing plate precursor and lithographic printing method using the same Is to provide.

As a result of intensive studies to achieve the above-mentioned problems, the inventor contains a compound represented by the following general formula (3) in the photosensitive composition forming the image forming layer of the lithographic printing plate precursor. As a result, the inventors have found that the above object can be achieved, and have accomplished the present invention.
That is, the present invention is as follows.
(1) A lithographic printing plate precursor in which an image forming layer containing a compound represented by the following general formula (3) is provided on a surface hydrophilic support.

In the formula, the cation moiety is a moiety composed of a functional group having a positive charge, and the anion moiety is
-A portion composed of a functional group having a charge, a and b represent natural numbers of 1 to 20, m, p,
Represents a natural number of 1 to 6 and C represents a number where m / Cp = 1.

(2) said that the image forming layer is further characterized by containing a radical polymerizable compound (1) Symbol mounting the lithographic printing plate precursor.
( 3 ) The lithographic printing plate precursor as described in (1) or (2) above, wherein the image forming layer further contains an infrared absorber.
( 4 ) The lithographic printing plate precursor as described in ( 1 ) to ( 3 ) above, wherein a protective layer is provided on the image forming layer.
( 5 ) The lithographic printing plate precursor as described in ( 1 ) to ( 4 ) above, which can be developed with an aqueous solution having a pH of 10 or less.
( 6 ) The lithographic printing plate precursor as described in ( 1 ) to ( 4 ) above, which can be mounted on a printing press and printed without any processing after image formation.

( 7 ) The lithographic printing plate precursor according to any one of ( 1 ) to ( 6 ) above is mounted on a printing press and imagewise exposed with a laser, or imagewise exposed with a laser and then printed. A lithographic printing method comprising: mounting on a machine; supplying printing ink and fountain solution to the lithographic printing plate precursor to remove unexposed portions of the image forming layer and printing.
( 8 ) The method for preparing a lithographic printing plate as described in ( 7 ) above, wherein the exposed lithographic printing plate precursor is further subjected to heat treatment between exposure and development.

According to the photosensitive composition of the present invention, the use of the lithographic printing plate precursor in the image forming layer allows the lithographic printing plate precursor to be written by infrared and semiconductor laser exposure, and on the cylinder of the printing press. The unexposed portion of the image-forming layer can be removed by mounting, fountain solution and / or ink, and can be developed on-machine, and can be developed in an acidic to neutral range, and its developability and sensitivity are excellent. In addition, it can be excellent in printing durability.

It will be described in detail below flat plate printing plate precursor and a lithographic printing method of the present invention. The present invention relates to the lithographic printing plate precursor and the lithographic printing method described in the above (1) to (8), but other matters are also described in this specification for reference.
First, the compound represented by the general formula (1) or (2), which is a feature of the photosensitive composition of the present invention, will be described.

As the polymerizable group in the general formulas (1) and (2), any functional group capable of radical polymerization can be preferably used. Such radical polymerizing functional groups include acrylic acid ester groups, methacrylic acid ester groups, itaconic acid ester groups, maleic acid ester groups, fumaric acid ester groups, acrylic acid amide groups, methacrylic acid amide groups, itaconic acid amide groups,
Examples thereof include a maleic acid amide group, a fumaric acid amide group, a vinyl ether group, a vinyl ester group, a vinyl phenyl group, a vinyl carbonyl group, and derivatives thereof. Among them, acrylic acid ester group, methacrylic acid ester group, itaconic acid ester group, maleic acid ester group, fumaric acid ester group, acrylic acid amide group, vinyl ether group, vinyl ester group,
A vinylphenyl group is preferable, and an acrylate group and a methacrylate group are particularly preferable.

The cation moiety in the general formula (1) is a moiety including a functional group having a positive charge. Such + charges are preferably formed by N +, S +, O +, I +, P +, and N +, P +
More preferably, it is formed by.
X ⁿ⁻ in the general formula (1) is an n-valent anion compound. Such anion compounds include halogen anions, halogen oxoacid anions (ClO ⁴⁻ , IO ³⁻ , BrO ^3−).
), Halogeno complex ions (BF ₄ ⁻ , PF ₆ ⁻ , AlCl ₄ ^−, etc.), sulfate anion, nitrate anion, phosphate anion, borate anion, carboxylate anion, sulfonate anion, phosphonate anion, metal complex anion ( [Fe (CN) ₆ ] ^4- etc.) And the like. Of these, a sulfonate anion, a carboxylate anion, and a phosphonate anion are preferable.

The anion moiety in the general formula (2) is a moiety including a functional group having a −charge. Such a charge is preferably formed by a carboxylate anion, a sulfonate anion, a phosphonate anion, a phosphate anion, a sulfate anion, a borate anion, and a carboxylate anion, a sulfonate anion, a phosphonate anion, a phosphate anion. More preferably, it is formed by.

In the general formula (2), M ^{q +} is a q-valent cation compound. Examples of such cationic compounds include alkali metal cations (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal cations (Mg ²⁺ , Ca ²⁺ etc.), IIB group metal cations (Zn ²⁺ etc.), IIIB group Metal cations (
Al ³⁺ etc.), group IVB metal cations (Sn ²⁺ etc.), transition metal cations (Fe ²⁺ , Fe ³⁺ ,
Ni ²⁺ , Cu ²⁺ , Co ²⁺ , Ag ^+, etc.), metal complex cations ([Fe (bpy) ₃ ] ^2+, etc.),
Examples include ammonium cation, phosphonium cation, iodonium cation, sulfonium cation, diazonium cation, pyridinium cation, and oxonium cation. Among them, ammonium cation, phosphonium cation, pyridinium cation, alkali metal cation, alkaline earth metal cation, transition metal cation, group IIB metal cation, group IIIB metal cation, group IVB metal cation are preferable, ammonium cation, phosphonium cation, alkaline earth More preferred are metal cations and transition metal cations.

The compound represented by the general formula (1) or (2) used in the present invention is a compound in which a polymerizable group as described above and a functional group having + charge or −charge are linked by an existing linking group. Any of them can be suitably used. What is preferable as such a compound is a compound having two or more polymerizable groups in the whole compound represented by the general formula (1) or (2). Specific examples of the compound represented by the general formula (1) or (2) are shown below. The present invention is not limited to these.

  Next, the compound represented by the general formula (3) used in the present invention will be described.

In the formula, the cation moiety is a moiety composed of a functional group having a positive charge, and the anion moiety is
-A portion composed of a functional group having a charge, a and b represent natural numbers of 1 to 20, m, p,
Represents a natural number of 1 to 6 and C represents a number where m / Cp = 1.

The compound represented by the general formula (3) used in the present invention is represented by the cationic compound having a polymerizable group and a cation moiety of the compound represented by the general formula (1) and the general formula (2). Any compound in which the polymerizable group of the compound and the anion compound having an anion portion form an ion pair can be suitably used. Specific examples of the compound represented by the general formula (3) used in the present invention are shown below. The present invention is not limited to these.

The molecular weight of the compound represented by the general formula (1), (2), or (3) used in the present invention is:
3000 or less is preferable and 2000 or less is more preferable.
The compounds represented by the general formula (1), (2) or (3) used in the present invention may be used alone or in combination of two or more.
The content of the compound represented by the general formula (1), (2), or (3) used in the present invention in the photosensitive composition is 0.1% by mass with respect to the total solid content of the photosensitive composition. The content is preferably 50% by mass or less and more preferably 0.5% by mass or more and 30% by mass or less.

(Synthesis of IM-577)
3-sulfopropyl methacrylate potassium salt: 12.32 g, 2-methacryloyloxyethyltrimethylammonium chloride (75% aqueous solution): 13.85 g, water: 25
g was mixed and dissolved completely. The solution was poured into 1 L of acetone and stirred as it was for 30 minutes. The obtained mixed solution was filtered and then concentrated under reduced pressure to obtain IM-577 (94.4).
Mass% aqueous solution): 23.25 g was obtained.

(Synthesis of IM-454)
p-Xylylene dibromide: 13.20 g, methacrylic acid-2-diethylaminoethyl: 20.38 g, isopropanol: 100 mL, p-methoxyphenol: 10 mg were mixed and stirred under reflux for 2 hours. Two hours later, the mixture was cooled to room temperature, and the precipitated white solid was filtered and washed with 10 mL of isopropanol cooled to 10 ° C. or lower. Dry under reduced pressure, I
M-454: 26.98 g was obtained as a white solid.

(Synthesis of IM-580)
IM-454: 6.35 g was dissolved in methanol: 10 mL. To this solution, an aqueous solution in which 7.39 g of potassium 3-sulfopropyl methacrylate was dissolved in 30 mL of water was added, and the mixture was stirred at room temperature for 3 hours. After 3 hours, methanol was removed under reduced pressure, and the resulting aqueous solution was extracted with chloroform: 50 mL. The chloroform solution and an aqueous solution prepared by dissolving 7.39 g of 3-sulfopropyl methacrylate potassium salt in water: 30 mL were mixed and stirred at room temperature for 30 minutes, and then the chloroform phase was separated and concentrated under reduced pressure to obtain IM-580: 8
. 0 g was obtained.

(Synthesis of IM-046)
Tetramethylenebis (triphenylphosphonium) bromide: 7.41 g was suspended in methanol: 30 mL and dissolved by heating. To the same solution cooled to room temperature, an aqueous solution in which 7.39 g of potassium 3-sulfopropyl methacrylate was dissolved in 30 mL of water was added, and the mixture was stirred at room temperature for 2 hours. After 2 hours, methanol was removed under reduced pressure, and the resulting aqueous solution was extracted with chloroform: 50 mL. The chloroform solution and an aqueous solution of 7.39 g of 3-sulfopropyl methacrylate potassium salt in water: 30 mL were mixed and stirred at room temperature for 30 minutes, and then the chloroform phase was separated. Salt: 7.39 g was mixed with an aqueous solution in 30 mL of water and stirred for 30 minutes.
The chloroform phase was separated and concentrated under reduced pressure to obtain IM-046: 9.86 g.

The photosensitive composition of this invention contains the radical polymerization initiator, the binder polymer, and the sensitizing dye with the compound represented by the said General formula (1), (2) or (3).

[Radical polymerization initiator]
The radical polymerization initiator used in the photosensitive composition of the present invention is a compound that generates radicals by light or thermal energy and initiates and accelerates polymerization of a compound having a polymerizable unsaturated group. As such a radical generator, a known radical polymerization initiator or a compound having a bond having a small bond dissociation energy can be appropriately selected and used.
Examples of the compounds that generate radicals include organic halogen compounds, carbonyl compounds, organic peroxides, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boron compounds, disulfone compounds, and oximes. Examples thereof include ester compounds and onium salt compounds.

Specific examples of the organic halogen compound include Wakabayashi et al., “Bull Chem.
c Japan "42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 53-133428, JP-A 55-32070. JP, 60-609736, JP 61-169835,
JP-A-61-169837, JP-A-62-258241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, P. Hutt,
“Journal of Heterocyclic Chemistry”, 1 (No.
3) The compound as described in (1970) is mentioned. Of these, oxazole compounds and S-triazine compounds substituted with a trihalomethyl group are preferred.

More preferably, at least one mono, di, or trihalogen substituted methyl group is s
-An s-triazine derivative bonded to a triazine ring and an oxadiazole derivative bonded to an oxadiazole ring. Specifically, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-
Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4, 6-
Bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2
, 4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6
-Bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6 -Tris (tribromomethyl) -s-triazine, 2-methyl-4,6
Examples include -bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, the following compounds, and the like.

Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy- 2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1- Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′
Acetophenone derivatives such as-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone,
Thioxanthone derivatives such as 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, ethyl p-dimethylaminobenzoate, p- Examples thereof include benzoic acid ester derivatives such as ethyl diethylaminobenzoate.

As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.

Examples of the organic peroxide include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3.
, 5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroper Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-oxa Noyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxy Isopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, ter -Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Examples of the metallocene compounds include JP-A-59-152396 and JP-A-61-15.
No. 1197, JP-A 63-41484, JP-A 2-249, JP-A 2-
Various titanocene compounds described in Japanese Patent No. 4705 and JP-A-5-83588, for example,
Di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-
Bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-
2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,
4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,
3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl -Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-methylcyclopentadienyl- Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1
-Yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-
Yl) phenyl) titanium, JP-A-1-304453, JP-A-1-152109
And iron-arene complexes described in the Japanese Patent Publication.

Examples of the hexaarylbiimidazole compound include Japanese Patent Publication No. 6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, and 4,622.
Various compounds described in the specification of No. 286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (
o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 , 5'-
Tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5
5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′
, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

Examples of the organoboron compound include, for example, JP-A-62-143044 and JP-A-62-2.
150242, JP-A-9-188865, JP-A-9-188686, JP-A-9-1
No. 88710, JP-A No. 2000-131737, JP-A No. 2002-107916,
Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz
Martin "Rad Tech '98. Proceeding April 19-2.
2, 1998, Chicago "etc., JP-A-6-157623
Organoboron sulfonium complexes or organoboron oxosulfonium complexes described in JP-A-6-175564 and JP-A-6-175561, JP-A-6-175554
And organoboron iodonium complexes described in JP-A-6-175553, JP-A-9
As the organoboron phosphonium complex described in JP-A-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-3 ester compounds, JCS Perkin II ( (1979) 1653-1660), JCSPerkin II (1979)
156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP200
Examples thereof include compounds described in JP-A 0-66385 and compounds described in JP-A 2000-80068. Specific examples include compounds represented by the following structural formula.

Examples of the onium salt compound include S.I. I. Schlesinger, Photo
ogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al,
Polymer, 21, 423 (1980), diazonium salt, US Pat. No. 4,0
69,055, JP-A-4-365049, etc., phosphonium salts described in US Pat. Nos. 4,069,055 and 4,069,056, European patents No. 104,143, U.S. Pat. Nos. 339,049, 410,201,580 and 3,604,581, the sulfonium salts described in J. Pat. V. Cr
ivello et al, Macromolecules, 10 (6), 1307 (1
977), J. et al. V. Crivello et al, J.A. Polymer Sci. , P
polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing
Examples include onium salts such as arsonium salts described in ASIA, p478 Tokyo, Oct (1988).

In the present invention, these onium salts function not as acid generators but as ionic radical polymerization initiators.

The onium salts preferably used in the present invention are represented by the following general formulas (RI-I) to (RI-II).
An onium salt represented by I).

In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms and a carbon number. 1-12 alkenyl groups, C1-C12 alkynyl groups, C1-C12 aryl groups, C1
-12 alkoxy group, C1-C12 aryloxy group, halogen atom, C1-C1
2 alkylamino groups, C1-C12 dialkylamino groups, C1-C12 alkylamide groups or arylamide groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups And a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ⁻ represents a monovalent anion, specifically, a halogen ion, a perchlorate ion, a hemoborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion,
A sulfate ion is mentioned. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion and sulfinate ion are preferable from the viewpoint of stability.

In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include 1 to 1 carbon atoms. 12 alkyl groups, C1-C12 alkenyl groups, C1-C12 alkynyl groups, C1-C1
2 aryl groups, C1-C12 alkoxy groups, C1-C12 aryloxy groups, halogen atoms, C1-C12 alkylamino groups, C1-C12 dialkylamino groups, C1-C1 12 alkylamide groups or arylamide groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoint of stability and reactivity.

In the formula (RI-III), R ₃₁ , R ₃₂ and R ₃₃ are each independently an aryl group, alkyl group, alkenyl group or alkynyl having 20 or less carbon atoms, which may have 1 to 6 substituents. Represents a group. Among them, an aryl group is preferable from the viewpoint of reactivity and stability. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, 1 carbon
~ 12 aryloxy group, halogen atom, C1-C12 alkylamino group, carbon number 1
-12 dialkylamino group, C1-C12 alkylamide group or arylamide group, carbonyl group, carboxyl group, cyano group, sulfonyl group, C1-C12 thioalkyl group, C1-C12 thioaryl group Is mentioned. Z ₃₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoints of stability and reactivity. More preferred are the carboxylate ions described in JP-A No. 2001-343742, and particularly preferred are the carboxylate ions described in JP-A No. 2002-148790.

The radical polymerization initiator is not limited to the above, but particularly from the viewpoint of reactivity and stability,
Triazine-based initiators, organic halogen compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boron compounds, oxime ester compounds, and onium salt compounds are preferable, and triazine-based initiators, organic halogen compounds, metallocene compounds, hexaarylbi compounds are more preferable. These are imidazole compounds and onium salt compounds.
When the photosensitive composition of the present invention is used for an image forming layer of a lithographic printing plate precursor, the radical polymerization initiator is preferably 0.1 to 50% by weight, more preferably based on the total solid content of the image forming layer. Can be added at a ratio of 0.5 to 30% by mass, particularly preferably 0.8 to 20% by mass.

[Sensitizing dye]
The sensitizing dye used in the photosensitive composition of the present invention is appropriately selected according to the application to be used, and is not particularly limited. For example, an infrared absorber or 360 is used.
Examples thereof include sensitizing dyes that absorb light of nm to 450 nm.

[Infrared absorber]
An infrared absorber is a component used to increase sensitivity to an infrared laser.
The infrared absorber has a function of converting absorbed infrared rays into heat. The infrared absorber used in the present invention is preferably a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.

Examples of the dye include commercially available dyes and, for example, “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, Showa 45).
The publicly known thing described in literature, such as an annual publication, can be utilized. 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, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

Preferred dyes include, for example, JP-A-58-125246 and JP-A-59-8435.
6, cyanine dyes described in JP-A-60-78787, JP-A-58-173
No. 696, JP-A 58-181690, JP-A 58-194595, etc., methine dyes, JP-A 58-112793, JP-A 58-224793, JP-A 59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like, and naphthoquinone dyes described in JP-A-58-112792, etc. Examples thereof include squarylium dyes and cyanine dyes described in British Patent No. 434,875.

In addition, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also suitable. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, and 58-2
20143, 59-41363, 59-84248, 59-84249,
Pyryllium compounds described in JP-A-59-146063 and JP-A-59-146061, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,4
No. 75, pentamethine thiopyrylium salt, etc., and Japanese Patent Publication Nos. 5-13514 and 5
A pyrylium compound disclosed in JP-A-19702 is also preferably used. In addition, as another preferred example of the dye, U.S. Pat. No. 4,756,993 describes formula (I), (
Mention may be made of the near-infrared absorbing dyes described as II).

Moreover, as another preferable example of the infrared absorbing dye, JP-A-20
Specific indolenine cyanine dyes described in JP-A-02-278057.

Particularly preferred among these dyes are cyanine dyes, squarylium dyes,
Examples include pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and one particularly preferred example is a cyanine dye represented by the following general formula (I).

In the general formula (I), X ¹ represents a hydrogen atom, a halogen atom, -NPh _2, X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 carbon atom containing a hetero atom.
-12 hydrocarbon groups are shown. Here, the hetero atom means N, S, O, a halogen atom,
Se is shown. Xa ⁻ is defined in the same manner as Za ⁻ described later, and R ^a is a hydrogen atom, an alkyl group,
It represents a substituent selected from a reel group, a substituted or unsubstituted amino group, and a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Preferred substituents include hydrocarbon groups having 12 or less carbon atoms,
Examples thereof include a halogen atom and an alkoxy group having 12 or less carbon atoms. Y ¹ and Y ² may be the same as or different from each other, may be the same or different from each other and each may be a sulfur atom or a dialkyl methyl having 12 or less carbon atoms, and may have a substituent. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (I) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably, from the storage stability of the recording layer coating solution.
Perchlorate ion, hexafluorophosphate ion, and aryl sulfonate ion.

Specific examples of the cyanine dye represented by formula (I) that can be suitably used in the present invention include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969.
] Can be mentioned.

Further, other particularly preferable examples include specific indolenine cyanine dyes described in JP-A-2002-278057 described above.

Examples of the pigment used in the present invention include commercially available pigments and color indexes (C.I.
. ) Handbook, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, 1986), “Printing Ink Technology”, published by CMC, published in 1984) Is available.

Examples of the pigment 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 ,
Loso pigments, nitro pigments, natural materials, 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 above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

The particle diameter of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. Within this range, good stability and uniformity of the pigment dispersion in the photosensitive composition can be obtained.

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).

  These infrared absorbers can be added by being encapsulated in microcapsules.

As the addition amount, when the photosensitive composition of the present invention is used as an image forming layer of a negative lithographic printing plate precursor, the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm of the image forming layer is reflected. It is preferable to add so that it may exist in the range of 0.3-1.3 by a measuring method, More preferably, it is the range of 0.4-1.2. Within this range, a uniform polymerization reaction proceeds in the depth direction of the image forming layer, and good film strength of the image area and adhesion to the support can be obtained.
The absorbance of the image forming layer can be adjusted by the amount of the infrared absorber added to the image forming layer and the thickness of the image forming layer. Absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, an image forming layer having a thickness appropriately determined in a range in which the coating amount after drying is necessary as a lithographic printing plate is formed, and the reflection density is set to the optical density. And a method of measuring with a spectrophotometer by a reflection method using an integrating sphere.

[Sensitizing dye absorbing light of 360 nm to 450 nm]
As a sensitizing dye that absorbs light of 360 nm to 450 nm, for example, the following general formula (I)
A merocyanine dye represented by the following general formula (II), a benzopyran represented by the following general formula (II), a coumarin, an aromatic ketone represented by the following general formula (III), an anthracene represented by the following general formula (IV), Etc.

(In the formula, A represents an S atom or NR ₆ , R ₆ represents a monovalent non-metallic atomic group, Y represents a basic nucleus of the dye in cooperation with the adjacent A and the adjacent carbon atom. Represents a non-metallic atomic group,
X1, X ₂ each independently represents a monovalent non-metallic atomic group, X _1, X ₂ may be bonded to form an acidic nucleus of the dye together. )

(In the formula, = Z represents a carbonyl group, a thiocarbonyl group, an imino group, or the partial structural formula (
I ′) represents an alkylidene group, and X ₁ and X ₂ have the same meaning as in general formula (II), and R ₇ to
R ₁₂ each independently represents a monovalent nonmetallic atomic group. )

(In the formula, Ar ₃ represents an aromatic group or a heteroaromatic group which may have a substituent, and R ₁₃
Represents a monovalent nonmetallic atomic group. R ₁₃ is more preferably an aromatic group or a heteroaromatic group, and Ar ₃ and R ₁₃ may be bonded to each other to form a ring. )

(In the formula, X ₃ , X ₄ and R _{14 to} R ₂₁ each independently represent a monovalent non-metallic atomic group, and more preferable X ₃ and X ₄ are electron donating groups having a negative Hammett's substituent constant. .)
Preferred examples of the monovalent nonmetallic atomic group represented by X ₁ to X ₄ and R ₆ to R ₂₁ in the general formulas (I) to (IV) include a hydrogen atom, an alkyl group (for example, a methyl group, Ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl A 2-ethylhexyl group,
2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl, chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl Group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-
Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonyl Butyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (
Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoyl Propyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group,
Diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α- Methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2 -Propynyl group, 2-butynyl group, 3-butynyl group, etc.), aryl group (eg, phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloro Methylphenyl group, hydroxyphenyl group, methoxyphenyl group, etho Shifeniru group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxy hydroxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group,
Carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl Group), heteroaryl group (for example, thiophene, thiathrene,
Furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine, Naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline,
Phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, etc.), alkenyl groups (eg vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-
1-ethenyl group, etc.), alkynyl group (eg, ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc.), halogen atom (—F, —Br, —Cl, —I),
Hydroxyl group, alkoxy 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-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyl group Oxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy 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-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group,
N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxy Carbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group 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—
Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N -Alkylsulfamoyl 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 conjugate base group (hereinafter referred to as “phosphonate group”), dialkylphosphono group (—PO ₃ (alkyl) ₂ )
, Diarylphosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (
alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl))
) And its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkylphosphonooxy group ( -OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (-OP
O ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter alkyl) Phosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (ary
l)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), cyano group,
A nitro group, and the like. Among these substituents, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, and an acyl group are particularly preferable.

Examples of the basic nucleus of the dye formed together with A adjacent to Y and the adjacent carbon atom in the general formula (I) include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocycles. A 5- or 6-membered heterocyclic ring is preferable.

Examples of nitrogen-containing heterocycles include, for example, LGBrooker et al., J. Am. Chem. Soc., 73,5326-
Any of those known to constitute a basic nucleus in the merocyanine dyes described in 5358 (1951). And references can be suitably used. Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, etc.), benzothiazoles (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzo Thiazole, 6
-Methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [2,1] thiazole 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, etc.), thianaphtheno-7 ', 6', 4,5-thiazoles For example, 4'-methoxy Chiana Fute Bruno -7 ',
6 ', 4,5-thiazole, etc.), oxazoles (for example, 4-methyloxazole, 5-
Methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-
Ethyl oxazole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5
, 6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole , 6-hydroxybenzoxazole, etc.), naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.) ), Benzoselenazoles (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (eg, Shift [1,2] selenazole, naphtho [2,1]
Selenazole etc.), thiazolines (eg thiazoline, 4-methylthiazoline etc.), 2-
Quinolines (eg, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxy Quinoline, 8-hydroxyquinoline, etc.), 4-
Quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, Isoquinoline, etc.), benzimidazoles (eg, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenines (eg, 3,3-dimethylindolenine, 3 ,
3,5, -trimethylindolenine, 3,3,7, -trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, etc.), 4-pyridine (for example, pyridine, etc.), etc. be able to.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.

Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1] Dithiol, etc.), dithiols (for example, 4,
5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonylbenzodithiols, 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyl Dithiol, 4
-Carboxymethyldithiol etc. can be mentioned.

As mentioned above, for the sake of convenience, the description used in the description of the heterocyclic ring has conventionally used the name of the heterocyclic mother skeleton, but when forming the basic skeleton partial structure of the sensitizing dye, for example, in the case of the benzothiazole skeleton It is introduced in the form of an alkylidene-type substituent with one degree of unsaturation, such as a 3-substituted-2 (3H) -benzothiazolidene group.

Among sensitizing dyes as compounds having an absorption maximum in a wavelength region of 360 nm to 450 nm,
A dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (V).

(In the general formula (V), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom or ═N (R ₃ ). R ₁ , R ₂ and R ₃ is independently
Represents a hydrogen atom or a monovalent non-metallic atomic group, and A and R ₁ and R ₂ and R ₃ are
They may be joined to form an aliphatic or aromatic ring. )
The general formula (V) will be described in more detail. R ₁ , R ₂ and R ₃ are each independently
A hydrogen atom or a monovalent nonmetallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom are represented.

Preferable examples of R ₁ , R ₂ and R ₃ 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, t-butyl group, isopentyl group, neopentyl group, 1
-Methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 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.

As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, 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-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino 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 groups, N'-alkyl-N-arylureido groups,
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-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N ' -Aryl-
N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- Arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, 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-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N- Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl 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 conjugate base group (hereinafter referred to as phosphonate group) ), dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkylaryl A phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group ( -PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group) , Dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), mono Alkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base Group (hereinafter referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group,
A heteroaryl group, an alkenyl group, and an alkynyl group are mentioned.

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

As the preferred heteroaryl group as R ₁ , R ₂ and R ₃ , a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used. Examples of particularly preferred heteroaryl groups Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline,
Examples thereof include phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, and the like. These may be further benzo-fused or may have a substituent.

Examples of preferable alkenyl groups as R ₁ , R ₂ and R ₃ include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like.
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G1 in the acyl group (G1CO-) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), an alkoxy group,
Aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N
-Arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group,
N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group, Phosphonooxy group,
A phosphonatooxy group, an aryl group, and an alkenyl group are mentioned.

On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferable substituted alkyl groups as R ₁ , R ₂ and R ₃ obtained by combining the substituent with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group,
Allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N -Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl Group, carbamoylmethyl group, N-methylcarbamoylethyl group,
N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfuric group Famoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-
N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphono Hexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, and the like.

Specific examples of preferred aryl groups as R ₁ , R ₂ and R ₃ 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, and among these, a phenyl group and a naphthyl group are more preferable. .

Specific examples of preferred substituted aryl groups as R ₁ , R ₂ and R ₃ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group described above. . 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, carboxy Eniru group, methoxycarbonylphenyl group, allyloxycarbonyl phenyl group, chlorophenoxy carbonyl phenyl group, carbamoyl phenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N-sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoyl Phenyl group, N
-Ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-
Tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl Group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2- A propynylphenyl group, a 2-butynylphenyl group, a 3-butynylphenyl group, and the like can be given.

Next, A in the general formula (V) will be described. A represents an aromatic ring or a hetero ring which may have a substituent. Specific examples of the aromatic ring or hetero ring which may have a substituent include R ₁ and R in the general formula (V). similar to those described in ₂ and R ₃ can be exemplified.

The sensitizing dye represented by the general formula (V) is a condensation of an acidic nucleus as shown above or an acidic nucleus having an active methylene group with a substituted or unsubstituted aromatic ring or heterocyclic ring. Although obtained by reaction, these can be synthesized with reference to JP-B-59-28329.

Preferred specific examples (D1) to (D41) of the compound represented by the general formula (V) are shown below. In addition, an isomer with a double bond connecting an acidic nucleus and a basic nucleus is not limited to either isomer.

The sensitizing dye that absorbs light of 360 nm to 450 nm is 1 in all components of the photosensitive composition.
. It is preferably used in the range of 0 to 10.0% by mass. More preferably 1.5 to 5.0
It is the range of mass%.

[Binder polymer]
As the binder polymer that can be used in the photosensitive composition of the present invention, a water-insoluble polymer is preferably used. Furthermore, the hydrophobic binder polymer that can be used in the present invention preferably contains substantially no acid group such as a carboxyl group, a sulfone group, and a phosphoric acid group. The acid value of the binder polymer (the acid content per gram of polymer) Is expressed as a chemical equivalent number) is 0
. It is preferably 3 meq / g or less, and more preferably 0.1 meq / g or less.

That is, the binder polymer that can be used in the present invention is preferably insoluble (hydrophobic) in water and an aqueous solution of pH 10 or higher, and the solubility of the binder polymer in water and an aqueous solution of pH 10 or higher is 0.5% by mass or less. Preferably, it is 0.1% by mass or less. By using such a binder polymer, the film strength, water resistance and fillability of the image forming layer are improved, and the printing durability is improved.

As long as it does not impair the performance of the photosensitive composition of this invention as a binder polymer, if it is the said range, a conventionally well-known thing can be used without a restriction | limiting, The linear organic polymer which has film property is preferable.

As an example of such a binder polymer, a polymer selected from an acrylic resin, a polyvinyl acetal resin, a polyurethane resin, a polyamide resin, an epoxy resin, a methacrylic resin, a styrene resin, and a polyester resin is preferable. Especially, an acrylic resin is preferable and a (meth) acrylic acid ester copolymer is preferable. More specifically, (meth) acrylic acid alkyl or aralkyl ester and (meth) acrylic acid ester residue (
To R of the -COOR) contains a -CH ₂ CH ₂ O- unit or a -CH ₂ CH ₂ NH- unit (meth)
A copolymer with an acrylate ester is particularly preferred. The preferable alkyl group of the (meth) acrylic acid alkyl ester is an alkyl group having 1 to 5 carbon atoms, and a methyl group is more preferable. Preferable (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate.

Further, the binder polymer can be cross-linked in order to improve the film strength of the image area.
In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization or may be introduced by a polymer reaction.
Here, the crosslinkable group is a group that crosslinks the polymer binder in the course of a radical polymerization reaction that occurs in the composition when the photosensitive composition is exposed. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, an onium salt structure etc. are mentioned, for example. Among these, an ethylenically unsaturated bond group is preferable, and the following general formula (
The functional groups represented by 1) to (3) are particularly preferable.

In the general formula (1), R ^{1 to} R ³ each independently represents a monovalent organic group, but R ¹
Preferred examples include a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R ²
And R ³ each independently has a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an aryl which may have a substituent Examples include an amino group, an alkylsulfonyl group that may have a substituent, and an arylsulfonyl group that may have a substituent. Among them, a hydrogen atom, carboxyl group, alkoxycarbonyl group, and A preferable alkyl group and an aryl group which may have a substituent are preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or N (R ¹² ) —, and R ¹² represents a hydrogen atom or 1
Represents a valent organic group. Here, R ¹² includes an alkyl group which may have a substituent, and the like.
Of these, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group,
Arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like can be mentioned.

In the general formula (2), R ⁴ to R ⁸ is each independently a monovalent organic group, R ⁴
To R ⁸ is preferably a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent,
An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent,
Examples include an arylsulfonyl group which may have a substituent. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent Is preferred.

Examples of the substituent that can be introduced are the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or N (R ¹² ) —. R ¹² has the same meaning as R ¹² in general formula (1), and preferred examples are also the same.

In the general formula (3), R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group has high radical reactivity. preferable. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent,
An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, an arylamino group that may have a substituent, a substituent Examples include an alkylsulfonyl group that may have, an arylsulfonyl group that may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group that may have a substituent, and a substituent An aryl group which may have a group is preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Also,
Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Examples of R ¹³ include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Among these, (meth) acrylic acid copolymers having a crosslinkable group in the side chain and polyurethane are more preferable.

For example, the binder polymer having a crosslinkable property has a free radical (
A polymerization initiating radical or a growth radical in the polymerization process of the polymerizable compound) is added, and addition polymerization is performed directly between polymers or via a polymerization chain of the polymerizable compound, and a crosslink is formed between the polymer molecules to be cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded to each other so that crosslinking between the polymer molecules occurs. Forms and cures.

The content of the crosslinkable group in the binder polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 per 1 g of the binder polymer.
mmol, more preferably 1.0-7.0 mmol, most preferably 2.0-5.5 mm
ol.

Further, when the photosensitive composition of the present invention is used for an image forming layer of a lithographic printing plate precursor, the binder polymer is preferably hydrophilic from the viewpoint of improving developability with respect to an aqueous solution, and from the viewpoint of improving printing durability. It is important that the binder polymer has good compatibility with the polymerizable compound contained in the image forming layer, that is, it is preferably oleophilic. From such a viewpoint, in the present invention, it is also effective to copolymerize a hydrophilic group and a lipophilic group in a hydrophobic binder polymer in order to improve developability and printing durability. Examples of the hydrophilic group include a hydroxy group, a carboxylate group, a hydroxyethyl group, an ethyleneoxy group, a hydroxypropyl group, a polyoxyethyl group, a polyoxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, and an ammonium group. And those having a hydrophilic group such as an amide group or a carboxymethyl group.

The binder polymer preferably has a mass average molecular weight of 5,000 or more and 10,000 to 3
More preferably, the number average molecular weight is 1,000 or more.
More preferably, it is 2000-250,000. Polydispersity (mass average molecular weight / number average molecular weight)
Is preferably 1.1-10.
The binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like, but is preferably a random polymer.
The hydrophobic binder polymer may be used alone or in combination of two or more.
Content of hydrophobic binder polymer is 5-90 mass% with respect to the total solid of a photosensitive composition, It is preferable that it is 10-70 mass%, and it is more that it is 10-60 mass%. preferable. Within this range, when the photosensitive composition of the present invention is used in the image forming layer of a lithographic printing plate precursor, good image area strength and image formability can be obtained.

[Co-sensitizer]
By using a certain kind of additive, the sensitivity of the photosensitive composition of the present invention can be further improved. Such a compound is referred to as a co-sensitizer in the present invention. 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 are broadly: (a)
Those that can be reduced to produce active radicals, (b) those that can be oxidized to produce active radicals, (c) react with less active radicals to convert to more active radicals, or chain transfer agents However, there are many cases where there is no general explanation as to which of these compounds each belongs to.

(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. Specifically, for example, ethanolamines,
N-phenylglycine, N-trimethylsilylmethylaniline, etc. are mentioned.
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. A compound having an S—S bond is also S.
Sensitization due to -S cleavage is known.
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]
Examples include -2-morpholinopronone-1 and oxime ethers obtained by reacting these with hydroxyamines and then etherifying N-OH.
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 donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. Specifically, for example, 2-
And mercaptobenzimidazoles.

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

These cosensitizers can also be subjected to various chemical modifications for improving the characteristics of the photosensitive composition of the present invention, as in the case of the above sensitizing dyes. For example, bonds with sensitizing dyes, titanocene, addition-polymerizable unsaturated compounds and other radical generating parts, introduction of hydrophilic sites, compatibility improvement, introduction of substituents to suppress crystal precipitation, substituents that improve 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 0.05 to 100 parts by mass, preferably 1 to 80 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated double bond.

Moreover, it is preferable that the photosensitive composition of this invention uses a radically polymerizable monomer together with the compound represented by the said general formula (1), (2) or (3).

The radical polymerizable monomer that can be used in the photosensitive composition of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably 2 It is selected from compounds having at least one. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These are, for example, monomers, prepolymers, i.e. dimers,
It has chemical forms such as trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.)
And esters thereof and amides. Preferably, amides of a carboxylic acid of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an aliphatic polyvalent amine compound are used.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group, and monofunctional or polyfunctional alcohols,
Addition reaction products with amines and thiols, as well as unsaturated carboxylic acid esters or amides having leaving groups such as halogen groups and tosyloxy groups, and monofunctional or polyfunctional alcohols, amines and thiols A substitution reaction product with is also suitable. 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) isocyanate, isocyanuric acid ethylene oxide (EO) modified triacrylate, polyester acrylate oligomer, and the like.

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. As crotonic acid ester,
Examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritolotonate 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, for example, Japanese Patent Publication No. 51-47334, Japanese Patent Laid-Open No. 57-19.
The aliphatic alcohol esters described in JP 6231 and the aromatic skeletons described in JP 59-5240, JP 59-5241, and JP 2-226149 Those having 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, xylylenemethacrylamide and the like. Examples of other preferable amide 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. The polyisocyanate compound having the following general formula (A)
And vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by the formula (1) is added.

_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH (A)
(However, R ₄ and R ₅ represent H or CH _3. )

JP-A-51-37193, JP-B-2-32293, JP-B-2-16
No. 765, urethane acrylates as described in Japanese Patent Publication No. 765, and Japanese Patent Publication No. 58-4986.
No. 0, JP-B 56-17654, JP-B 62-39417, JP-B 62
Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. -39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. Can be mentioned. 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, 300-3
Those introduced as photocurable monomers and oligomers on page 08 (1984) can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of the final photosensitive composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured product, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.

In addition, other components in the photosensitive composition (for example, a binder polymer, a radical polymerization initiator,
The selection and use of polymerizable compounds is also an important factor for compatibility and dispersibility with colorants, etc. For example, compatibility is improved by using low-purity compounds or using two or more types in combination. There is something that can be done.

The polymerizable compound is preferably 5 to 8 with respect to the total solid content of the photosensitive composition of the present invention.
It is used in the range of 0% by mass, more preferably 25-75% by mass. These may be used alone or in combination of two or more. In addition, as for the method of using the polymerizable compound, an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, and the like.

(Other photosensitive composition components)
The photosensitive composition of the present invention can further contain various additives as necessary. These will be described below.

[Surfactant]
In the photosensitive composition of the present invention, when used in the image forming layer of a lithographic printing plate precursor, it is preferable to use a surfactant in order to promote developability and improve the coated surface. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters,
Propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil , Polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, polyethylene And a copolymer of glycol and polypropylene glycol.

The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.
Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. JP-A-62-170950, JP-A-62-226143 and JP-A-60-168144.
Fluorosurfactants described in the publication of No. are also preferably mentioned.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 7% by mass with respect to the total solid content of the photosensitive composition.

<Hydrophilic polymer>
In the photosensitive composition of the present invention, a hydrophilic polymer can be contained in order to improve developability and microcapsule dispersion stability.
Examples of the hydrophilic polymer include hydroxy group, carboxyl group, carboxylate group, hydroxyethyl group, polyoxyethyl group, hydroxypropyl group, polyoxypropyl group, amino group, aminoethyl group, aminopropyl group, ammonium group, Preferred examples include those having a hydrophilic group such as an amide group, carboxymethyl group, sulfonic acid group, and phosphoric acid group.

Specific examples include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate,
Vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, hydroxy Homopolymers and copolymers of pyrrole methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, homopolymers and copolymers of hydroxybutyl methacrylate, homopolymers and copolymers of hydroxybutyl acrylate, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, water Decomposition degree is 60 mol% or more, preferably 80 mol%
Hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, homopolymers and copolymers of acrylamide, homopolymers and polymers of methacrylamide, homopolymers and copolymers of N-methylol acrylamide, polyvinyl pyrrolidone, alcohol soluble nylon, 2 , 2-bis-
And polyether of (4-hydroxyphenyl) -propane and epichlorohydrin.

The hydrophilic polymer preferably has a mass average molecular weight of 5000 or more, more preferably 10,000 to 300,000. The hydrophilic polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.
The content of the hydrophilic polymer in the photosensitive composition is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total solid content of the photosensitive composition.

[Colorant]
In the photosensitive composition of the present invention, a dye having a large absorption in the visible light region and an image colorant can be added. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Industrial Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555)
), Methyl violet (CI42535), ethyl violet, rhodamine B (CI)
145170B), malachite green (CI42000), methylene blue (CI52)
015) and the like, and dyes described in JP-A-62-293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.
When the photosensitive composition of the present invention is used for the image forming layer of the lithographic printing plate precursor, it is preferable to add these colorants since the image portion and the non-image portion can be easily distinguished after image formation. In addition, the addition amount has a preferable ratio of 0.01-10 mass% with respect to the photosensitive composition.

(Polymerization inhibitor)
It is preferable to add a small amount of a thermal polymerization inhibitor to the photosensitive composition of the present invention in order to prevent unnecessary thermal polymerization of the radical polymerizable compound during use or storage.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-
Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4
'-Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4
-Methyl-6-t-butylphenol) and N-nitroso-N-phenylhydroxylamine aluminum salts are preferred.
The addition amount of the thermal polymerization inhibitor is about 0.01 to about 5% by mass relative to the total solid content of the photosensitive composition.
Is preferred.

[Higher fatty acid derivatives, etc.]
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the photosensitive composition of the present invention, and it is applied to the surface of the coating layer during the drying process after coating. It may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably about 0.1 to about 10% by mass relative to the total solid content of the photosensitive composition.

[Plasticizer]
The photosensitive composition of the present invention may contain a plasticizer. Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate; Glycol esters such as glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioct Ruazereto, aliphatic dibasic acid esters such as dibutyl maleate; polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate in. The content of the plasticizer is about 30% by mass with respect to the total solid content of the photosensitive composition.
It is preferable that:

[Inorganic fine particles]
When the photosensitive composition of the present invention is used as an image forming layer of a lithographic printing plate precursor, it may contain inorganic fine particles in order to improve the strength of the cured film in the image area. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like. The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to form a non-image portion excellent in hydrophilicity that is stably dispersed in the photosensitive composition, sufficiently retains the film strength, and hardly causes stains during printing.

The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total solid content of the photosensitive composition.

[Low molecular hydrophilic compounds]
When the photosensitive composition of the present invention is used as an image forming layer of a lithographic printing plate precursor, it may contain a hydrophilic low molecular weight compound for improving on-press developability. Examples of the hydrophilic low-molecular compound include water-soluble organic compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof, organic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and the like Examples thereof include organic carboxylic acids such as salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, and amino acids, and salts thereof.

The photosensitive composition of the present invention can be used as a lithographic printing plate precursor by providing it as an image forming layer on a surface hydrophilic support.
As a method for applying the photosensitive composition of the present invention to the image forming layer of a lithographic printing plate precursor, several embodiments can be used. One is an aspect in which the constituent components are dissolved and applied in a suitable solvent as described in, for example, JP-A-2002-287334, and the other is, for example, JP-A-2001-277740, As described in JP-A-2001-277742, it is an embodiment (microcapsule type photosensitive-thermosensitive layer) in which the constituent components of the image forming layer are encapsulated in microcapsules and contained in the image forming layer. Further, in the microcapsule type image forming layer, the constituent component may be contained outside the microcapsule. In the microcapsule type image forming layer, it is a more preferable embodiment that the hydrophobic constituent component is encapsulated in the microcapsule and the hydrophilic constituent component is contained outside the microcapsule.

As a method for microencapsulating the above-mentioned image forming layer constituent components, known methods can be applied. For example, as a method for producing a microcapsule, a method using coacervation found in US Pat. Nos. 2,800,547 and 2,800,498, US Pat.
No. 287154, JP-B-38-19574, JP-A-42-446, a method based on an interfacial polymerization method, US Pat. Nos. 3,418,250 and 3,660,304, by precipitation of a polymer. US Pat. No. 3,796,669, US Pat. No. 3,796,669, US Pat. No. 3,914,511, US Pat. No. 3,914,511, US Pat.
No. 376, No. 4089802, a method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming material, US Pat. No. 40254
No. 45, a method using a wall material such as melamine-formaldehyde resin, hydroxycellulose, etc., an in situ method by monomer polymerization shown in JP-B Nos. 36-9163 and 51-9079, British Patent No. 930422, US Pat. No. 3,111,140
No. 7 spray drying method, British Patent Nos. 952807 and 9670
Although there is an electrolytic dispersion cooling method or the like found in each specification of No. 74, it is not limited thereto.

A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. Further, a compound having a crosslinkable functional group such as an ethylenically unsaturated bond capable of introducing the binder polymer may be introduced into the microcapsule wall.
The average particle size of the microcapsules is preferably 0.01 to 3.0 μm. 0.05 ~
2.0 μm is more preferable, and 0.10 to 1.0 μm is particularly preferable. Within this range, good resolution and stability over time can be obtained.
In the present invention, each component of the above-described image forming layer, particularly preferably each of the above-described infrared absorbers, may be included in resin fine particles.
Such an embodiment is achieved by preparing a resin fine particle dispersion obtained by dissolving each component in a solvent and then mixing it with a polymer solution (preferably a polymer aqueous solution) and a homogenizer or the like. it can.

Examples of the solvent that can be used at this time include ethyl acetate, methyl ethyl ketone (ME
K), diisopropyl ether, dichloromethane, chloroform, toluene, dichloroethane, and mixed solvents thereof.
Examples of the polymer include polyvinyl alcohol (PVA), polyacrylic acid, sodium polyacrylate, polyacrylamide, polymethacrylic acid, polysodium methacrylate, polymethacrylamide, polystyrene sulfonic acid, sodium polystyrene sulfonate, acrylic acid. Examples include, but are not limited to, methyl acrylate copolymer, methacrylic acid-methyl methacrylate copolymer, styrene-sodium styrene sulfonate copolymer and the like.
These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

The image-forming layer using the photosensitive composition of the present invention is formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeatedly applying and drying a plurality of times. It is also possible.
The coating amount (solid content) of the image forming layer on the support obtained after coating and drying varies depending on the use, but generally 0.3 to 3.0 g / m ² is preferable. Within this range, good sensitivity and good film properties of the image forming layer can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

[Protective layer]
The lithographic printing plate precursor using the photosensitive composition of the present invention for the image forming layer (hereinafter also referred to as the lithographic printing plate precursor of the present invention) is used to block the diffusion and penetration of oxygen that interferes with the polymerization reaction during exposure. ,
A protective layer (oxygen barrier layer) is preferably provided on the image forming layer. The protective layer used in the present invention has an oxygen permeability A of 1.0 ≦ A ≦ 20 (mL / m ² · day) at 25 ° C. and 1 atm.
It is preferable that When the oxygen permeability A is extremely low at less than 1.0 (mL / m ² · day), unnecessary polymerization reaction occurs at the time of production and raw storage, and unnecessary fogging and image streaking occur during image exposure. The problem that fatness arises arises. Conversely, the oxygen permeability A is 20 (mL / m ²
-If it is too high exceeding (day), the sensitivity is lowered. The oxygen permeability A is more preferably 1.5 ≦ A ≦ 12 (mL / m ² · day), and further preferably 2.0 ≦ A ≦ 10.0 (mL
/ M ² · day). In addition to the oxygen permeability described above, the properties desired for the protective layer further do not substantially inhibit the transmission of light used for exposure, and have excellent adhesion to the image forming layer.
It is also desirable that it can be easily removed in the development process after exposure. A device for such a protective layer has been conventionally used. US Pat. No. 3,458,311 and JP-B-55-49729
It is described in detail in the Gazette.

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, vinyl alcohol / vinyl phthalate copolymer, vinyl acetate / vinyl are used. Examples include water-soluble polymers such as alcohol / vinyl phthalate copolymer, vinyl acetate / crotonic acid copolymer, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, polyacrylic acid, and polyacrylamide. Or they can be mixed. Of these, the use of polyvinyl alcohol as the 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 mol% and a polymerization repeating unit in the range of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PV
A-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PV
A-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-61
3, L-8 and the like, and these can be used alone or in combination. As a preferred embodiment, the content of polyvinyl alcohol in the protective layer is 20 to 95% by mass, more preferably 30%.
90% by mass.

Moreover, well-known modified polyvinyl alcohol can also be used preferably. For example, various hydrophilic modification sites such as anion modification sites modified with anions such as carboxyl groups and sulfo groups, cation modification sites modified with cations such as amino groups and ammonium groups, silanol modification sites, and thiol modification sites are randomly selected. Polyvinyl alcohol having various degrees of polymerization, the anion-modified site, the cation-modified site, the silanol-modified site, the thiol-modified site, the alkoxyl-modified site, the sulfide-modified site, and the ester modification of vinyl alcohol and various organic acids. Examples thereof include polyvinyl alcohol having various polymerization degrees having various modified sites such as a site, an ester-modified site of the anion-modified site and alcohols, an epoxy-modified site, and the like.

As a component to be used by mixing with polyvinyl alcohol, polyvinyl pyrrolidone or a modified product thereof is preferable from the viewpoints of oxygen barrier properties and development removability, and the content in the protective layer is 3.
It is 5-80 mass%, Preferably it is 10-60 mass%, More preferably, it is 15-30 mass%.

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 higher the film thickness, the higher the oxygen barrier property and the more advantageous in terms of sensitivity. The molecular weight of the (co) polymer such as polyvinyl alcohol (PVA) can be in the range of 2000 to 10 million, preferably 2
A range of 10,000 to 3,000,000 is appropriate.

As another composition of the protective layer, glycerin, dipropylene glycol and the like can be added in an amount corresponding to several mass% with respect to the (co) polymer to provide flexibility. Anionic surfactants such as sodium acid salts; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers to the (co) polymer Mass% can be added.

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 image forming layer, film peeling due to insufficient adhesion tends to occur, and the separated portion 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, in U.S. Patent Application No. 292,501 and U.S. Patent Application No. 44,563, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer is contained in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and laminating on the image forming layer. 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 in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.

Further, the protective layer in the lithographic printing plate precursor according to the invention preferably contains an inorganic layered compound for the purpose of improving oxygen barrier properties and image forming layer surface protection. Here, the inorganic layered compound is a particle having a thin flat plate shape. For example, the following general formula A (B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂
[However, A is any of K, Na, and Ca, B and C are Fe (II), Fe (III)
, Mn, Al, Mg, or V, and D is Si or Al. And mica groups such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate and the like represented by the formula 3MgO.4SiO.H ₂ O.

In the mica group, examples of natural mica include muscovite, soda mica, phlogopite, biotite and sericite. As the synthetic mica, fluorine phlogopite KMg ₃ (AlSi ₃ O ₁₀
) F ₂ , Potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) Non-swelling mica such as F ₂ , and Na tetrasilicic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (N
_{a, Li) Mg 2 Li (} Si 4 O 10) F 2, montmorillonite of Na or Li hectorite _{(Na, Li) 1/8 Mg 2} /5 Li 1/8 (Si 4 O 10) F 2 , etc. Examples include swelling mica. Synthetic smectite is also useful.

In the present invention, among the inorganic layered compounds, fluorine-based swellable mica, which is a synthetic inorganic layered compound, is particularly useful. That is, this swelling synthetic mica and swellable viscosity minerals such as montmorillonite, saponite, hectorite, bentonite, etc.
It has a laminated structure composed of unit crystal lattice layers with a thickness of about ˜15 mm, and the substitution of metal atoms in the lattice is significantly larger than other viscosity minerals. As a result, the lattice layer is deficient in positive charges, and cations such as Na ⁺ , Ca ²⁺ and Mg ²⁺ are adsorbed between the layers in order to compensate for this. The cations present between these layers are called exchangeable cations and exchange with various cations. In particular, when the cation between the layers is Li ⁺ or Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small,
The mass ratio is preferably 5/1 to 1/100. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of these inorganic layered compounds is preferably the above-described mass ratio.

Next, an example of a general dispersion method of the inorganic layered compound used for the protective layer will be described. First, 5 to 10 parts by mass of the swellable layered compound mentioned above as a preferred inorganic layered compound is added to 100 parts by mass of water, and the mixture is thoroughly swelled and swollen, and then dispersed by a disperser. Examples of the disperser used here include various mills that disperse mechanically by applying a direct force, a high-speed stirring disperser having a large shearing force, and a disperser that provides high-intensity ultrasonic energy. Specifically, ball mills, sand grinder mills, visco mills, colloid mills, homogenizers, tisol bars, polytrons, homomixers, homoblenders, ketdy mills,
Examples thereof include a jet agitator, a capillary emulsifying device, a liquid siren, an electrostrictive ultrasonic generator, and an emulsifying device having a Paulman whistle. 5 to 1 of the inorganic layered compound dispersed by the above method
The dispersion of 0% by mass is highly viscous or gelled, and the storage stability is very good. When preparing a protective layer coating solution using this dispersion, it is preferably prepared by diluting with water and stirring sufficiently, and then blending with a binder solution.

In addition to the inorganic layered compound, known additives such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film can be added to the protective layer coating solution.
Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. A water-soluble (meth) acrylic polymer can also be added. Furthermore, a known additive for improving the adhesion to the image forming layer and the temporal stability of the coating solution may be added to the coating solution.

The protective layer coating solution thus prepared is applied onto the image forming layer provided on the support and dried to form a protective layer. The coating solvent can be appropriately selected in relation to the binder, but when a water-soluble polymer is used, it is preferable to use distilled water or purified water. The method for applying the protective layer is not particularly limited, and a known method such as the method described in US Pat. No. 3,458,311 or Japanese Patent Publication No. 55-49729 can be applied. . Specific examples of the protective layer include blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, and bar coating.

The coating amount of the protective layer is preferably in the range of 0.05 to 10 g / m ^{2 in} terms of the coating amount after drying. When the inorganic layered compound is contained, 0.1 to 0.5 g / More preferably in the range of m ² , 0.5 to 5 g when no inorganic layered compound is contained.
More preferably, it is in the range of / m ² .

[Support]
The support used for the lithographic printing plate precursor according to the invention is not particularly limited as long as it is a dimensionally stable plate-like hydrophilic support. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum,
Zinc, copper, etc.), plastic films (eg, 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 on which the above-mentioned metal is laminated or vapor-deposited. Preferable supports include a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of different elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. 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 preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology.
It may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm, and even more preferably from 0.2 to 0.3 mm.

Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it becomes easy to improve hydrophilicity and secure adhesion between the image forming layer and the support. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.
The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).

As a method for the mechanical surface roughening treatment, 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.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.

The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.
As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.
The conditions for anodizing treatment vary depending on the electrolyte used and cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5
-60 A / dm ² , voltage 1-100 V, electrolysis time 10 seconds to 5 minutes are preferred. The amount of the anodic oxide film to be formed is preferably 1.0 to 5.0 g / m ² , and 1.5 to 4.
More preferably, it is 0 g / m ² . Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained.

As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is, but for further improvement in adhesion to the upper layer, hydrophilicity, resistance to contamination, heat insulation and the like. If necessary, it contains a micropore enlargement treatment, a micropore sealing treatment, and a hydrophilic compound described in Japanese Patent Application Laid-Open Nos. 2001-253181 and 2001-322365. A surface hydrophilization treatment immersed in an aqueous solution can be selected as appropriate. Of course, these enlargement processing and sealing processing are not limited to those described above, and any conventionally known method can be performed.

Sealing treatment includes vapor sealing, single treatment with zirconic fluoride, treatment with an aqueous solution containing an inorganic fluorine compound such as treatment with sodium fluoride, vapor sealing with addition of lithium chloride, sealing with hot water. Hole processing is also possible.
Of these, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and sealing treatment with hot water are preferable.

As hydrophilization treatment, U.S. Pat. Nos. 2,714,066, 3,181,461,
There are alkali metal silicate methods as described in the specifications of US Pat. Nos. 3,280,734 and 3,902,734. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the method of treating with potassium zirconate fluoride described in JP-B 36-22063, US Pat. No. 3,276
No. 868, No. 4,153,461 and No. 4,689,272, and the like.

When using a support with insufficient surface hydrophilicity such as a polyester film as the support of the present invention, it is desirable to apply a hydrophilic layer to make the surface hydrophilic. As the hydrophilic layer, at least one element selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony, and a transition metal described in JP-A-2001-199175 A hydrophilic layer formed by coating a coating solution containing a colloid of oxide or hydroxide, or organic hydrophilicity obtained by crosslinking or pseudo-crosslinking an organic hydrophilic polymer described in JP-A-2002-79772 A hydrophilic layer having a hydrophilic matrix, a hydrophilic layer having an inorganic hydrophilic matrix obtained by sol-gel conversion comprising hydrolysis, condensation reaction of polyalkoxysilane, titanate, zirconate or aluminate, or a metal oxide A hydrophilic layer made of an inorganic thin film having a surface is preferred. Arbitrariness. Among these, a hydrophilic layer formed by applying a coating solution containing a silicon oxide or a hydroxide colloid is preferable.

Moreover, when using a polyester film etc. as a support body of this invention, it is preferable to provide an antistatic layer in the hydrophilic layer side of a support body, the opposite side, or both sides. In the case where the antistatic layer is provided between the support and the hydrophilic layer, it also contributes to improving the adhesion with the hydrophilic layer. As the antistatic layer, a polymer layer in which metal oxide fine particles or a matting agent are dispersed as described in JP-A-2002-79772 can be used.

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image forming layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as the reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.

(Undercoat layer)
In the lithographic printing plate precursor according to the invention, it is preferable to provide an undercoat layer of a compound containing a polymerizable group on a support. When an undercoat layer is used, the image forming layer is provided on the undercoat layer. The undercoat layer enhances the adhesion between the support and the image forming layer in the exposed portion, and in the unexposed portion, the image forming layer is easily peeled off from the support, so that the developability is improved. .

Specific examples of the undercoat layer include a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679,
The phosphorus compound etc. which have the ethylenic double bond reactive group of 304441 gazette etc. are mentioned suitably. Particularly preferred compounds include compounds having a polymerizable group such as a methacryl group and an allyl group and a support-adsorbing group such as a sulfonic acid group, a phosphoric acid group, and a phosphoric acid ester group. A compound having a hydrophilicity-imparting group such as an ethylene oxide group in addition to the polymerizable group and the support-adsorbing group can also be exemplified as a suitable compound.
The coating amount (solid content) of the undercoat layer is preferably 0.1 to 100 mg / m ² ,
More preferably, it is 30 mg / m ² .

[Back coat layer]
After the surface treatment is performed on the support or after the undercoat layer is formed, a back coat can be provided on the back surface of the support, if necessary.

Examples of the back coat include hydrolysis and polycondensation of organic polymer compounds described in JP-A-5-45885, organometallic compounds or inorganic metal compounds described in JP-A-6-35174. A coating layer made of a metal oxide obtained in this manner is preferred. Among them, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ S
It is preferable to use silicon alkoxy compounds such as i (OC ₄ H ₉ ) ₄ because the raw materials are inexpensive and easily available.

〔exposure〕
(1) The lithographic printing plate precursor according to the invention is used after imagewise exposure with an infrared laser. Although the infrared laser used in this case is not particularly limited, a solid laser and a semiconductor laser that emit infrared rays having a wavelength of 760 to 1200 nm are preferable. The output of the infrared laser is preferably 100 mW or more. In order to shorten the exposure time, it is preferable to use a multi-beam laser device.

The exposure time per pixel is preferably within 20 μsec. Moreover, it is preferable that irradiation energy amount is 10-300 mJ / cm < ² >.
(2) On the other hand, as a laser light source, a 405 nm or 830 nm semiconductor laser,
An FD-YAG laser or the like is used. In recent years, from the viewpoint of system cost and handleability, 4
CTP systems equipped with 05 nm semiconductor lasers are in widespread use.

The plate-making method of the lithographic printing plate precursor according to the invention is obtained by changing the above-described lithographic printing plate precursor from 360 nm to 450 nm.
By the plate making method using an inner drum exposure apparatus equipped with a light source having an oscillation wavelength in the range of nm, the exposure apparatus has a light beam spot shape of a light beam emitted from the light source, and the light beam is an ordinary ray and an extraordinary ray. And the two beam spots are arranged adjacent to each other in the sub-scanning direction so that they partially overlap each other, and after the lithographic printing plate precursor is placed on an inner drum exposure device, the light It is also possible to perform image recording by exposure with a beam spot shape.

The plate making process will be further described in detail.
In the present invention, as described above, the development treatment may be performed immediately after the exposure step, but a heat treatment step may be provided between the exposure step and the development step. This heat treatment has the effect of improving the printing durability and further improving the uniformity of the image curing degree within the plate surface, and the conditions can be appropriately set within the range where these effects are present. Examples of the heating means include a conventional convection oven, an IR irradiation device, an IR laser, a microwave device, a Wisconsin oven, and the like. Specifically, it can be carried out by holding the plate surface temperature in the range of 70 to 150 ° C. for 1 second to 5 minutes. Preferably, the temperature is 80 ° C to 140 ° C for 5 to 1 minute, more preferably 90 ° C to 130 ° C for 10 to 30 seconds. This range is preferable in that the above effect can be obtained efficiently and there is no adverse effect such as deformation of the printing plate due to heat.
In the present invention, a development processing step is performed after the above-described exposure step and preferably the heat treatment step to obtain a lithographic printing plate. The plate setter used in the exposure process, the heat treatment means used in the heat treatment, and the developing device used in the development process are preferably connected to each other and automatically continuously processed. Specifically, it is a plate making line in which a plate setter and a developing device are coupled by a conveying means such as a conveyor. A heat treatment unit may be provided between the plate setter and the developing device, and the heating unit and the developing device may be integrated.

When the printing plate to be used is easily affected by ambient light in the work environment, it is preferable that the plate making line is shielded by a filter or a cover.
After the image is formed as described above, the entire surface may be exposed with an actinic ray such as ultraviolet light to accelerate the curing of the image area. Examples of the light source for the entire surface exposure include a carbon arc lamp, a mercury lamp, a gallium lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, and various laser lights. Further, in order to obtain a sufficient printing durability, the overall exposure is preferably at least 10 mJ / cm ² or more, more preferably 100 mJ / cm ² or more.
Heating may be performed simultaneously with the entire surface exposure, and further improvement in printing durability is recognized by heating. Examples of the heating device include a conventional convection oven, an IR irradiation device, an IR laser, a microwave device, a Wisconsin oven, and the like. At this time, the plate surface temperature is preferably 30 ° C to 150 ° C, more preferably 35 ° C to 130 ° C, and still more preferably 40 ° C to 120 ° C.

[Printing method]
In the case of the above (1), the lithographic printing plate precursor of the present invention is imagewise exposed with an infrared laser and heated entirely by the above-described method, and then the oil-based ink and the aqueous component are mixed without any development processing steps. Can be supplied and printed.

Specifically, the lithographic printing plate precursor is exposed with an infrared laser, and the entire surface of the plate is heated in an oven, and then mounted on a printing press without passing through a development processing step. And a method of printing without passing through a development processing step after exposing the entire surface of the plate on the printing machine.

For example, in an embodiment of a negative on-press development type lithographic printing plate precursor, an aqueous component and an oily composition are exposed without undergoing a development processing step such as a wet development processing step after exposing the lithographic printing plate precursor imagewise with an infrared laser. When ink is supplied and printing is performed, in the exposed portion of the image forming layer, the image forming layer cured by exposure forms an oil-based ink receiving portion having a lipophilic surface. On the other hand, in the unexposed area, the uncured image forming layer is dissolved or dispersed and removed by the supplied aqueous component and / or oil-based ink, and a hydrophilic surface is exposed in that area.

As a result, the aqueous component adheres to the exposed hydrophilic surface, and the oil-based ink is exposed to the photosensitive region in the exposed area.
The heat-sensitive layer is deposited and printing is started. Here, an aqueous component or an oil-based ink may be first supplied to the plate surface, but the oil-based ink is firstly used in order to prevent the aqueous component from being contaminated by the light-sensitive layer in the unexposed area. Is preferably supplied. As the aqueous component and oil-based ink, a dampening water and printing ink for ordinary lithographic printing are used.
In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.

In the case of the above (2), in the plate-making method of the lithographic printing plate precursor according to the present invention, after exposure, the plate surface is rubbed with a rubbing member in the presence of a developer having a pH of 2 to 10 by an automatic processor equipped with a rubbing member. By rubbing, the image forming layer in the non-exposed area is removed to obtain a lithographic printing plate.
In the present invention, as described above, the exposed lithographic printing plate precursor may be entirely heated between exposure and development as necessary. By such heating, an image forming reaction in the image forming layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. In addition, when a protective layer is provided on the image forming layer, it is also preferable to perform a water washing treatment before the development treatment.
In the present invention, the lithographic printing plate after the rubbing treatment can be optionally washed with water, dried and desensitized. In the desensitizing treatment, a known desensitizing solution can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. In addition, Examples 2-3, 5, 7-8, 11, 13-17, and 22 shall be read as “reference examples”.

[Example 1]
(Preparation of hydrophilic support)
Using an aluminum plate according to JIS-A-1050 having a thickness of 0.3 mm, the following steps (a) to (k) were performed in this order.

(A) Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12 and water as an abrasive slurry to the surface of aluminum, it is mechanically rotated by a rotating nylon nylon brush. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of nylon brush is 6
10 nylon, hair length 50 mm, hair diameter was 0.3 mm. Nylon brush is Φ3
A hole was made in a 00 mm stainless steel tube so that it was densely planted. Three rotating brushes were used. The distance between the two support rollers (Φ200 mm) at the bottom of the brush was 300 mm.
The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The obtained aluminum plate was sprayed with an aqueous NaOH solution at a temperature of 70 ° C. (concentration: 26 mass%, aluminum ion concentration: 6.5 mass%) to carry out an etching treatment.
Dissolved in g / m ² . Thereafter, washing with water was performed using well water.
(C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a nitric acid 10.5 g / liter aqueous solution (aluminum ion 5 g / liter) at a temperature of 50 ° C. AC power supply waveform has zero time TP until the current value reaches the peak from zero
. Using a trapezoidal rectangular wave alternating current for 8 ms, a DUTY ratio of 1: 1, an electrochemical roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, washing with water was performed using well water.

(E) Alkaline etching treatment An aluminum plate is made of caustic soda concentration of 26% by mass and aluminum ion concentration of 6.5% by mass.
The etching process by spraying is performed at 32 ° C., 0.20 g / m ^{2 of} aluminum plate is dissolved, and the aluminum hydroxide produced when electrochemical roughening is performed using alternating current in the previous stage is mainly used. The smut component was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water. The etching amount was 3.5 g / m ² .
(F) Desmutting treatment A 15% by mass aqueous solution of nitric acid having a temperature of 30 ° C. (including 4.5% by mass of aluminum ions)
Then, the desmut treatment was performed by spraying, and then washed with water using well water.
The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time is a 7.5 g / liter aqueous solution of hydrochloric acid (containing 5 g / liter of aluminum ions).
The temperature was 35 ° C. The AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Thereafter, washing with water was performed using well water.
(H) Alkaline etching treatment An aluminum plate is made with caustic soda concentration of 26% by mass and aluminum ion concentration of 6.5% by mass.
Etching treatment by spraying at 32 ° C., dissolving 0.10 g / m ^{2 of} aluminum plate, and mainly using aluminum hydroxide produced when electrochemical surface roughening treatment was performed using alternating current in the previous stage. The smut component to be removed was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.

(I) Desmutting treatment An aqueous solution containing 25% by mass of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions)
A desmut treatment was performed, and then water was washed by spraying using well water.
(J) Anodizing treatment As the electrolytic solution, sulfuric acid was used. All electrolytes had a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), and the temperature was 43 ° C. Then use well water
Then, water washing by spray was performed. Both current densities were about 30 A / dm ² . The final chemical film coating amount was 2.7 g / m ² .
(K) Alkali metal silicate treatment An alkali metal silicate treatment (silicate treatment) was performed by immersing the obtained aluminum plate in a treatment layer of a 1 mass% aqueous solution of sodium silicate No. 3 at a temperature of 30 ° C. for 10 seconds. ) Then, the aluminum support body is produced by performing the water washing by the spray using well water. The amount of silicate adhering at that time was 3.6 mg / m ² .

Creation of lithographic printing plate precursor (1) (formation of lower layer)
On the obtained support, a copolymer represented by the following polymer compound (1) (mass average molecular weight 3
5000) methanol solution was applied with a wire bar and dried at 80 ° C. for 60 seconds to form a lower layer. The coating amount was 0.01 g / m ² .

(Formation of image forming layer)
Subsequently, the image-forming layer coating solution (1) having the following composition was bar-coated and then oven-dried at 70 ° C. for 60 seconds to form an image-forming layer having a dry coating amount of 1.0 g / m ² to form a lithographic printing plate. Original version (
1) was obtained.

Image forming layer coating solution (1)
・ The following binder polymer (1) 0.50 g
・ Polymerizable compound 1.00g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The following polymerization initiator (1) 0.20 g
・ The following infrared absorber (1) 0.05 g
・ IM-577 (as solid content) 0.18g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

[Example 2]
Preparation of lithographic printing plate precursor (2) A lithographic printing plate precursor (2) in the same manner as the lithographic printing plate precursor (1) except that the image forming layer coating solution (1) is changed to the following image forming layer coating solution (2). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 0.9 g / m ² .

Image forming layer coating solution (2)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 1.00g
Dipentaerythritol pentaacrylate ・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ IM-454 0.12g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

Example 3
Preparation of the lithographic printing plate precursor (3) The lithographic printing plate precursor (3) was prepared in the same manner as the lithographic printing plate precursor (1) except that the image forming layer coating solution (1) was changed to the following image forming layer coating solution (3). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.1 g / m ² .

Image forming layer coating solution (3)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 0.50g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ IM-046 0.60g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

Example 4
Preparation of lithographic printing plate precursor (4) The lithographic printing plate precursor (4) was prepared in the same manner as the lithographic printing plate precursor (1) except that the image forming layer coating solution (1) was changed to the following image forming layer coating solution (4). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.0 g / m ² .

Image forming layer coating solution (4)
・ Binder polymer (1) 0.50g
・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ IM-580 1.00g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

Example 5
Preparation of lithographic printing plate precursor (5) A lithographic printing plate precursor (5) was prepared in the same manner as the lithographic printing plate precursor (1) except that the image forming layer coating solution (1) was changed to the following image forming layer coating solution (5). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.0 g / m ² .

Image forming layer coating solution (5)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 1.00g
Dipentaerythritol pentaacrylate ・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ IM-029 0.15g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

[Comparative Example 1]
Preparation of lithographic printing plate precursor (6) The lithographic printing plate precursor (6) was prepared in the same manner as the lithographic printing plate precursor (1) except that the image forming layer coating solution (1) was changed to the following image forming layer coating solution (6). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.0 g / m ² .

Image forming layer coating solution (6)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 1.18 g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The following polymerization initiator (1) 0.20 g
・ The following infrared absorber (1) 0.05 g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

[Comparative Example 2]
Preparation of lithographic printing plate precursor (7) The lithographic printing plate precursor (7) was prepared in the same manner as the lithographic printing plate precursor (1) except that the image forming layer coating solution (1) was changed to the following image forming layer coating solution (7). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.0 g / m ² .

Image forming layer coating solution (7)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 1.12 g
・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

Example 6
Preparation of lithographic printing plate precursor (8) (formation of lower layer)
On the aluminum support obtained as described above, a methanol solution of the copolymer (mass average molecular weight 35000) represented by the polymer compound (1) was applied with a wire bar, and dried at 80 ° C. for 60 seconds. To form a lower layer. The coating amount was 0.02 g / m ² .

(Synthesis of microcapsule (1))
As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., SR444) 3.15 g, The following infrared absorber (2) 0.3
5 g and 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) were dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The microcapsule liquid (1) thus obtained was diluted with distilled water so that the solid content concentration became 20% by mass. All of the average particle diameters were 0.3 μm.

(Formation of image forming layer)
Subsequently, an image-forming layer coating solution (8) having the following composition was bar-coated, followed by oven-drying at 70 ° C. for 60 seconds to form an image-forming layer having a dry coating amount of 1.1 g / m ² to form a lithographic printing plate. Original version (
8) was obtained.

Image forming layer coating solution (8)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 1.00g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The above polymerization initiator (1) 0.20 g
・ 0.05 g of the above infrared absorber (2)
・ Microcapsule liquid (1) 2.00g
・ IM-577 (as solid content) 0.15g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

Example 7
Preparation of lithographic printing plate precursor (9) The lithographic printing plate precursor (9) was prepared in the same manner as the lithographic printing plate precursor (8) except that the image forming layer coating solution (8) was changed to the following image forming layer coating solution (9). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.1 g / m ² .

Image forming layer coating solution (9)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 0.80g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ Microcapsule liquid (1) 2.00g
・ IM-046 0.35g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

[Comparative Example 3]
Preparation of lithographic printing plate precursor (10) The lithographic printing plate precursor (10) was prepared in the same manner as the lithographic printing plate precursor (8) except that the image forming layer coating solution (8) was changed to the following image forming layer coating solution (10). )created. The image forming layer of the obtained lithographic printing plate precursor had a coating amount of 1.0 g / m ² .

Image forming layer coating solution (10)
・ Binder polymer (1) 0.50g
・ Polymerizable compound 1.15 g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ Microcapsule liquid (1) 2.00g
・ The following fluorosurfactant (1) 0.05g
・ 1-Methoxy-2-propanol 18.00g

Example 8
Preparation of lithographic printing plate precursor (11) (formation of lower layer)
On the aluminum support obtained as described above, a methanol solution of the copolymer (mass average molecular weight 35000) represented by the polymer compound (1) was applied with a wire bar, and dried at 80 ° C. for 60 seconds. To form a lower layer. The coating amount was 0.02 g / m ² .
(Formation of image forming layer)
An image-forming layer coating solution (11) having the following composition is bar-coated on the support having an undercoat layer, and then oven-dried at 100 ° C. for 60 seconds to form an image having a dry coating amount of 1.1 g / m ² . A layer was formed. The image forming layer coating solution (11) was obtained by mixing and stirring the following photosensitive solution (1) and microcapsule solution (2) immediately before coating.

Photosensitive solution (1)
・ The binder polymer (1) 0.162 g
・ The above polymerization initiator (1) 0.160 g
・ The following polymerization initiator (2) 0.180 g
・ The following infrared absorber (3) 0.020 g
・ Polymerizable compound 0.385 g
Aronix M-215 (manufactured by Toa Gosei Co., Ltd.)
・ IM-454 0.060g
・ 0.044 g of the above fluorosurfactant (1)
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.210 g

Microcapsule liquid (2)
-Microcapsule (2) synthesized as follows: 2.640 g
・ Water 2.425g

Synthesis of microcapsule (2) As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate D-110N, 75 mass% ethyl acetate solution) 10 g, Aronix SR-399 ( Toagosei Co., Ltd.) 6.00 g and Pionein A-41C (Takemoto Yushi Co., Ltd.) 0.12 g were dissolved in ethyl acetate 16.67 g. PVA- as water phase component
37.5 g of a 4% by weight aqueous solution of 205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to distilled water 2
The mixture was added to 5 g, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 2 hours. The microcapsule solution thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass.
The average particle size was 0.2 μm.

The following protective layer coating solution (1) is bar-coated on the image forming layer, followed by oven drying at 125 ° C. for 75 seconds to form a protective layer having a dry coating amount of 0.15 g / m ² to form a lithographic printing plate precursor Got.

Protective layer coating solution (1)
・ Polyvinyl alcohol (6% by mass aqueous solution) 2.24 g
Kuraray PVA105, degree of saponification 98.5 mol%, degree of polymerization 500)
・ Polyvinylpyrrolidone (K30) 0.0053g
-Surfactant (Emalex 710 manufactured by Kao Corporation) 1 mass% aqueous solution 2.15 g
Scale-like synthetic mica (3.4% by mass aqueous dispersion) 3.75 g
(MEB3L manufactured by UNICOO Co., Ltd., average particle diameter of 1 to 5 μmΦ)
・ Distilled water 10.60g

Example 9
Preparation of lithographic printing plate precursor (12) A lithographic printing plate precursor (12) was prepared in the same manner as the lithographic printing plate precursor (11) except that the photosensitive solution (1) was changed to the following photosensitive solution (2). The resulting lithographic printing plate precursor had an image forming layer of 1.2.
The coating amount was g / m ² .

Photosensitive solution (2)
・ The binder polymer (1) 0.162 g
・ The above polymerization initiator (1) 0.160 g
-0.180 g of the above polymerization initiator (2)
・ 0.020 g of the above infrared absorber (3)
・ Polymerizable compound 0.185g
Aronix M-215 (manufactured by Toa Gosei Co., Ltd.)
・ IM-580 0.260g
・ 0.044 g of the above fluorosurfactant (1)
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.210 g

[Comparative Example 4]
Preparation of lithographic printing plate precursor (13) A lithographic printing plate precursor (13) was prepared in the same manner as the lithographic printing plate precursor (11) except that the photosensitive solution (1) was changed to the following photosensitive solution (3). The resulting lithographic printing plate precursor has an image forming layer of 1.0.
The coating amount was g / m ² .

Photosensitizer (3)
・ The binder polymer (1) 0.162 g
・ The above polymerization initiator (1) 0.160 g
・ Polymerization initiator (2) 0.180 g
・ 0.020 g of the above infrared absorber (3)
・ Polymerizable compound 0.385 g
Aronix M-215 (manufactured by Toa Gosei Co., Ltd.)
・ 0.044 g of the above fluorosurfactant (1)
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.210 g

2. Exposure and printing The above-mentioned lithographic printing plate precursors are manufactured by Creo Corporation equipped with a water-cooled 40W infrared semiconductor laser.
The exposure was performed using an ndsetter 3244VX under conditions of an output of 9 W, an outer drum rotation speed of 210 rpm, and a resolution of 2400 dpi. The obtained exposed original plate was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. Dampening solution (EU-3 (Etch solution manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G (N) black ink (Dainippon Ink and Chemicals, Inc.) After supplying dampening water and ink, printing was performed at a printing speed of 6000 sheets per hour.

3. Evaluation (1) Developability The on-machine developability is the number of print sheets required until the on-press development on the printing press of the unexposed portion of the image recording layer is completed and the ink is not transferred to the print paper. Measured.
(2) Printing durability As described above, as the number of printed sheets was increased, the image recording layer was gradually worn out and the ink acceptability was lowered, so that the ink density in the printing paper was lowered. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing.
Table 2 shows the evaluation results of (1) and (2) for each example and comparative example.

As is clear from Table 1, by using the compound represented by the general formula (1), (2) or (3) of the present invention, developability and printing durability compared to a lithographic printing plate precursor not used. Improves.

Example 10
(Production of support)
In order to remove rolling oil on the surface of an aluminum plate (material 1050) having a thickness of 0.3 mm, 1
After degreasing treatment at 50 ° C. for 30 seconds using a 0 mass% sodium aluminate aqueous solution, three bundle-planted nylon brushes having a bristle diameter of 0.3 mm and a pumice-water suspension having a median diameter of 25 μm (specific gravity 1
. 1 g / cm ³ ), and the aluminum surface was grained and washed thoroughly with water. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time is a 1% by mass aqueous solution of nitric acid (containing 0.5% by mass of aluminum ions), a liquid temperature of 5
It was 0 ° C. In the AC power supply waveform, the time TP until the current value reaches the peak from zero is 0.
An electrochemical roughening treatment was performed using a trapezoidal rectangular wave alternating current of 8 msec, a duty ratio of 1: 1, and a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
The amount of electricity in the nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode.
Then, water washing by spraying was performed.

Next, a 0.5 mass% hydrochloric acid aqueous solution (containing 0.5 mass% aluminum ions), a liquid temperature of 50
An electrolytic surface roughening treatment was performed in the same manner as in nitric acid electrolysis under the conditions of an electrolytic amount of 50 ° C./dm ² when the aluminum plate was an anode when the aluminum plate was an anode, and then washed with water by spraying. .
The plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using 15% by mass sulfuric acid (containing 0.5% by mass of aluminum ions) as an electrolytic solution, then washed with water and dried.
The centerline average roughness Ra (JIS B0601) of the surface of the support thus obtained is 2 in diameter.
It was 0.51 μm when measured using a μm needle.

Furthermore, after applying the following undercoat liquid (1) to a bar, it was oven-dried at 80 ° C. for 10 seconds to apply a dry coating amount of 10 mg / m ² , and a support having an undercoat layer used in the following experiments. Produced.

<Undercoat liquid (1)>
・ Undercoat compound (1) 0.017 g
・ Methanol 9.00 g
・ Water 1.00g

Preparation of lithographic printing plate precursor (14) On the support provided with the above-mentioned undercoat layer, an image-forming layer coating solution (14) having the following composition was bar-coated and then oven-dried at 70 ° C for 60 seconds, followed by dry coating. A photosensitive layer having an amount of 1.1 g / m ² was formed, and a protective layer coating solution (2) having the following composition was applied thereon using a bar so that the dry coating amount was 0.75 g / m ² . After that, it is dried at 125 ° C. for 70 seconds, and then the planographic printing plate precursor (14
)

(Image forming layer coating solution (14))
-0.54g of the following binder polymer (1)
・ Polymerizable compound 0.40g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
・ Polymerizable compound Ethoxylated trimethylolpropane triacrylate 0.08 g
(Nippon Kayaku Co., Ltd., SR9035, EO addition mole number 15, molecular weight 1000)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate / 1-methoxy-2-propanol = 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt, the following water-soluble fluorosurfactant (1) 0.001 g
・ IM-577 0.05g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

(Protective layer coating solution (2))
Polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) 40 g
Polyvinylpyrrolidone (molecular weight 50,000) 5g
Poly (vinyl pyrrolidone / vinyl acetate (1/1)) molecular weight 70,000 0.5g
Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.5g
950g of water

Furthermore, when the oxygen permeability of the protective layer was measured under the following conditions, the oxygen permeability of the protective layer was 3.8 ml / (m ² · day · atom).

Example 11
Preparation of lithographic printing plate precursor (15) A lithographic printing plate precursor (15) was prepared in the same manner as the lithographic printing plate precursor (14) except that the image forming layer coating solution (14) was changed to the image forming layer coating solution (15) shown below. 15) was created. The image forming layer of the obtained lithographic printing plate precursor (15) had a dry coating amount of 1.1 g / m ² .

(Image forming layer coating solution (15))
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.48g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate / 1-methoxy-
2-propanol = 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-454 0.05g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Example 12
Preparation of lithographic printing plate precursor (16) A lithographic printing plate precursor (14) was prepared in the same manner as the lithographic printing plate precursor (14) except that the image forming layer coating solution (14) was changed to the image forming layer coating solution (16) shown below. 16) was prepared. The image forming layer of the obtained lithographic printing plate precursor (16) had a dry coating amount of 1.2 g / m ² .

(Image forming layer coating solution (16))
・ Binder polymer (1) 0.54g
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate / 1-methoxy-
2-propanol = 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-580 0.53g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Example 13
Preparation of lithographic printing plate precursor (17) A lithographic printing plate precursor (14) was prepared in the same manner as the lithographic printing plate precursor (14) except that the image forming layer coating solution (14) was changed to the image forming layer coating solution (17) shown below. 17) was created. The image forming layer of the resulting lithographic printing plate precursor (17) had a dry coating amount of 1.1 g / m ² .

(Image forming layer coating solution (17))
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.30g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass, dissolved
Agent Cyclohexanone / Methoxypropyl Acetate / 1-Methoxy-2
-Propanol = 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-046 0.23g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Example 14
Preparation of the lithographic printing plate precursor (18) The lithographic printing plate precursor (14) was prepared in the same manner as the lithographic printing plate precursor (14) except that the image forming layer coating solution (14) was changed to the 3.5 g image forming layer coating solution (18) shown below. A printing plate precursor (18) was prepared. The image forming layer of the obtained lithographic printing plate precursor (18) had a dry coating amount of 1.1 g / m ² .

(Image forming layer coating solution (18))
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.40g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
・ Polymerizable compound 0.08g
Ethoxylated trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., SR9035, EO addition mole number 15,
Molecular weight 1000)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate /
1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-029 0.23g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

[Comparative Example 5]
Preparation of lithographic printing plate precursor (19) A lithographic printing plate precursor (14) was prepared in the same manner as the lithographic printing plate precursor (14) except that the image forming layer coating solution (14) was changed to the image forming layer coating solution (19) shown below. 19) was created. The image forming layer of the obtained lithographic printing plate precursor (19) had a dry coating amount of 1.0 g / m ² .

(Image forming layer coating solution (19))
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.40g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
・ Polymerizable compound 0.08g
Ethoxylated trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., SR9035, EO addition mole number 15,
Molecular weight 1000)
・ The following sensitizing dye (1) 0.06 g
-0.07 g of the following polymerization initiator (1)
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt ・ The following water-soluble fluorosurfactant (1) 0.001 g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Example 15
Preparation of lithographic printing plate precursor (20) Except for changing the image forming layer coating solution (14) to an image forming layer coating solution (20) having the following composition, the same procedure as in the preparation of the lithographic printing plate precursor (14) was performed. A lithographic printing plate precursor (20) was obtained. The image forming layer of the obtained lithographic printing plate precursor (20) had a dry coating amount of 1.1 g / m ² .

<Image forming layer coating solution (20)>
・ The above polymerization initiator (1) 0.20 g
-Sensitizing dye (1) 0.10 g
・ Binder polymer (1) 3.00 g
・ Polymerizable compound 6.20 g
Isocyanuric acid EO-modified diacrylate (Aronix M-215 manufactured by Toa Gosei Co., Ltd.)
・ Royco Crystal Violet 0.20g
・ 0.10 g of the above-mentioned fluorosurfactant (1)
・ The following microcapsule liquid (3) 25.00 g
・ IM-039 0.11g
・ Methyl ethyl ketone 35.00g
・ 1-methoxy-2-propanol 35.00g

(Synthesis of microcapsule (3))
As oil phase components, trimethylolpropane and xylene diisocyanate adduct (Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, isocyanuric acid EO-modified diacrylate (Toa Gosei Co., Ltd. Aronix M-215) 4 .15 g, and Pionein A-
0.1 g of 41C (manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 17 g of ethyl acetate. PV as water phase component
40 g of a 4% by mass aqueous solution of A-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to distilled water 2
The mixture was added to 5 g, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The microcapsule liquid (3) thus obtained was diluted with distilled water so that the solid content concentration became 20% by mass. The average particle size was 0.25 μm.

Example 16
Preparation of lithographic printing plate precursor (21) Except that the image forming layer coating solution (14) was changed to an image forming layer coating solution (21) having the following composition, the same procedure as in the preparation of the lithographic printing plate precursor (14) was performed. A lithographic printing plate precursor (21) was obtained. The image forming layer of the obtained lithographic printing plate precursor (21) had a dry coating amount of 1.2 g / m ² .

<Image forming layer coating solution (21)>
・ The above polymerization initiator (1) 0.20 g
-Sensitizing dye (1) 0.10 g
・ Binder polymer (1) 3.00 g
・ Polymerizable compound 6.00 g
Isocyanuric acid EO-modified diacrylate (Aronix M-215 manufactured by Toa Gosei Co., Ltd.)
・ Royco Crystal Violet 0.20g
・ 0.10 g of the above-mentioned fluorosurfactant (1)
・ The above microcapsule liquid (3) 25.00 g
・ IM-521 0.31g
・ Methyl ethyl ketone 35.00g
・ 1-methoxy-2-propanol 35.00g

Example 17
Preparation of lithographic printing plate precursor (22) Except that the image forming layer coating solution (14) was changed to an image forming layer coating solution (22) having the following composition, the same procedure as in the preparation of the lithographic printing plate precursor (14) was performed. A lithographic printing plate precursor (22) was obtained. The image forming layer of the obtained lithographic printing plate precursor (22) had a dry coating amount of 1.1 g / m ² .

<Image forming layer coating solution (22)>
・ The above polymerization initiator (1) 0.20 g
-Sensitizing dye (1) 0.10 g
・ Binder polymer (1) 3.00 g
・ Polymerizable compound 5.80 g
Isocyanuric acid EO-modified diacrylate (Aronix M-215 manufactured by Toa Gosei Co., Ltd.)
・ Royco Crystal Violet 0.20g
・ 0.10 g of the above-mentioned fluorosurfactant (1)
・ The above microcapsule liquid (3) 35.00 g
・ IM-366 0.51g
・ Methyl ethyl ketone 35.00g
・ 1-methoxy-2-propanol 35.00g

Example 18
Preparation of lithographic printing plate precursor (23) Except that the image forming layer coating solution (14) was changed to the image forming layer coating solution (23) having the following composition, A lithographic printing plate precursor (23) was obtained. The image forming layer of the obtained lithographic printing plate precursor (23) had a dry coating amount of 1.2 g / m ² .

<Image forming layer coating solution (23)>
・ The above polymerization initiator (1) 0.20 g
-Sensitizing dye (1) 0.10 g
・ Binder polymer (1)
・ Royco Crystal Violet 0.20g
・ 0.10 g of the above-mentioned fluorosurfactant (1)
・ The above microcapsule liquid (3) 25.00 g
・ IM-615 6.31g
・ Methyl ethyl ketone 35.00g
・ 1-methoxy-2-propanol 35.00g

[Comparative Example 6]
Preparation of lithographic printing plate precursor (24) Except that the image forming layer coating solution (14) was changed to an image forming layer coating solution (24) having the following composition, A lithographic printing plate precursor (24) was obtained. The image forming layer of the obtained lithographic printing plate precursor (24) had a dry coating amount of 1.0 g / m ² .

<Image forming layer coating solution (24)>
・ The above polymerization initiator (1) 0.20 g
-Sensitizing dye (1) 0.10 g
・ Binder polymer (1) 3.00 g
・ Polymerizable compound 6.00 g
Isocyanuric acid EO-modified diacrylate (Aronix M-215 manufactured by Toa Gosei Co., Ltd.)
・ Royco Crystal Violet 0.20g
・ 0.10 g of the above-mentioned fluorosurfactant (1)
・ The above microcapsule liquid (3) 25.00 g
・ Methyl ethyl ketone 35.00g
・ 1-methoxy-2-propanol 35.00g

Example 19
Preparation of planographic printing plate precursor (25) The image forming layer coating solution (14) is changed to an image forming layer coating solution (25) having the following composition, and the protective layer coating solution (2) is protected layer having the following composition. Change to (3), the dry coating amount is 0.2 g /
A lithographic printing plate precursor (25) was obtained in the same manner as in the production of the lithographic printing plate precursor (14) except that it was applied using a bar so as to be m ² . The image forming layer of the resulting lithographic printing plate precursor (25) had a dry coating amount of 1.1 g / m ² .

<Image forming layer coating solution (25)>
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.25g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-573 0.28g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Protective layer coating solution (3)
・ The following mica dispersion (1): 13.00 g
Polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) 1.30 g
-Sodium 2-ethylhexyl sulfosuccinate 0.20 g
・ Poly (vinyl pyrrolidone / vinyl acetate = 1/1) molecular weight 70,000 g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.05g
・ Water 33.00g

(Preparation of mica dispersion (1))
To 368 g of water, 32 g of synthetic mica (“Somasif ME-100”: manufactured by Co-op Chemical Co., Ltd., aspect ratio: 1000 or more) is added and dispersed using an homogenizer until the average particle size (laser scattering method) is 0.5 μm. A mica dispersion (1) was obtained.

Example 20
Preparation of lithographic printing plate precursor (26) Except that the image forming layer coating solution (25) was changed to an image forming layer coating solution (26) having the following composition, the production of the lithographic printing plate precursor (25) was performed, A lithographic printing plate precursor (26) was obtained. The image forming layer of the obtained lithographic printing plate precursor (26) had a dry coating amount of 1.2 g / m ² .

<Image forming layer coating solution (26)>
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.30g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-611 0.23g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Example 21
Preparation of lithographic printing plate precursor (27) Except that the image forming layer coating solution (25) was changed to an image forming layer coating solution (27) having the following composition, A lithographic printing plate precursor (27) was obtained. The image forming layer of the resulting lithographic printing plate precursor (27) had a dry coating amount of 1.1 g / m ² .

<Image forming layer coating solution (27)>
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.40g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-667 0.13g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

[Comparative Example 7]
Preparation of lithographic printing plate precursor (28) Except for changing the image forming layer coating solution (25) to an image forming layer coating solution (28) having the following composition, A lithographic printing plate precursor (28) was obtained. The image forming layer of the obtained lithographic printing plate precursor (28) had a dry coating amount of 1.1 g / m ² .

<Image forming layer coating solution (28)>
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.53g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

[Example 22]
Preparation of lithographic printing plate precursor (29) On the following support 3, an image forming layer coating solution (29) having the following composition was applied by bar coating, followed by 70 ° C,
Oven-dried in 60 seconds to form an image forming layer having a dry coating amount of 1.1 g / m ² , and a protective layer coating solution (2) having the above composition is formed on the image forming layer, and the dry coating amount is 0.75 g / m ^2. After coating using a bar, the plate was dried at 125 ° C. for 70 seconds to obtain a lithographic printing plate precursor (29).

<Image forming layer coating solution (29)>
-0.54g of the following binder polymer (1)
・ Polymerizable compound 0.40g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
・ Polymerizable compound 0.08g
Ethoxylated trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., SR9035, EO addition mole number 15,
Molecular weight 1000)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate / 1-methoxy-2-propanol = 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt ・ The following water-soluble fluorosurfactant (1) 0.001 g
・ IM-021 0.05g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Production of Support 3 An aluminum plate having a thickness of 0.3 mm was etched by being immersed in 10% by weight sodium hydroxide at 60 ° C. for 25 seconds, washed with running water, neutralized and washed with 20% by weight 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. Anodization was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² under the condition of dm ² . The centerline average roughness (Ra) of the surface was measured and found to be 0.3 μm.

After applying the following undercoat liquid (2) to the aluminum plate thus treated with a bar, 80
It was oven-dried at 20 ° C. for 20 seconds, and coated so that the dry coating amount was 10 mg / m ² to prepare a support.

Undercoat liquid (2)
・ 100g of the following sol solution
・ Methanol 900g

(Sol solution)
・ Hosmer PE (Unichemical Co., Ltd.) 5g
・ Methanol 45g
・ Water 10g
・ 85% phosphoric acid 5g
・ Tetraethoxysilane 20g
・ 3-Methacryloxypropyltrimethoxysilane 15g

Example 23
Preparation of lithographic printing plate precursor (30) A lithographic printing plate precursor (29) is prepared in the same manner as the preparation of a lithographic printing plate precursor (29) except that the image forming layer coating solution (29) is changed to an image forming layer coating solution (30) having the following composition. A printing plate precursor (30) was obtained. The image forming layer of the obtained lithographic printing plate precursor (30) had a dry coating amount of 1.1 g / m ² .

<Image forming layer coating solution (30)>
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.10g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ IM-615 0.43g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

[Comparative Example 8]
Preparation of lithographic printing plate precursor (31) A lithographic printing plate precursor (29) is prepared in the same manner as the preparation of a lithographic printing plate precursor (29) except that the image forming layer coating solution (29) is changed to an image forming layer coating solution (31) having the following composition. A printing plate precursor (31) was obtained. The image forming layer of the obtained lithographic printing plate precursor (31) had a dry coating amount of 1.0 g / m ² .

<Image forming layer coating solution (31)>
・ Binder polymer (1) 0.54g
・ Polymerizable compound 0.53g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ The chain transfer agent (1) 0.07 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant Binder polymer (1): 10 parts by mass,
Solvent cyclohexanone / methoxypropyl acetate
/ 1-methoxy-2-propanol
= 15 parts by mass / 20 parts by mass / 40 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

[Examples 10 to 23, Comparative Examples 5 to 8]
(1) Exposure, development and printing For each of the above lithographic printing plate precursors (22) to (44), imagewise exposure was performed using a 405 nm semiconductor laser with an output of 100 mW while changing the energy density.
Thereafter, the developing solution (1) having the following composition was used, and development processing was carried out with an automatic developing processor having a structure shown in FIG. The pH of the developer was about 5. The automatic processor is an automatic processor having two rotating brush rolls, and the rotating brush roll is a first brush roll,
Using a 90 mm outer diameter brush roll in which fibers made of polybutylene terephthalate (hair diameter: 200 μm, hair length: 17 mm) were used, and rotated 200 times per minute in the same direction as the conveying direction (peripheral speed of the brush tip: 0.94 m) / Sec), and the second brush roll has an outer diameter 60 in which fibers made of polybutylene terephthalate (hair diameter 200 μm, hair length 17 mm) are implanted.
Using a brush roll of mm, it was rotated 200 times per minute in the direction opposite to the conveying direction (peripheral speed of the brush tip 0.63 m / sec).
The developer was showered from the spray pipe with a circulation pump and supplied to the plate surface. The tank capacity of the developer was 10 liters.

Developer (1)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether (oxyethylene average number n = 13) 1.00 g
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Arabic gum 1.00g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g

Subsequently, the developed lithographic printing plate is attached to a printing machine SOR-M manufactured by Heidelberg, and dampening water (EU-3 (Etchi solution manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol =
1/89/10 (volume ratio)) and TRANS-G (N) black ink (Dainippon Ink Chemical Co., Ltd.)
And a printing speed of 6000 sheets per hour.

(2) Evaluation Using the lithographic printing plate precursor prepared previously, the developability, sensitivity, and printing durability were evaluated as follows. The results are shown in Table 2.
<Developability>
Under the above development conditions, the developability was evaluated based on the conveyance speed necessary for completely removing the non-image portion of the lithographic printing plate precursor. The faster the conveyance speed, the higher the developability.
<Sensitivity>
After 100 sheets were printed as described above and it was confirmed that a printed matter having no ink stains in the non-image area was obtained, 500 sheets were printed continuously. In the total 600th printed matter, the exposure amount with no unevenness in the ink density in the image area was measured as sensitivity.
<Print durability>
As described above, as the number of printed sheets is increased, the image recording layer gradually wears and the ink acceptability is lowered, so that the ink density in the printing paper is lowered. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing.

Example 24
The lithographic printing plate precursor (14) was image-exposed in the same manner as in Example 10, and within 30 seconds, the lithographic printing plate precursor was placed in an oven and hot air was blown to heat the entire surface of the lithographic printing plate precursor. Hold at 110 ° C. for 15 seconds. Thereafter, the same development processing and printing as in Example 10 were performed within 30 seconds.
By the heat treatment, the developability did not change to 130 cm / min, the sensitivity was 0.05 mJ / cm ² , and the printing durability was 110,000 sheets.

Example 25
The lithographic printing plate precursor (14) was subjected to image exposure using a Violet semiconductor laser plate setter Vx9600 (equipped with InGaN semiconductor laser 405 nm ± 10 nm emission / output 30 mW) manufactured by FUJIFILM Electronic Imaging Ltd. The image was drawn using a FM screen (TAFFETA 20) manufactured by Fuji Photo Film Co., Ltd. with a resolution of 2438 dpi, and a 35% flat screen was drawn with a plate exposure of 0.05 mJ / cm ² . Within 30 seconds after image exposure of the exposed lithographic printing plate precursor, development processing was carried out using an automatic processor LP1250PLX manufactured by Fuji Photo Film Co., Ltd. The automatic processor is configured in the order of heating unit / washing unit / developing unit / rinsing unit / finishing unit. The heating condition of the heating unit is 100 ° C. for 10 seconds, and the washing unit, developing unit, rinsing unit All the baths in the unit / finishing unit were charged with the developer (2). The temperature of the developer was 28 ° C., and the planographic printing plate was transported at a transport speed of 130 cm / min.
After development, the non-image area and the image of the lithographic printing plate were visually confirmed. As a result, the photosensitive layer did not remain in the non-image area, and a uniform flat net image without unevenness was formed. Further, when this lithographic printing plate was printed under the above-mentioned printing conditions, 110,000 sheets of good printed matter having a uniform flat net image with no non-image area stains and no unevenness were obtained.

  As is clear from Table 2 and the like, the developability, sensitivity, and resistance to resistance of the lithographic printing plate precursor not used by using the compound represented by the general formula (1), (2) or (3) of the present invention are improved. Printability is improved.

It is explanatory drawing which shows the structure of an automatic developing processor.

Explanation of symbols

61 Rotating brush roll 62 Receiving roll 63 Conveying roll 64 Conveying guide plate 65 Spray pipe 66 Pipe line 67 Filter 68 Feeding plate 69 Discharging plate 70 Developer tank 71 Circulating pump 72 Plate

Claims (8)

On the surface hydrophilic support, a lithographic printing plate precursor provided with an image forming layer containing a compound represented by the following general formula (3).

In the formula, the cation part is a part composed of a functional group having a + charge, the anion part is a part composed of a functional group having a − charge, a and b represent natural numbers of 1 to 20, m , P each represents a natural number of 1 to 6, and C represents a number where m / Cp = 1. The lithographic printing plate precursor as claimed in claim 1 , wherein the image forming layer further contains a radical polymerizable compound. The lithographic printing plate precursor as claimed in claim 1 or 2 , wherein the image forming layer further contains an infrared absorber. The lithographic printing plate precursor as claimed in any one of claims 1 to 3, wherein a protective layer is provided on the image forming layer. The lithographic printing plate precursor as claimed in any one of claims 1 to 4, which can be developed with an aqueous solution having a pH of 10 or less. The lithographic printing plate precursor according to any one of claims 1 to 4, which can be mounted on a printing machine and printed without any processing after image formation. The lithographic printing plate precursor according to any one of claims 1 to 6 is mounted on a printing press and imagewise exposed with a laser, or imagewise exposed with a laser and then mounted on a printing press. A lithographic printing method in which printing ink and fountain solution are supplied to the lithographic printing plate precursor to remove an unexposed portion of the image forming layer and print. 8. The method for producing a lithographic printing plate according to claim 7 , further comprising heat-treating the exposed lithographic printing plate precursor between exposure and development.