JP2002268239A - Method for making printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for making a high sensitivity photosensitive planographic printing plate by which light fog is suppressed and the improvement of processing stability due to the decrease of scum in a developing solution is achieved. SOLUTION: A photosensitive planographic printing plate containing a sensitizing dye of formula (II) or (III) (where T is -S- or -NR<3> -, R<3> is H, alkyl or aryl; Y is a nonmetallic atomic group forming the basic nucleus of the dye together with the adjacent T or N and adjacent C; R<1> and R<2> are each H or a monovalent nonmetallic atomic group and may bond to each other to form the acidic nucleus of the dye; X is O, S or =NR<4> and R<4> is H or a monovalent nonmetallic atomic group) is photoengraved by carrying out exposure with laser light and development with a non-silicate developing solution containing an inorganic alkali agent and a nonionic compound of the formula A-W (where A is a hydrophobic organic group which satisfies (logP of A-H)>=1.5 and W is a nonionic hydrophilic organic group which satisfies (logP of W-H)<1.0).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate making method for developing a photosensitive lithographic printing plate containing a specific dye using a specific developer. More specifically, the present invention relates to a method of making a lithographic printing plate, which can obtain a very high-contrast image in which printing smear due to light fog is hardly observed and greatly reduces development scum.

[0002]

2. Description of the Related Art Hitherto, many highly sensitive photosensitive lithographic printing plates have been known. For example, JP-A-9-272096, JP-A-8-2
No. 62715, JP-A-2000-206690 and the like disclose a very high-sensitivity photosensitive composition for printing plates using a combination initiation system of a titanocene photoinitiator and a sensitizing dye. However, in these high-sensitivity printing plates, the polymer component in the photosensitive layer is cured by polymerization due to a small amount of leaked light during handling, storage, exposure, etc., and that part is not removed by development, and it is not removed in the non-image area. There is a problem that printing stains occur, that is, so-called light fogging easily occurs. In particular, when performing exposure with an inner drum type (inner drum type) laser exposure machine, such a high-sensitivity printing plate uses reflected light (flare light).
Light fogging is likely to occur. For example, when a negative type plate is used as a photosensitive material, when an image such as a solid image is exposed on one side of the plate, if the opposite side is a non-image part, fogging such as development failure becomes thin, and the opposite side (light source) If the opposite side is 180 °, the dot is approximately 140 to 220 °), there is a problem that the dot becomes thick, and it is difficult to reproduce a minute image or highlight portion. Was wanted. Further, in these printing plates, if the developing process is continued for a long time, unnecessary substances accumulate in the developing solution, coagulate and settle, and become a developing residue, which is a factor of destabilizing the developing process.

[0003]

Accordingly, the present invention overcomes the above-mentioned disadvantages of the prior art, suppresses light fog,
Another object of the present invention is to provide a photosensitive lithographic printing plate having high sensitivity and improving the processing stability by reducing the developer scum, and a method of making the printing plate.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by the following plate making method. (1) A photosensitive lithographic printing plate containing at least one of the sensitizing dyes represented by the following general formulas (II) and (III) is exposed to laser light, and an inorganic alkali agent and A plate-making method comprising developing using a non-silicate developer containing a non-ionic compound represented by formula (I).

AW (I) (In the formula (I), A represents a hydrophobic organic group having a logP of AH of 1.5 or more, and W represents a non-organic group having a logP of WH of less than 1.0. Represents an ionic hydrophilic organic group.)

[0006]

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(In the formula (II) or (III), T represents a sulfur atom or —NR ³ —, R ³ represents a hydrogen atom, an alkyl group or an aryl group. Y represents an adjacent T or nitrogen atom, and Represents a non-metallic atomic group which forms a basic nucleus of the dye in cooperation with an adjacent carbon atom, and R ¹ and R ² are each independently a hydrogen atom or a monovalent non-metallic atomic group; X represents an oxygen atom, a sulfur atom or ＮＲNR ^4, and R ⁴ represents a hydrogen atom or a monovalent nonmetallic atomic group.)

(2) The sensitizing dye is represented by the following general formulas (IV) and (V)
And the plate-making method according to the above (1), which is at least one of the sensitizing dyes represented by (VI).

[0009]

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(In the formulas (IV) to (VI), R ^{5 to} R ¹⁴ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group;
Represents an aromatic ring which may have a substituent or a hetero ring which may have a substituent. Also, R ⁷ and R ⁸ and R ¹¹
And R ¹² may combine with each other to form an acidic nucleus of the dye. )

(3) The method of making a lithographic printing plate as described in (1) or (2) above, wherein the developer contains a chelating agent for a divalent metal. (4) The lithographic printing plate as described in any one of (1) to (3) above, wherein the developer has a pH of 10.0 to 12.5 and an electric conductivity of 3 to 30 mS / cm. Plate making method.

The developing solution used in the present invention has a lower permeability than conventional developing solutions, and is characterized in that it is dissolved from the surface without damaging the inside of the photocured portion or the surface of the support. .
When this developer is used, the developer penetrates into the cured portion,
The image area does not peel off from the support, and the image can be developed in a form corresponding to the degree of curing of the photosensitive layer. The part that has been cured by a very small amount of light, such as flare light, has a low degree of cure, while the laser-exposed image area has a sufficiently high degree of cure. The non-image portion slightly cured by the flare light is developed properly, and the laser exposed portion is not developed, so that a firm image portion can be formed. That is, the present inventors have found that by using the plate making method of the present invention, it is possible to form a very hard image using a printing plate having extremely high sensitivity, and have reached the present invention.

In particular, in the present invention, as a result of diligent studies on the developer composition, it has been found that a developer composed of a special component makes it possible to achieve both stain during printing and printing durability without impairing the image-forming properties, and Thus, the developer insoluble compound described above can be dissolved or dispersed and stabilized for a long time, and the processing stability can be improved.

At present, it is considered that the special developer satisfies the following requirements as a developer composition. First, it has a very good effect on image forming properties (the unexposed part has high developability, the permeability of the developing solution to the exposed part is low. The dissolution behavior of the photosensitive layer is non-swelling, Dissolve in order from the photosensitive layer surface). Secondly, the photosensitive layer in the unexposed area can be completely removed, and the surface of the support can be reproduced as a hydrophilic surface free from printing stains. Third, in order to stably disperse or solubilize the above-mentioned insoluble compounds for development, the non-ionic compound of the above general formula (I) having a hydrophobic site that interacts with these insoluble compounds and a hydrophilic site that is dispersed and stabilized in water. Contains an active compound.
Fourth, in order to prevent salting out and a reduction in development speed, the salt concentration must be low (it is non-silicate, and the pH must be lower than that of a conventional alkali developer). Fifth, a chelating agent for removing divalent metals such as Ca ions contained in water, which is a cause of instability during development processing, is contained. Of these, the first,
Regarding the second, the characteristics of the photosensitive layer components are also important factors.
There is no particular restriction on the photosensitive layer of a photopolymerizable lithographic printing plate. Is considered important in obtaining

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a high-sensitivity photosensitive lithographic printing plate which suppresses light fog and improves processing stability by reducing developer scum, and a method of making a printing plate therefor, according to the present invention, will be described. This will be described in detail.

[Photosensitive planographic printing plate] First, the photosensitive planographic printing plate used in the present invention will be described.

[Photosensitive layer] Among them, the photosensitive layer of the photosensitive lithographic printing plate used in the present invention will be described first. The photosensitive layer of the photosensitive lithographic printing plate used in the present invention,
Although not particularly limited, a negative-type photopolymerizable photosensitive layer capable of laser drawing is preferable. The main components of the photopolymerizable photosensitive layer are: a) a photopolymerization initiation system, b) a compound having an ethylenically unsaturated double bond capable of addition polymerization, and c) a polymer soluble or swellable in an aqueous alkali solution. Yes, various compounds such as a coloring agent, a plasticizer, and a thermal polymerization inhibitor are added as needed.

A) Photopolymerization Initiation System The photopolymerization initiation system in the present invention comprises a combination of a sensitizing dye having a specific structure and various known photopolymerizable initiators. Hereinafter, description will be made in order.

The sensitizing dye of the present invention is represented by the above general formula (I)
It has a structure represented by I) and / or (III). These dyes have been found to significantly improve sensitivity when combined with a photoinitiator. For example, Japanese Patent Application No. Hei 11-3185
No. 18 describes a combination of thioxanthone, a dithiol compound and an acylphosphine, and Japanese Patent Application No. 2000-306431 describes a combination of a borate, a lyazine compound and a sensitizing dye. The reason for this very efficient sensitizing action is considered as follows. That is, since the dye of the present invention has a high emission intensity, the life of the excited state after light absorption is prolonged, and it is considered that the efficiency of the dye sensitization reaction is high. The sensitizing dyes having these structures have sharp absorption peaks and have strong absorption in a specific wavelength range. Therefore, when a light source having a single wavelength such as laser light is used as a light source, it is possible to absorb energy very efficiently by selecting a sensitizing dye whose absorption characteristics are matched, and also to increase efficiency. I think it works in terms of advantage.

Hereinafter, the sensitizing dye represented by formula (II) or (III) will be described in detail. T is -S- or-
NR ³ - represents, R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, Y together with the adjacent T or nitrogen atom and the adjacent carbon atoms, the dye Represents a non-metallic atomic group forming a basic nucleus.

Preferred examples of R ³ will be specifically described. Examples of preferred alkyl groups include those having 1 carbon atom.
To 20 linear, branched, and cyclic alkyl groups, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1- Methyl butyl group,
Isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-
Norbornyl groups can be mentioned. Among them, a straight chain having 1 to 12 carbon atoms, 3 carbon atoms.
From 12 to 12 and from 5 to 10 carbon atoms
More preferred are cyclic alkyl groups up to.

As a substituent of the substituted alkyl group, hydrogen is
A monovalent non-metallic atomic group excluding is used, and as a preferable example,
Represents a halogen atom (-F, -Br, -Cl, -I),
Droxyl group, alkoxy group, aryloxy group, merka
Group, alkylthio group, arylthio group, alkyldi
Thio group, aryldithio group, amino group, N-alkyl
Mino group, N, N-dialkylamino group, N-aryla
Mino group, N, N-diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyl
Oxy group, N-alkylcarbamoyloxy group, N-A
Reel carbamoyloxy group, N, N-dialkyl carb
Bamoyloxy group, N, N-diarylcarbamoylo
Xy group, N-alkyl-N-arylcarbamoyloxy
Si group, alkylsulfoxy group, arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacyla
A mino group, an N-arylacylamino group, a ureido group,
N'-alkylureido group, N ', N'-dialkyl
Raid group, N'-arylureido group, N ', N'-di
Arylureido group, N'-alkyl-N'-aryl
Ureido group, N-alkyl ureido group, N-aryl
A raid group, an 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-ali
Ureureid group, N ', N'-diaryl-N-alkyl
Luureido group, N ', N'-diaryl-N-aryl
Ureido group, N'-alkyl-N'-aryl-NA
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, aryl
Roxycarbonyl group, carbamoyl group, N-alkyl
Rubamoyl group, N, N-dialkylcarbamoyl group, N
-Arylcarbamoyl group, N, N-diarylcarba
Moyl group, N-alkyl-N-arylcarbamoyl
Group, alkylsulfinyl group, arylsulfinyl group
Group, alkylsulfonyl group, arylsulfonyl group,
Ruho group (-SO_ThreeH) and its conjugated base group (hereinafter referred to as sulf
Honato group), alkoxysulfonyl group, arylo
Xisulfonyl group, sulfinamoyl group, N-alkyl
Sulfinamoyl group, N, N-dialkylsulfinamo
Yl group, N-arylsulfinamoyl group, N, N-di
Arylsulfinamoyl group, N-alkyl-N-ali
Sulfinamoyl group, sulfamoyl group, N-al
Killsulfamoyl group, N, N-dialkylsulfamo
Yl group, N-arylsulfamoyl group, N, N-dia
Reel sulfamoyl group, N-alkyl-N-aryl
Sulfamoyl group, phosphono group (-PO_ThreeH_Two) And that
Conjugate base group (hereinafter referred to as phosphonate group), dial
A killed phosphono group (-PO_Three(alkyl)_Two), Diarylho
Suphono group (-PO_Three(aryl)_Two), Alkyl aryl phos
Phono group (-PO_Three(alkyl) (aryl)), monoalkyl phos
Phono group (-PO_ThreeH (alkyl)) and its conjugated base group (hereinafter
Later referred to as an alkylphosphonato group),
Suphono group (-PO _ThreeH (aryl)) and its conjugate base group
(Hereinafter referred to as arylphosphonate group), phosphono
Oxy group (-OPO_ThreeH_Two) And its conjugated base group (hereinafter, referred to as
A phosphonatooxy group), a dialkylphosphono
Oxy group (-OPO_Three(alkyl)_Two), Diarylphospho
Nooxy group (-OPO_Three(aryl)_Two), Alkylarylho
Sulfonooxy group (-OPO_Three(alkyl) (aryl)), monoa
Alkylphosphonooxy group (-OPO_ThreeH (alkyl)) and
The conjugate base group (hereinafter referred to as alkylphosphonatooxy group
), A monoarylphosphonooxy group (-OPO
_ThreeH (aryl)) and its conjugated base group (hereinafter referred to as aryl
Sulfonatooxy group), cyano group, nitro group, ant
, Heteroaryl, alkenyl, alkynyl
Groups.

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

As the heteroaryl group, nitrogen, oxygen,
A monocyclic or polycyclic aromatic ring containing at least one sulfur atom is used, and preferably a 5- or 6-membered aromatic substituent such as furan, pyrrole, pyridine and the like can be used.

Examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ₁ in the acyl group (G ₁ CO ⁻ ) include hydrogen and the above-described alkyl and aryl groups. Of these substituents, still more preferred are halogen atoms (-F, -Br, -Cl,
-I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N
-Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-
Alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphono Examples include an oxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a straight-chain alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms.

Of the substituted alkyl groups preferred as R ³ obtained by combining the above substituent with an alkylene group,
Specific examples include a chloromethyl group, a bromomethyl group,
-Chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyl Oxymethyl 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-ethylsulfamoylmethyl 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 , 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, and the like.

Specific examples of preferred aryl groups for R ³ include those in which one to three benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Yes, specific examples include a phenyl group,
Examples include a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

Specific examples of preferred substituted aryl groups as R ³ include those having a monovalent nonmetallic atomic group as a substituent on the ring-forming carbon atom of the above-mentioned aryl group. Examples of preferred substituents include the aforementioned alkyl groups,
Examples of the substituted alkyl group include those described above as the substituent for the substituted alkyl group. Preferred specific examples of such a substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. , Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group,
Diethylaminophenyl, morpholinophenyl, acetyloxyphenyl, benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methylbenzoylaminophenyl, carboxyphenyl Methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, carbamoylphenyl, N-methylcarbamoylphenyl, N, N-
Dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N-
(Sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N
-Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, Diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-
Butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2
-Butynylphenyl group, 3-butynylphenyl group, and the like.

Next, R ¹ and R ² in the general formulas (II) and (III) will be specifically described. R ¹ and R ²
Are each independently a hydrogen atom or a monovalent non-metallic atomic group, for example, a halogen atom (-F, -Br, -Cl,-
I) a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an 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-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,
An N ′, N′-dialkyl-N-alkylureido group,
An N ′, N′-dialkyl-N-arylureido group,
N'-aryl-N-alkylureido groups, N'-aryl-N-arylureido groups, N ', N'-diaryl-N-alkylureido groups, N', N'-diaryl-N-arylureido groups, 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-dialkyl A carbamoyl group, an N-arylcarbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-An arylcarbamoyl group, an alkylsulfinyl group,
An arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- Arukirusu Rufinamoyl 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 a phosphonate group), a dialkylphosphono group (—PO ₃ (alky
l) ₂ ), a diarylphosphono group (—PO ₃ (aryl) ₂ ),
An alkylarylphosphono group (—PO ₃ (alkyl) (ary
l)), monoalkyl phosphono group (-PO ₃ H (alkyl))
And its conjugated base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (-PO ₃ H (ary
l)) and its conjugate base group (hereinafter, referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter, referred to as phosphonatooxy group), dialkylphosphonoxy group (-OPO ₃ (alky
l) ₂ ), a diarylphosphonooxy group (—OPO ₃ (ary
l) ₂ ), an alkylarylphosphonoxy group (-OP
O ₃ (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO3H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonatooxy group), a monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter, referred to as arylphosphonatooxy group), cyano group, nitro group, substituted or unsubstituted aryl group, heteroaryl group, alkenyl group, and alkynyl group. Are more specific examples described for R ³ above.

R ¹ and R ² are bonded to each other to form
LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5
358 (1951). And the references may constitute an acidic nucleus in merocyanine dyes.

Specific examples of the acidic nucleus include 1,3-dicarbonyl nucleus (for example, 1,3-indandione, 1,3-
Cyclohexanedione, 5,5-dimethylcyclohexanedione, 1,3-dioxane-4,6-dione, etc.),
Pyrazolinone nucleus (for example, 3-methyl-1-phenyl-
2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3-
Methyl-2-pyrazolin-5-one, etc.), isoxazolinone nucleus (for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5)
-One or the like), an oxindole nucleus (for example, 1-alkyl-2,3-dihydro-2-oxindole or the like),
2,4,6-trioxohexahydropyrimidine nucleus (for example, barbituric acid or 2-thiobarbituric acid and its N-substituted derivative, for example, 1,3-diethylbarbituric acid, 1,3-diethyl-2-thiobarbituric acid, 1,
3-dibutyl barbituric acid, 1,3-dibutyl-2-thiobarbituric acid, 1,3-diphenyl barbituric acid,
1,3-diphenyl-2-thiobarbituric acid, 1,3-
Dimethoxycarbonylmethylbarbituric acid, 1,3-dimethoxycarbonylmethyl-2-thiobarbituric acid and the like, 2-thio-2,4-thiazolidinedione nucleus (for example, rhodanine and its N-substituted derivative, for example, 3-
Methylrhodanine, 3-ethylrhodanine, 3-phenylrhodanine, 3-allylrhodanine, 3-benzylrhodanine, 3-carboxymethylrhodanine, 3-carboxyethylrhodanine, 3-methoxycarbonylmethylrhodanine, 3-hydroxyethylrhodanine, 3-
Morpholinoethylrhodanine, etc.), 2-thio-2,
A 4-oxazolidinedione nucleus (i.e., 2-thio-
2,4- (3H, 4H) -oxazoledione nucleus, for example, 2-ethyl-2-thio-2,4-oxazolidinedione, etc., and tianaphthenone nucleus (for example, 3 (2H) -thianaphthenone, 3 (2H)- Tianaphthenone-1,1-
A 2-thio-2,5-thiazolidinedione nucleus (for example, 3-ethyl-2-thio-2,5-thiazolidinedione) and a 2,4-thiazolidinedione nucleus (for example, 2,4-thiazolidine) Dione, 3-ethyl-2,
4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.), thiazolidinone nucleus (for example,
Thiazolidinone, 3-ethyl-4-thiazolidinone, 2
-Ethylmercapto-4-thizolidinone, 2-methylphenylamino-4-thizolidinone, etc.), 2-imino-2
-An oxazoline-4-one nucleus (i.e., a pseudohydantoin nucleus), a 2,4-imidazolidinedion nucleus (i.e., a hydantoin nucleus such as 2,4-imidazolidinedione, 3
-Ethyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, etc., 2-thio-2,4-imidazolidinedione nucleus (that is, thiohydantoin nucleus, for example, 2- Thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, 1,3-diethyl-2-thio-2,4-imidazolidinedione, etc.), imidazoline-5- On nucleus (eg, 2-propylmercapto-2-imidazoline-5)
-One), furan-5-one nucleus, 4-hydroxy-2
(1H) -pyridinone nucleus (for example, N-methyl-4-hydroxy-2 (1H) -pyridinone, N-methyl-4-
Hydroxy-2 (1H) -quinolinone, N-butyl-4
-Hydroxy-2 (1H) -quinolinone, etc.), 4-hydroxy-2H-pyran-2-one nucleus (for example, 4-hydroxycoumarin and the like), thioindoxyl nucleus (for example, 5
-Methylthioindoxyl, etc.), and these acidic nuclei may further have a substituent.

In the general formulas (II) and (III), X represents an oxygen atom, a sulfur atom or ＮＲNR ⁴ , and R ⁴ represents a hydrogen atom or a monovalent nonmetallic atomic group. Specific examples of R ⁴ include the same as those described for R ¹ and R ² above.

Next, Y in the general formulas (II) and (III) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in combination with the above-described T or nitrogen atom and an adjacent carbon atom. As such a heterocyclic ring, 5,
Examples thereof include a 6- or 7-membered nitrogen-containing or sulfur-containing heterocyclic ring, and preferably a 5- or 6-membered heterocyclic ring.

Examples of the nitrogen-containing heterocycle include LGBrooker
et al., J. Am. Chem. Soc., 73, 5326-5358 (1951); and any of those known as constituting a basic nucleus in merocyanine dyes described in References are preferably used. be able to. 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,
Benzothiazoles (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6- Methylbenzothiazole,
5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 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 (e.g., 4'-methoxythianaphtheno-7 ',
6 ′, 4,5-thiazole, etc.), oxazoles (for example, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 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.), Naphthooxazoles (e.g., naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (e.g., 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (e.g., For example, benzo selenazole, 5-chlorobenzo selenazole, 5-methoxy benzo selenazole, 5-hydroxy benzo selenazole, tetrahydro benzo selenazole, etc.), naphtho selenazoles (for example, naphtho [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-hydroxyquinoline, 8-hydroxyquinoline, etc., 4-quinolines (for example, quinoline, 6-methoxyquinoline, 7-methyl) Quinoline, 8-methylquinoline, etc.), 1-isoquinolines (e.g., isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (e.g., isoquinoline, etc.), benzimidazoles (e.g., 1,3
-Diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (eg, 3,3-dimethylindolenin, 3,3,5, -trimethylindolenin, 3, 3,
7, -trimethylindolenine, etc.), 2-pyridines (eg, pyridine, 5-methylpyridine, etc.), 4-
Pyridine (for example, pyridine and the like) can be exemplified.

Examples of the sulfur-containing heterocyclic ring include, for example, a dithiol partial structure in dyes described in JP-A-3-296759. Specific examples of dithiols include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.) and naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2 , 1] dithiol, etc.), dithiols (eg, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonylbenzodithiols, 4,5-ditrifluoro Methyldithiol, 4,5-dicyanodithiol, 4-
Methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

Of the sensitizing dyes represented by the general formulas (II) and (III) described above, the dyes having the structures represented by the general formulas (IV), (V) and (VI) are: It is preferable because it has high contrast and high sensitivity, and further suppresses generation of development scum when combined with the developer of the present invention.

[0038] In the above formula (IV) ~ (VI), R 5 ~R
^{As the} non-metallic atomic group represented by ¹⁴ and the acidic nucleus of the dye that can be formed by combining R ⁷ and R ⁸ or R ¹¹ and R ¹² with each other, those similar to those described above for R ¹ and R ² can be used. Can be mentioned. In the general formula (VI), examples of the aromatic ring which may have a substituent represented by B include the above-mentioned R
^{The same} as the aryl group which may have a substituent described in ³ can be exemplified. As the heterocycle which may have a substituent group B represents, it can be the same as the heteroaryl mentioned above R ^3.

Hereinafter, examples of the sensitizing dye of the present invention will be described in more detail by describing the chemical structural formulas (C-1) to (C-67), (D
-1) to (D-37) and (E-1) to (E-39), and any of the sensitizing dyes satisfying the above structural requirements can be suitably used as the sensitizing dye of the present invention. Is not limited by the following chemical formula:

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The sensitizing dyes of the present invention represented by the formulas (II) to (VI) can be easily synthesized by using known synthesis methods and related synthesis methods. A more specific synthesis method is shown below.
For example, the sensitizing dye represented by the general formula (II) is disclosed in
The compound can be synthesized with reference to JP-A-244050 and JP-B-6-97339. The dyes represented by formulas (III) and (VI) can be synthesized with reference to Japanese Patent Publication No. 2-30321.
The sensitizing dyes represented by the general formulas (IV) and (V)
F. M. Hammer et al., `` The Cyanine Soybeans and Related Compounds '' (FMHameret al.,
"The Cyanine Dyes and Related Compounds") No. 51
KAI ARNE J, described on pages 1 to 611 (1964)
ENSEN and LARS HENRIKSEN are ACTA CHEMICA SCANDIN
It can be synthesized by referring to the method described in AVICA, Vol. 22, pp. 1107 to 1128 (1968), Japanese Patent Publication No. 25552550, and the like.

The sensitizing dye of the present invention can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, by combining a sensitizing dye with an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, it is possible to increase the strength of the exposed film or to increase the exposure. Unwanted precipitation of the dye from the subsequent film can be suppressed. In addition, a sensitizing dye and a titanocene compound described later and other radical generating parts (for example, reductively decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, etc., borate, amine, trimethylsilylmethyl) Oxidatively cleavable sites such as carboxymethyl, carbonyl, and imine), thereby significantly increasing the photosensitivity, particularly in the case where the concentration of the starting system is low. further,
For the purpose of enhancing the suitability for processing in an (alkali) aqueous developer, which is a preferred mode of use of the present photosensitive layer, a hydrophilic site (such as a carboxyl group and its ester, a sulfonic acid group and its ester, an ethylene oxide group, etc.) The introduction of an acid group or a polar group) is effective. Particularly, the ester-type hydrophilic group has a relatively hydrophobic structure in the photosensitive layer and thus has excellent compatibility, and in a developing solution, generates an acid group by hydrolysis to increase the hydrophilicity. Have.

In addition, for example, a substituent can be appropriately introduced to improve compatibility in the photosensitive layer and suppress crystal precipitation. For example, in some kinds of photosensitive systems, an unsaturated bond such as an aryl group or an allyl group may be very effective in improving the compatibility. By introducing an obstacle, crystal precipitation can be significantly suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, it is possible to improve the adhesion to inorganic substances such as metals and metal oxides. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

The method of using these sensitizing dyes can be arbitrarily set in accordance with the performance design of the light-sensitive material, similarly to the above-mentioned addition-polymerizable compound. For example, by using two or more sensitizing dyes in combination, the compatibility with the photosensitive layer can be increased. In selecting a sensitizing dye, the molar extinction coefficient at the emission wavelength of the light source used is an important factor in addition to the photosensitivity. By using a dye having a large molar extinction coefficient, the amount of the dye added can be relatively small, which is economical and advantageous from the viewpoint of the physical properties of the photosensitive layer. Since the photosensitivity, resolution and physical properties of the exposed film are greatly affected by the absorbance at the light source wavelength,
The addition amount of the sensitizing dye is appropriately selected in consideration of these. For example, sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation.
However, for the purpose of hardening a thick film having a thickness of, for example, 5 μm or more, such a low absorbance may sometimes increase the degree of hardening. In a high region where the absorbance is 3 or more, most of the light is absorbed on the surface of the photosensitive layer, and the curing inside is more hindered. Will be inadequate. When used as a lithographic printing plate having a relatively thin film thickness, the amount of the sensitizing dye to be added is such that the absorbance of the photosensitive layer is in the range of 0.1 to 1.5, preferably in the range of 0.25 to 1. It is preferable to set so that When used as a lithographic printing plate, this is usually 0.05 to 30 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the photosensitive layer component.
0 parts by weight, more preferably 0.2 to 10 parts by weight.

As the photopolymerization initiator contained in the photosensitive layer of the photosensitive lithographic printing plate used in the present invention, various photoinitiators known in patents and literatures, Combination system of two or more photo initiators (photo initiation system)
Can be appropriately selected and used.

For example, a complex initiation system of a dye and an amine (JP-B-44-20189), hexaarylbiimidazoles (JP-B-47-2528, JP-A-54-155292, JP-A-59-155292)
140203, JP-A-10-36354, etc.), cyclic cis-α-dicarbonyl compounds (JP-A-48-84183, etc.), triazine compounds (JP-A-54-151024, etc.), JP-A-59-1504, JP-A-59-140203, JP-A-59-1893
No. 40, JP-A-62-174203, JP-B-62-1641, U.S. Pat.
No. JP-A-2-63054), borate compounds (JP-A-62
-143044, JP-A-1-229003, JP-A-9-188685,
JP-A-9-188686, JP-A-9-188710, etc.) and titanocene compounds (JP-A-63-221110, JP-A-4-221958)
No., JP-A-4-219756, JP-A-6-2955061, JP-A-8
-334897).

Further, an auxiliary such as an amine compound or a thiol compound may be added to the photopolymerization initiator used in the present invention, if necessary. The addition of these hydrogen-donating compounds further enhances the photopolymerization initiation ability. be able to.
The use amount of these photopolymerization initiators is 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 100 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound.
It can be used in the range of 50 parts by weight.

B) Addition-Polymerizable Compound Having an Ethylene Unsaturated Double Bond The compound containing an addition-polymerizable ethylenic double bond has at least one, preferably two or more, terminal ethylenically unsaturated bonds. It can be arbitrarily selected from compounds. For example, those having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and their copolymers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated esters Examples include amides of carboxylic acids and aliphatic polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, 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 pentaacrylate, dipentaerythritol hexaacrylate, sorbitol Triacry Over DOO, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. The crotonic acid ester includes ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Another example is JP-B-48-417.
JP-A-08-0838, in which a hydroxyl-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. And vinyl urethane compounds containing two or more polymerizable vinyl groups.

CH ₂ ＣC (R ²¹ ) COOCH ₂ CH (R ²² ) OH (A)

(Where R ²¹ and R ²² are H or CH ₃
Is shown. )

Further, urethane acrylates described in JP-A-51-37193 and JP-B-2-32293, JP-A-48-64183, JP-B-49-64193.
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-43191 and JP-B-52-30490 can be exemplified. . Further, the Journal of the Adhesion Society of Japan, vol.
20, no. 7, pages 300-308 (1984)
Those described as photocurable monomers and oligomers can also be used. In addition, the use amount of these is 5 to 70% by weight (hereinafter abbreviated as%), preferably 10 to 50% with respect to all components.

C) High-molecular polymer soluble or swellable in aqueous alkali solution The high-molecular polymer soluble or swellable in alkaline water contained in the photosensitive layer of the photosensitive lithographic printing plate used in the present invention is The composition is selected and used not only as a film-forming agent of the composition but also according to the use of an alkaline water developer. For example, when a water-soluble organic high molecular polymer is used as the organic high molecular polymer, water development becomes possible. Examples of such organic high-molecular polymers include addition polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615 and JP-B-54-34327.
No., JP-B-58-12577, JP-B-54-2595
7, JP-A-54-92723, JP-A-59-538.
No. 36, JP-A-59-71048, namely, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, There are esterified maleic acid copolymers and the like.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth)
Acrylate (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer is preferred.
In addition, polypinylpyrrolidone, polyethylene oxide, and the like are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamides and polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. No. 7-120040, No. 7-120
No.041, No.7-120042, No.8-12
424, JP-A-63-287944, JP-A-63-287944
No. 287947, JP-A-1-271174, JP-A-1
The polyurethane resin described in 1-35-2691 is also useful for the use of the present invention.

These polymers can improve the strength of the cured film by introducing a radical reactive group into the side chain. Examples of functional groups capable of undergoing an addition polymerization reaction include an ethylenically unsaturated bond group, an amino group, an epoxy group, and the like. Functional groups capable of forming a radical upon irradiation with light include mercapto groups, thiol groups, halogen atoms, triazine structures, onium salts. The structure includes a carboxyl group and an imide group as the polar group. The functional group capable of undergoing the addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acryl group, a methacryl group, an allyl group, and a styryl group.
Also useful are functional groups selected from amino groups, hydroxy groups, phosphonic acid groups, phosphoric acid groups, carbamoyl groups, isocyanate groups, ureido groups, ureylene groups, sulfonic acid groups, and ammonium groups. In order to maintain the developability of the composition, the polymer of the present invention preferably has an appropriate molecular weight and acid value. In order to develop with the above-mentioned developer, the weight average molecular weight is 5000 to 300,000, and the acid value is 0.2 to 5.0 m.
It is preferable to use a high molecular weight polymer of eq / g.

Any of these organic high molecular weight polymers can be incorporated in the whole composition. However, if it exceeds 90% by weight, no favorable result is obtained in terms of the strength of the formed image and the like. Preferably it is 10-90%, more preferably 30-80%. In addition, the photopolymerizable ethylenically unsaturated compound and the organic high molecular weight are 1/9 to weight ratio.
It is preferred to be in the range of 9/1. A more preferred range is 2/8 to 8/2, and still more preferably 3/7 to 7/3.
It is.

In the present invention, in addition to the basic components described above, in order to prevent unnecessary thermal polymerization of an ethylenically unsaturated compound which can be polymerized during the production or storage of the photosensitive composition for the photosensitive layer. It is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-
p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-
6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-
And nitrosophenylhydroxylamine aluminum salt. The addition amount of the thermal polymerization inhibitor is preferably from about 0.01% to about 5% based on the weight of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. Good. The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

Further, a coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the colorant include phthalocyanine pigments (CI Pigment Blue 1).
5: 3.15: 4, 15: 6, etc.), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of the dye or pigment added is preferably about 0.5% to about 20% of the total solids in the photosensitive layer. In addition, to improve the physical properties of the cured film, inorganic fillers and dioctyl phthalate, dimethyl phthalate,
An additive such as a plasticizer such as tricresyl phosphate may be added. The addition amount of these is preferably 10% or less of the total solid content of the photosensitive layer.

When the above-mentioned photosensitive layer is coated on a support described later, the composition for a photosensitive layer is dissolved in various organic solvents before use. The solvent used here is acetone,
Methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 1 to 50% by weight.

A surfactant can be added to the composition for a photopolymerizable photosensitive layer in order to improve the coated surface quality. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably, 0.
It is 3 to 5 g / m ² . More preferably, 0.5 to 3 g /
m ² .

[Acid value of photosensitive layer] The acid value of the photosensitive layer in the present invention refers to the photosensitive composition coated on the support of the photosensitive lithographic printing plate (the photosensitive composition coated on the photosensitive layer). overcoat layer that, for example, a layer of oxygen-barrier layer is not included), an equal amount of pKa9 following acids contained per 1g. Although it can be experimentally determined by directly titrating the photosensitive layer with an aqueous sodium hydroxide solution, it can also be determined by calculation from the content of a compound having an acid group with a pKa of 9 or less in the photosensitive composition. Specifically, the method for changing the acid value of the photosensitive layer is to change the content ratio of a crosslinking agent monomer / acid group-containing binder polymer (linear polymer) which is a photosensitive layer component and a low acid value binder polymer having a small acid group. Use is conceivable. The low acid value binder polymer preferably has an acid value of 1.5 meq / g or less. More preferably, 1.
It is 2 meq / g or less. The photosensitive layer of the present invention preferably has an acid value of 1.0 meq / g. Acid value 0.2
It is more effective to apply to a lithographic printing plate having a photosensitive layer of 0 to 0.60 meq / g. Further, it preferably has a photosensitive layer of 0.30 to 0.50 meq / g in view of image forming properties.

(Support) The support of the photosensitive lithographic printing plate used in the present invention is not particularly limited as long as it is a dimensionally stable plate, but an aluminum support is preferable. Aluminum support is a dimensionally stable aluminum-based aluminum and aluminum-containing (eg, alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, etc.) alloy Or a plastic film or paper on which aluminum or an aluminum alloy is laminated or vapor-deposited. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 may be used. The aluminum support is appropriately subjected to a substrate surface treatment described later.

(Graining treatment) Graining treatment methods include mechanical graining, chemical etching, and electrolytic graining as disclosed in JP-A-56-28893. Furthermore, an electrochemical graining method of electrochemically graining in a hydrochloric acid or nitric acid electrolyte, a wire brush graining method in which the aluminum surface is scratched with a metal wire, and a ball in which the aluminum surface is grained with a polishing ball and an abrasive. A mechanical graining method such as a grain method, a brush grain method for graining the surface with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.

Among them, a method of producing a surface roughness usefully used in the present invention is an electrochemical method of chemically graining in a hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100 C / dm ² to 100 C / dm ² . It is in the range of 400 C / dm ² . More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm ² ~400C / dm ² Is preferably performed. The aluminum support thus grained is chemically etched with an acid or an alkali. When an acid is used as an etching agent, it takes time to destroy a fine structure, which is disadvantageous in industrially applying the present invention. However, it can be improved by using an alkali as an etching agent. Alkali agent preferably used in the present invention, caustic soda,
Using sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, etc., the preferred ranges of concentration and temperature are 1 to 50%, respectively.
20-100 ° C. Al dissolution amount of 5 to 20 g / m
^The condition that becomes ³ is preferable.

After the etching, pickling is performed in order to remove dirt (smut) remaining on the surface. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. In particular, the method for removing the smut after the electrochemical surface-roughening treatment is preferably a method for removing the smut from 50 to 50 as described in JP-A-53-12739.
A method of contacting with sulfuric acid of 15 to 65% by weight at a temperature of 90 ° C. and a method of alkali etching described in Japanese Patent Publication No. 48-28123 are exemplified. The surface roughness of the Al support effectively used in the present invention is (Ra)
Is 0.3 to 0.7 μm.

(Anodic Oxidation Treatment) The aluminum support thus treated is further subjected to an anodic oxidation treatment. The anodizing treatment can be performed by a method conventionally performed in this field. Specifically, sulfuric acid, phosphoric acid,
Chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or the like or a combination of two or more of them can form an anodized film on the surface of an aluminum support by flowing a direct current or an alternating current to aluminum in an aqueous solution or a non-aqueous solution. . Since the conditions of the anodizing treatment vary depending on the electrolytic solution used, they cannot be unconditionally determined,
Generally, the concentration of the electrolyte is 1 to 80%, and the temperature of the electrolyte is 5 to 70%.
° C, current density 0.5-60 amps / dm ² , voltage 1 ~
A range of 100 V and an electrolysis time of 10 to 100 seconds is appropriate.

Among these anodizing treatments, those described in British Patent No. 1,412,768 are particularly useful.
The method of anodizing at a high current density in sulfuric acid and the method of anodizing phosphoric acid as an electrolytic bath described in US Pat. No. 3,511,661 are preferred. In the present invention, the anodized film is preferably from ^{1~10g / m 2, 1g / m} 2 plate to easily enter the wound is not more than, 10 g / m ² or more is great power is required for the production Is economically disadvantageous. Preferably, 1.5 to 7 g /
m ² . More preferably, it is ² to 5 g / g ² . Further, in the present invention, after graining and anodizing,
The aluminum support may be subjected to a sealing treatment.
Such a sealing treatment is performed by immersing the substrate in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. The aluminum support may be subjected to a surface treatment such as a treatment other than silicate treatment with an alkali metal silicate, for example, immersion treatment in an aqueous solution of potassium fluorozirconate, phosphate or the like.

As the support of the photosensitive lithographic printing plate of the present invention, in addition to the above-mentioned aluminum support, the following dimensionally stable plate-like materials are suitably used. For example, paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate (eg,
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.) And paper or plastic film on which metal is laminated or vapor-deposited.

It is also preferable that these supports are subjected to a surface hydrophilization treatment according to the supports. Examples of the surface hydrophilization treatment include treatment by a chemical reaction such as etching, oxidation, reduction, and sol-gel coating, and coating with a specific compound that is adsorbed on the surface of the support. For example, in the case of an anodized aluminum support, an organic compound having a phosphoric acid group (phosphoric acid, phosphonic acid, phosphinic acid) is preferably used. By forming the above-mentioned photosensitive layer on the above support, the photosensitive lithographic printing plate of the present invention is produced, but an organic or inorganic undercoat layer may be formed as necessary before coating the photosensitive layer. It may be provided.

(Oxygen-blocking protective layer) The photosensitive lithographic printing plate of the present invention may have an oxygen-blocking protective layer mainly composed of a water-soluble vinyl polymer on the photopolymerizable photosensitive layer. Good. Examples of the water-soluble vinyl polymer contained in the oxygen-barrier protective layer include polyvinyl alcohol, and its partial esters, ethers, and acetal, or a substantial amount of an unsubstituted vinyl alcohol unit having water solubility required for them. And copolymers thereof. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization degree of 300 to 2400. Specifically, Kuraray's PVA-105,
PVA-110, PVA-117, PVA-117H,
PVA-120, PVA-124, PVA-124H,
PVA-CS, PVA-CST, PVA-HC, PVA
-203, PVA-204, PVA-205, PVA-
210, PVA-217, PVA-220, PVA-2
24, PVA-217EE, PVA-220, PVA-
224, PVA-217EE, PVA-217E, PV
A-220E, PVA-224E, PVA-405, P
VA-420, PVA-613, L-8 and the like. Examples of the above-mentioned copolymer include polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal which have been hydrolyzed 88 to 100%, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

The solvent used for coating the oxygen-barrier protective layer is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight.
Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film may be added to the oxygen-barrier protective layer. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth) acrylic polymer or the like may be added. The amount of the coating is about 0.1 g /
range of m ² ~ about 15 g / m ² are suitable. More preferably 1.0 g / m ² ~ about 5.0 g / m ^2.

[Plate making process] Next, the plate making process of the present invention will be described. As the plate making process of the photosensitive lithographic printing plate of the present invention, if necessary, before exposure, during exposure,
The entire surface may be heated between exposure and development. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement of sensitivity and printing durability and stabilization of sensitivity can be brought about. Further, for the purpose of improving image strength and printing durability, it is also effective to post-heat or expose the entire surface of the developed image. Normally heating before development is 15
It is preferable to carry out the reaction under mild conditions of 0 ° C. or less. If the temperature is too high, there arises a problem that a non-image portion is covered. Very strong conditions are used for heating after development. Usually, it is in the range of 200 to 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

The method for exposing a photosensitive lithographic printing plate according to the present invention comprises:
Known methods can be used without limitation. A laser is preferred as the light source. For example, as an available laser light source having a wavelength of 350 to 450 nm, the following can be used. As a gas laser, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), a Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), H
e-Cd laser (441 nm, 325 nm, 1 mW-100
mW), Nd: YAG (YVO4) as a solid-state laser
And SHG crystal x 2 times (355mm, 5mW ~ 1
W), Cr: Combination of LiSAF and SHG crystal (4
30nm, 10mW), KNbO as a semiconductor laser system
_3. Ring resonator (430 nm, 30 mW), combination of waveguide type wavelength conversion element and AlGaAs or InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), combination of waveguide type wavelength conversion element and AlGaInP, AlGaAs semiconductor (300 nm to 350nm, 5mW ~ 100mW),
AlGaInN (350 nm to 450 nm, 5 mW to 30 m
W) and other N ₂ lasers (33
7 nm, pulse 0.1 to 10 mJ), XeF (351 nm,
(Pulse 10-250mJ)

In particular, an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 n
m, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

Other light sources available from 450 nm to 700 nm include Ar + laser- (488 nm), YAG
-SHG laser (532 nm), He-Ne laser (633 nm), He-Cd laser, red semiconductor laser (650-690 nm), and 700 nm-120
A semiconductor laser (800
850 nm), Nd-YAG laser (1064 nm)
Can be suitably used.

In addition, ultrahigh-pressure, high-pressure, medium-pressure, and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, ultraviolet laser lamps (ArF excimer laser, KrF excimer laser, etc.), and radiation as electrons X-rays, ion beams, far-infrared rays, etc. can also be used, but the above-mentioned laser light source having a wavelength of 350 nm or more is preferable in terms of inexpensiveness. An InGaN-based semiconductor laser of 400 to 410 nm which can provide safety is particularly preferable.

The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type and the like. The photosensitive layer components of the photosensitive lithographic printing plate of the present invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one. After the lithographic printing plate is loaded on a printing press, a system such as exposure-development can be performed on the printing press.

The photosensitive lithographic printing plate that has been developed is
As described in JP-A-54-8002, JP-A-55-115045, JP-A-59-58431, etc., washing water, a rinsing liquid containing a surfactant and the like, gum arabic and starch derivatives, etc. Is post-treated with a desensitizing solution containing For the post-processing of the photosensitive lithographic printing plate of the present invention, these processings can be used in various combinations. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets.

The effects of the present invention can be obtained by developing the above-described photosensitive lithographic printing plate using a developing solution described below to form an image.

(Developer) The developer component will be described in detail. The developer of the present invention contains a nonionic compound represented by the following general formula (I).

A-W (I)

In the formula (I), A has a log P of AH of 1.
W represents a hydrophobic organic group of 5 or more, and W represents a nonionic hydrophilic organic group having a log P of WH of less than 1.0.

[0099] logP is C. Hansch, A. Leo, "Substi
tuent Constants for CorrelationAnalysis in Chemist
ry and Biology ", J. Will & Sons, 1979. It is commonly used as a hydrophobicity parameter for the octanol / water bilayer system of the molecules of interest (AH and WH). , Defined as the logarithm of the equilibrium concentration ratio P calculated from the ratio distributed to each layer. A hydrogen atom is conveniently bonded to each organic group,
For AH and WH structures, AKGhose, et. al. J.
Comput. Based on the method described in Chem. 9, 80 (1988).

Specifically, the structure includes organic groups A, W
Is different from each other and represents a monovalent organic residue satisfying the above logP. More preferably, the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, and may contain an unsaturated bond,
Heterocyclic group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, carboxylate group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, Represents a substituted phosphono group, a phosphonate group, a substituted phosphonate group, a cyano group, or a nitro group.

Examples of the hydrocarbon group which may have a substituent and may contain an unsaturated bond include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group and a substituted alkenyl group. And alkynyl groups and substituted alkynyl groups.

The alkyl group has 1 to 2 carbon atoms.
Examples thereof include a linear, branched, or cyclic alkyl group up to 0, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group,
Isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl be able to. Among these, straight-chains having 1 to 12 carbon atoms, 3 to 12 carbon atoms.
And a cyclic alkyl group having 5 to 10 carbon atoms is more preferred.

The substituted alkyl group is constituted by a bond between a substituent and an alkylene group. As the substituent, a monovalent nonmetallic atomic group other than hydrogen is used. As a preferred example, a 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-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ary Rucarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N ′
An alkylureido group, an N ′, N′-dialkylureido group, an N′-arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an 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 groups, 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 and its conjugate base group (hereinafter, referred to as carboxylate), 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, sulfonato group) ), Alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl , N-alkyl-N-arylsulfinamoyl, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-arylsulfamoyl, N, N-diarylsulfamoyl Group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl)) and its conjugate base group , N-
Arylsulfonylsulfamoyl group (—SO ₂ NHS
O ₂ (aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base Group, alkoxysilyl group (-Si (Oalkyl) ₃ ), aryloxysilyl group (-Si (Oaryl) ₃ ), hydroxysilyl group (-Si
(OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H
₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), dialkylphosphono group (-PO ₃ (alkyl) _2), diaryl phosphono group (-PO ₃ (aryl) _2), alkyl aryl phosphono group ( —PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as an alkylphosphonate group), a monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonato group), phosphonooxy group (-OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group ( -OPO ₃ (alkyl) _2), diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono group (- OPO ₃ H (alkyl))及A conjugated base group thereof (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group , A nitro group, an aryl group, an alkenyl group, and an alkynyl group.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and mesityl groups. , Cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylca Ba carbamoylphenyl group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group,
Examples include a phosphonatophenyl group. Examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-
Examples thereof include a 1-ethenyl group, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group,
Examples include a trimethylsilylethynyl group and a phenylethynyl group.

As the above-mentioned acyl group (R ³¹ CO—),
R ³¹ is a hydrogen atom or the above-mentioned alkyl group, aryl group, alkenyl group and alkynyl group. On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the above-described hydrogen atoms on the alkyl group having 1 to 20 carbon atoms and forming a divalent organic residue. Examples thereof include a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, Luthiomethyl 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, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group,

[0106]

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A phosphonobutyl group, a phosphonatohexyl group, a diethylphosphonobutyl group, a diphenylphosphonopropyl group, a methylphosphonobutyl group, a methylphosphonatobutyl group, a tolylphosphonohexyl group, a tolylphosphonatohexyl group, a phosphonooxy group Propyl 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. Can be mentioned.

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Groups, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group and the like. Of these, a phenyl group and a naphthyl group are more preferred.

The substituted aryl group is a group in which a substituent is bonded to an aryl group, and those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on a ring-forming carbon atom of the aforementioned aryl group are used. Can be Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of these substituted aryl groups include a biphenyl group, a tolyl group, a 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, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxy Phenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfa Moylphenyl 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, tolylphosphonatophenyl group, allyl group, -Propenylmethyl group, 2 Butenyl, 2-methyl-allyl phenyl group, 2-methyl propenyl phenyl group, 2-propynyl phenyl group, 2-butynyl phenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group include those described above. A substituted alkenyl group is a compound in which a substituent is replaced by a hydrogen atom of an alkenyl group and bonded to the alkenyl group. As the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group is the above-mentioned alkenyl group. Can be. Examples of preferred substituted alkenyl groups include

[0111]

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And the like. Examples of the alkynyl group include those described above. A substituted alkynyl group is a substituent in which a substituent is replaced by a hydrogen atom of an alkynyl group and bonded to the alkynyl group, and the substituent is the substituent in the above-mentioned substituted alkyl group, while the alkynyl group uses the alkynyl group described above. be able to.

A heterocyclic group is a monovalent group obtained by removing one hydrogen on a heterocyclic ring, and further removing one hydrogen from the monovalent group, and the substituent in the above-mentioned substituted alkyl group is bonded. The resulting monovalent group (substituted heterocyclic group). Examples of preferred heterocycles include

[0114]

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[0115]

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And the like.

As the substituted oxy group (R ³² O—), R ³²
Is a monovalent nonmetallic atomic group excluding hydrogen. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy. Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Examples include a phosphonooxy group and a phosphonatoxy group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Examples of the acyl group (R ⁶ CO—) in the acyloxy group include those in which R ⁶ is the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group,
Arylsulfoxy groups and the like are more preferred. Specific examples of preferred substituted oxy groups include a methoxy group, an ethoxy group,
Propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxyethyloxy, methoxycarbonylethyloxy, ethoxycarbonylethyloxy , Methoxyethoxy group, phenoxyethoxy group,
Methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group,
Tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, phenylsulfonyloxy group, phosphonooxy group , Phosphonatoxy and the like.

As the substituted thio group (R ³³ S-), those wherein R ³³ is a monovalent non-metallic atomic group other than hydrogen can be used. Preferred examples of the substituted thio group include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group, those can be cited shown as substituted aryl group, R ⁶ acyl group in the acylthio group (R ⁶ CO-) in As described above. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include
Examples include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group, and a methoxycarbonylthio group.

The substituted amino group (R³⁴NH-, (R³⁵)
(R³⁶) N-) is R³⁴, R³⁵, R ³⁶Removes hydrogen
Monovalent non-metallic atomic groups can be used. Substituted amino
Preferred examples of the group include an N-alkylamino group, N,
N-dialkylamino group, N-arylamino group, N,
N-diarylamino group, N-alkyl-N-aryl
Amino group, acylamino group, N-alkylacylamino
Group, N-arylacylamino group, ureido group, N'-
Alkyl ureido group, N ', N'-dialkyl ureide
Group, N'-arylureido group, N ', N'-diary
Luureido group, N'-alkyl-N'-arylurei
Group, N-alkyl ureido group, N-aryl ureide
Group, N'-alkyl-N-alkylureido group, N'-
Alkyl-N-arylureido group, N ', N'-dia
Alkyl-N-alkylureido group, N ', N'-dial
A kill-N-arylureido group, N'-aryl-N-
Alkyl ureido group, N'-aryl-N-aryl
Raid group, N ', N'-diaryl-N-alkylurea
Id group, N ', N'-diaryl-N-arylurei
Group, N'-alkyl-N'-aryl-N-alkyl
Ureido group, N'-alkyl-N'-aryl-NA
Reelureido group, alkoxycarbonylamino group,
Reeloxycarbonylamino group, N-alkyl-NA
Lucoxycarbonylamino group, N-alkyl-N-ali
-Roxycarbonylamino group, N-aryl-N-al
Coxycarbonylamino group, N-aryl-N-ary
And a roxycarbonylamino group. In these
Examples of the alkyl group and the aryl group include the above-described alkyl group,
Substituted alkyl group, aryl group, substituted aryl group
And acylamino.
Group, N-alkylacylamino group, N-arylacyl
An acyl group (R³³R of CO-)³³Is mentioned above
It is as follows. Of these, more preferred
Is an N-alkylamino group, an N, N-dialkylamino
Group, N-arylamino group, acylamino group and the like.
It is. Specific examples of preferred substituted amino groups include methyl
Amino group, ethylamino group, diethylamino group, morpho
Lino group, piperidino group, pyrrolidino group, phenylamino
Group, benzoylamino group, acetylamino group and the like.
It is.

As the substituted carbonyl group (R ³⁷ —CO—), those in which R ³⁷ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include 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 and the like can be mentioned. As the alkyl group and the aryl group in these, the above-mentioned alkyl group, substituted alkyl group,
And the aryl groups and the substituted aryl groups. Among these, more preferred substituents include a formyl group, an acyl group, a carboxyl group,
Alkoxycarbonyl group, aryloxycarbonyl group,
Carbamoyl group, N-alkylcarbamoyl group, N, N
-Dialkylcarbamoyl group, N-arylcarbamoyl group and the like, and still more preferred are formyl group, acyl group, alkoxycarbonyl group and aryloxycarbonyl group. Specific examples of preferred substituents include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, allyloxycarbonyl, N-methylcarbamoyl,
-Phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ³⁸ -SO-), those wherein R ³⁸ is a monovalent nonmetallic atomic group can be used. Preferred examples include an alkylsulfinyl group, an arylsulfinyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N, N-dialkylsulfinamoyl group, an N-arylsulfinamoyl group, and an N, N-diarylsulfinamoyl. And N-alkyl-N-arylsulfinamoyl groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Among these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R ³⁹ —SO ₂ —), those in which R ³⁹ is a monovalent nonmetallic atomic group can be used.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples include the substituted alkyl group, the aryl group, and the substituted aryl group. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

[0123] sulfonato group (-SO ₃ -) are as described above, means a conjugate base anion group of a sulfo group (-SO ₃ H), is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , C ⁺
a ²⁺ , Zn ^2+, etc.).

As described above, the carboxylate group (—CO ₂ —) means a conjugate base anion group of the carboxyl group (CO ₂ H), and is usually preferably used together with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (N
a ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphono group means one or two of the hydroxyl groups on the phosphono group substituted by another organic oxo group. Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group Examples include an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, and a diphenylphosphono group.

[0126] phosphonate group ^{_{(-PO 3 2-, -PO 3 H}} -)
As I mentioned above the means phosphono group (-PO ₃ H _2), first dissociation or acid, a conjugated base anion group derived from the second dissociation acid. Usually it is preferred to use it with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums: aziniums, etc.), and metal ions (Na
⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphonate group is a conjugate base anion group obtained by substituting one hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups. ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)) can be given. Usually it is preferred to use it with a counter cation. As such counter cations, those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (N
a ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

In the general formula (I), each structure of A and W is more preferably an organic group in which A is an aromatic group, W
Is a nonionic organic group containing a polyoxyalkylene group.

The specific examples of AH and WH are shown below.

[0130]

Embedded image

[0131]

Embedded image

Further, specific examples of the non-ionic compound of the general formula (I) are shown below.

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

More preferred nonionic compounds of the above general formula (I) are those represented by the following formulas (IA) or (IB).

[0137]

Embedded image

(R ₁ and R ₂ are H or C ₁ to C 100)
And n and m are integers of 0 to 100. )

Examples of the compound represented by the general formula (IA) include polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and the like. Examples of the compound represented by the general formula (IB) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, and polyoxyethylene nonyl naphthyl ether.

In the compounds of formulas (IA) and (IB), the number of repeating units of the polyoxyethylene chain is preferably 3 to 50, more preferably 5 to 30. The number of repeating units of the polyoxypropylene chain is preferably 0 to 10, more preferably 0 to 5. The polyoxyethylene portion and the polyoxypropylene portion may be random or block copolymers. The general formula (I-
The nonionic aromatic ether-based activators represented by A) and (IB) are used alone or in combination of two or more.

In the present invention, it is effective to add 1 to 20% by weight, preferably 2 to 10% by weight, of the nonionic compound represented by the general formula (I) in the developer.
Here, if the addition amount is too small, the developability and the solubility of the photosensitive layer components decrease, and if it is too large, the printing durability of the printing plate decreases.

[Chelating Agent] The developing solution of the present invention comprises
May be contained. As a chelating agent,
If Na_TwoP_TwoO₇, Na_FiveP_ThreeO_Three, Na_ThreeP_ThreeO₉, Na_TwoO_FourP
(NaO_ThreeP) PO_ThreeNa _Two, Calgon (Nato polymetaphosphate
Polyphosphates, such as ethylenediamine
Tetraacetic acid, its potassium salt, its sodium salt;
Tylenetriaminepentaacetic acid, its potassium salt, sodium
Salt: triethylenetetramine hexaacetic acid, potassium
Salt, sodium salt thereof; hydroxyethyl ethylene
Diaminetriacetic acid, its potassium salt, its sodium
Salts: nitrilotriacetic acid, its potassium salt, its sodium
Salt; 1,2-diaminocyclohexanetetraacetic acid;
Potassium salt, sodium salt thereof; 1,3-diamino-
2-propanoltetraacetic acid, its potassium salt, its sodium salt
Other than aminopolycarboxylic acids such as thorium salts 2
-Phosphonobutanetricarboxylic acid-1,2,4,
Lithium salt and its sodium salt; 2-phosphonobutanone
Licarboxylic acid-2,3,4, its potassium salt, its nato
Lithium salt; 1-phosphonoethanetricarboxylic acid-1,
2, 2, its potassium salt, its sodium salt;
Roxyethane-1,1-diphosphonic acid, its potassium
Salt, its sodium salt; aminotri (methylenephosphone)
Acid), its potassium salt, its sodium salt, etc.
Organic phosphonic acids can be mentioned. Such a key
The optimal amount of rate agent depends on the hardness of the hard water used and its use.
Varies depending on the dose, but generally the developer
0.01 to 5% by weight, more preferably 0.01 to
It is contained in the range of 0.5% by weight.

[Alkali agent] The developer used in the present invention is an aqueous alkali solution containing a nonionic compound represented by the above general formula (I). The contained alkaline agent,
For example, sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium And inorganic alkali agents such as lithium. Monomethylamine, dimethylamine, trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Organic alkali agents such as triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, and tetramethylammonium hydroxide are also used. These alkali agents are used alone or in combination of two or more.

[Surfactant] The developer used in the present invention may further contain other surfactants described below in addition to the nonionic compound represented by the above formula (I). . As other surfactants, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and the like Polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan triole Sorbitan alkyl esters such as ethate, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate Nonionic surfactants such as sodium: alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfonates such as sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, and sodium octylnaphthalenesulfonate. , Anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, and sulfosuccinate salts such as sodium dilauryl sulfosuccinate: alkyl betaines such as lauryl betaine and stearyl betaine; While amphoteric surfactants such as amino acids can be used, particularly preferred are anionic surfactants such as alkylnaphthalene sulfonates. These surfactants can be used alone or in combination. The content of these surfactants in the developer is preferably from 0.1 to 20% by weight in terms of the active ingredient.

[Other Components] In the developer used in the present invention, in addition to the above components, the following components can be used in combination, if necessary. For example, benzoic acid, phthalic acid, p-ethylbenzoic acid, pn-propylbenzoic acid,
p-isopropylbenzoic acid, pn-butylbenzoic acid,
pt-butylbenzoic acid, pt-butylbenzoic acid, p
Organic carboxylic acids such as -2-hydroxyethylbenzoic acid, decanoic acid, salicylic acid and 3-hydroxy-2-naphthoic acid; organic acids such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol Solvents; chelating agents, reducing agents, dyes, pigments,
Hard water softeners, preservatives and the like can be mentioned. Further, when the plate making method of the present invention is subjected to development processing using an automatic developing machine, the developer becomes fatigued according to the processing amount, so that the processing ability is restored by using a replenisher or a fresh developer. Is also good.

Next, the properties of the developer will be described in detail. [PH] The developer of the present invention is an aqueous alkaline solution having a pH of 12.5, and more preferably a pH of 10.0 from the viewpoint of development speed.
１12.5, most preferably pH 11.0-1.
2.5. [Electrical Conductivity] The electric conductivity of the developing solution of the present invention is 30 mS / cm or less, and more preferably 3 to 30 mS in terms of developing speed.
/ Cm, most preferably 3 to 15 mS / cm.

[Fontability] 30 ml of the developer is put into a 100 ml transparent glass bottle having an inner diameter of 3 cm, and the glass bottle is shaken up and down at 25 ° C. three times per second for 1 minute. Then, it is left still and the time until the bubbles disappear (defoaming time) is measured. The shorter the time, the lower the foaming property and the better (the higher the defoaming property). The developing solution of the present invention preferably has a low foaming property and a defoaming time of 5 minutes or less, and does not disturb the developing process during developing process.

[Color] The developer of the present invention is colorless, preferably colored to the extent that visibility is obtained for the purpose of preventing erroneous recognition with water. [Viscosity] The viscosity of the developer of the present invention is preferably 1.0 to 10.0 cp at 25 ° C. in a water-diluted state, so that a smooth developing process can be performed.

[0149]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

[Production Example of Support] (Support 1: Production of anodized aluminum support) An aluminum plate made of material 1S having a thickness of 0.30 mm was treated with a No. 8 nylon brush and an aqueous suspension of 800 mesh pumicestone. After use, the surface was grained and washed well with water. 1
After etching by immersing in 0% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, washed with water, neutralized with 20% HNO ₃ , and washed with water. This was conducted in a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
The electrolytic surface-roughening treatment was performed with an amount of electricity at the anode of Coulomb / dm ² . The surface roughness was measured to be 0.45 μm (R
a). After immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes,
When a cathode was placed on a grained surface in a 20% H ₂ SO ₄ aqueous solution at 20 ° C. and anodized for 50 seconds at a current density of 5 A / dm ² , the thickness was 2.7 g / m ² . This was designated as support 1.

(Production of Support 2) The undercoat liquid composition 1 for surface treatment described below was coated on the support 1 with a P content of about 0.05 g /
The support 2 was coated so as to have a m ² and dried at 100 ° C. for 1 minute.

<Liquid Composition 1 for Undercoat> Phenylphosphonic acid 2 parts by weight Methanol 800 parts by weight Water 50 parts by weight

(Manufacture of Support 3) The undercoat liquid composition 2 for surface treatment described below was applied to the support 1 described above, with a Si content of about 0.001.
g / m ² was applied and dried at 100 ° C. for 1 minute to obtain a support 3.

<Liquid composition 2 for undercoat> The following components were mixed and stirred. After about 5 minutes, heat generation was observed. After reacting for 60 minutes, the content was transferred to another container, and methanol was further added to 30,000 parts by weight. The addition was used as Liquid Composition 2.

Phosmer PE 20 parts by weight, Unichemical Co., Ltd. 20 parts by weight Methanol 130 parts by weight Water 20 parts by weight Paratoluenesulfonic acid 5 parts by weight Tetraethoxysilane 50 parts by weight 3-methacryloxypropyltriethoxysilane 50 parts by weight

[Production Example of Sensitive Material] A photopolymerizable composition having the following composition was coated on the above-mentioned supports 1 to 3 so that the dry coating weight was as shown in Table 1, and dried at 90 ° C. Then, a photosensitive layer was formed. Subsequently, 3 wt% of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 500) was formed on the photosensitive layer.
Was applied at a dry application weight of 2.5 g / m ² and dried at 100 ° C. for one and a half minutes to obtain a photosensitive lithographic printing plate (light-sensitive material).

(Coating solution for photoconductive layer (photopolymerizable composition): Details are described in Table 1 below) Ethylene unsaturated bond-containing compound (A) a part by weight Linear organic high molecular polymer (B) b part by weight Parts Sensitizer (C) 0.15 parts by weight Photoinitiator (D) 0.30 parts by weight Additive (S) 0.50 parts by weight Fluorinated surfactant 0.03 parts by weight (Megafac F-177: Thermal polymerization inhibitor 0.01 part by weight (N-nitrosohydroxylamine aluminum salt) ε-type copper phthalocyanine dispersion 0.2 part by weight Methyl ethyl ketone 30.0 parts by weight Propylene glycol monomethyl ether 30.0 parts by weight

The ethylenically unsaturated bond-containing compound (A), the linear organic polymer (B), the sensitizer (C), the photoinitiator (D), and the additives used in the photosensitive layer coating solution. (S)
Is shown below.

[0159]

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[0160]

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[0161]

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[0162]

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[0163]

[Table 1]

* The acid value of the photosensitive layer is an actually measured value calculated by measuring the amount of acid contained per 1 g of the photosensitive layer by sodium hydroxide titration.

[Example of developer] A developer having the following composition was prepared.

(Examples: Developers 1 to 20: Details are shown in Table 2 below) Alkali (X) x g Compound (Y) of general formula (I) 5.0 g Chelating agent (Z) 0.1 g Additive 1 (P) 1.0 g Additive 2 (Q) 1.0 g Water (92.9-x) g

The chelating agent (Z), additive 1 (P), and additive 2 (Q) used in the developer are shown below.

[0168]

Embedded image

[0169]

[Table 2]

[Developer Properties Test] The results of investigations on the physical properties of the developers in Table 2 above according to the respective inspection methods described in the present specification are shown in Table 3 below.

[0171]

[Table 3]

[Evaluation of Printing, etc.]
Table 4 below summarizes the results obtained when the developers were combined. The following exposure, printing and development conditions were used. (Evaluation of Developability) After developing the above-mentioned coated photographic material without exposure, the color of the plate was visually evaluated. If there is a residual film, the color of the photosensitive layer remains.

(Evaluation of Printing Durability and Print Smudge Resistance) The above-mentioned coated photographic material was exposed to 405 nm, 30 mW violet LD (internal drum type experimental machine) at 100 μ / cm ² (standard exposure condition) at 4,000 dpi for 175. Scanning exposure of a solid image and a 1-99% halftone image (in 1% increments) under line / inch conditions, followed by automatic development using various developing solutions and finishing gum solution FP-2W (Fuji Photo Film) Standard processing was performed using a machine (LP-850P2 manufactured by Fuji Photo Film Co., Ltd.) to obtain a lithographic printing plate. (The preheating after the exposure is performed at a plate surface temperature of 100 ° C. and a immersion time in a developer of 15 seconds.) Then, the obtained lithographic printing plate was tested for printing stain resistance with a diamond IF2 type printer manufactured by Mitsubishi Heavy Industries, Ltd. Printing was performed using GEOS G Beni (S) manufactured by Dainippon Ink and the ink stains in the non-image areas were visually evaluated.

(Evaluation of Developing Scrap) The above-mentioned coated photosensitive material 20 m
² was developed in the above-mentioned developing solution (1 liter), and was left standing for one month to examine the presence or absence of settling. This result is also shown in the table.
It is shown in FIG.

[0175]

[Table 4]

As is evident from Table 4, the developer of the present invention has good developability, achieves both sensitivity and print smear, and has good processing stability without developing scum.

[Development Behavior Investigation] Table 5 shows the results of investigation of the development behavior and the like of the examples and comparative examples in Table 4 by the inspection method described in this specification.

[0178]

[Table 5]

[0179]

According to the present invention, a specific sensitizing dye-containing photosensitive lithographic printing plate is developed using a specific developing solution to form a plate, whereby a very high contrast is hardly seen due to light fog. A good image was obtained, and the processing stability was able to be improved by greatly reducing the development residue.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shunichi Kondo 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. BB02 BB04 BB13 CC05 2H096 AA06 BA05 BA06 CA03 EA04 EA23 GA09 GA10 GA11 GA12 GA13 2H114 AA04 AA14 AA16 AA22 AA23 BA02 DA04 DA73 EA02 GA03 GA05 GA06 GA09

Claims (4)

[Claims] 1. A photosensitive lithographic printing plate containing at least one of sensitizing dyes represented by the following general formulas (II) and (III) is exposed to a laser beam, and an inorganic alkali agent and And a developing method using a non-silicate developer containing a non-ionic compound represented by the following general formula (I). A-W (I) (wherein A is the logP of A-H
Represents a hydrophobic organic group of 1.5 or more, and W is logP of WH.
Represents a nonionic hydrophilic organic group of less than 1.0. ) (In the formula (II) or (III), T is a sulfur atom or -NR ^3-
And R ³ represents a hydrogen atom, an alkyl group or an aryl group. Y represents a nonmetallic atomic group which forms a basic nucleus of the dye in cooperation with an adjacent T or nitrogen atom and an adjacent carbon atom, and R ¹ and R ² each independently represent a hydrogen atom or a monovalent nonmetallic It is an atomic group and may combine with each other to form an acidic nucleus of the dye. X represents an oxygen atom, a sulfur atom or ＮＲNR ⁴ . R ⁴ represents a hydrogen atom or a monovalent nonmetallic atomic group. ) 2. The plate-making method according to claim 1, wherein the sensitizing dye is at least one of the sensitizing dyes represented by the following formulas (IV), (V) and (VI). Embedded image (In the formulas (IV) to (VI), R ^{5 to} R ¹⁴ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and B represents an aromatic ring or a substituent which may have a substituent. And R ⁷ and R ⁸ and R ¹¹ and R ¹² may combine with each other to form an acidic nucleus of the dye.) 3. The method according to claim 1, wherein the developer contains a chelating agent for a divalent metal. 4. A developer having a pH of 10.0 to 12.5,
The method of making a lithographic printing plate according to any one of claims 1 to 3, wherein the conductivity is 3 to 30 mS / cm.