JP2003050474A - Plate making method for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plate making method for a planographic printing plate in which an IR absorbing dye such as a cyanine dye contained in an image forming layer is prevented from precipitating or depositing in washing and finishing sections in a plate making process and with which a high sharpness clear image can be obtained. SOLUTION: In the plate making method for a planographic printing plate in which an IR sensitive planographic printing plate having an image forming layer containing an IR absorbing dye is exposed to IR, developed and treated with a plate surface treating solution, the plate surface treating solution contains a compound having two or more phosphonic acid groups.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for making a lithographic printing plate.
For more details on the law, please refer to the image containing infrared absorbing dye.
For plate making method of infrared-sensitive lithographic printing plate having image forming layer
Related. [0002] [0002] In recent years, the development of lasers has been remarkable.
Solid-state laser with a light emitting region from near infrared to infrared, semiconductor
Body lasers with high output and small size are readily available
The plate making directly from this digital data
These lasers are not suitable as exposure light sources for systems
Always useful. Image recording material suitable for laser writing
For example, Japanese Patent Laid-Open No. 7-285275 discloses a fee.
A binder such as a resole resin generates heat by absorbing light
And pyrolytic properties such as quinonediazide
In the state before decomposition, the solubility of the binder is substantially reduced.
Type image recording material containing a compound capable of lowering
Fees have been proposed. This is because the exposed part is irradiated with infrared rays.
Substances that absorb heat and generate heat in minutes
To make the exposed part alkali soluble (heat mode)
Is absorbed by the support aluminum.
Low thermal efficiency and alkali in the development process
Solubility in developer is not satisfactory
It was. For this reason, increase the alkali concentration of the developer,
Has been secured. However, a heat-mode type lithographic printing plate precursor
The plate is the image area under high-concentration alkaline conditions as described above.
Have low resistance to dissolution in alkaline processing solutions.
The surface of the recording material is melted with a slight scratch on the surface of the image
There were problems such as causing defects. In particular, alkaline water
Positive type using high molecular compound that is highly soluble in liquid
The trend was more pronounced in the lithographic printing plate precursors
It was. Therefore, it is necessary to prevent the residual film from forming in the non-image area
There is a limit to increasing the alkali concentration of the developer. Also, recent infrared laser exposure type images.
Along with improvements in recording materials, compared to conventional infrared absorbing dyes
Difficult to dissolve in alkaline developer, for example cyanine
There is a tendency to use infrared absorbing dyes such as dyes,
When this image recording material is developed with an alkali developing solution
In addition, insoluble matter of infrared absorbing dye is discharged into the developing solution.
There is a tendency to. This is the component of binder polymer and water
Further insoluble matter is formed by interaction with inorganic substances
These insoluble materials adhere to the plate and interfere with the image.
Or in a washing bath or finishing bath.
It is deposited and deposited and deposited, which is negative for the maintenance of the treatment bath.
It causes inconvenience such as causing burden. This situation
For example, with a residual film on the non-image area,
If the process is applied, the remaining film will carbonize and become dirty during printing.
There is also. Therefore, insoluble matter caused by infrared absorbing dyes
To avoid the inconvenience caused by the
Without forming a sharp and clear image, especially
In fine images including dots and fine lines,
Sharpening and improving reproducibility are required. [0005] SUMMARY OF THE INVENTION The present invention provides a plate making process.
Infrared such as cyanine dye contained in the image forming layer
Line absorbing dye is precipitated and deposited in the water washing and finishing parts.
Can obtain a sharp, clear image.
It is to provide a method for making a planographic printing plate. [0006] [Means for Solving the Problem]
As a result of intensive research to achieve
Infrared photosensitive lithographic printing having an image-forming layer containing a colorant
After exposing and developing the plate, treat it with a specific processing solution.
And see that the above tasks can be achieved.
And the present invention has been completed. Therefore, the present invention
Infrared having an image forming layer containing an infrared absorbing dye
After exposing and developing the photosensitive lithographic printing plate with infrared rays, the plate surface
A process for making a lithographic printing plate including treatment with a treatment liquid.
The plate surface treatment solution has two or more phosphonic acid groups.
Planographic printing plate making comprising a compound
Regarding the method. [0007] The present invention will be described in detail below.
The “plate surface processing solution” as used in the present invention is used after development processing.
This means washing water and finishing liquid.
The finishing liquid is a so-called rinsing liquid surfactant.
Aqueous solutions containing, and generally containing water-soluble polymer compounds
Includes surface protection liquid. Rinse solution and plate protection in this specification
The liquids are collectively called finishing liquids. “Two or more photos” used in the plate making method of the present invention.
As specific examples of the compound having a sulfonic acid group, the following formula
Organic phosphonic acids represented by (I), (II) and (III)
There is no salt. (In the formula (I), R₁, R₂And R_ThreeAre each a hydrogen atom or
Is an expression (Where M¹And M²Are hydrogen atom, Na, NH, respectively._Fouror
Represents K. ), But R₁, R₂And R_ThreeNo
At least two of these represent the group. ) [0009] (In formula (II), M¹And M²Are hydrogen atom, Na, N respectively
H_FourOr represents K. ) [0010] (In the formula (III), R_Four, R_Five, R₆, R₇And R₈Each
Hydrogen atom or formula (In the formula, q represents an integer of 1 to 4, and M¹And M²Is that
Hydrogen atom, Na, NH _FourOr represents K. ) Group
However, R_Four, R_Five, R₆, R₇And R₈At least
2 represents the group, m represents an integer of 1 to 4, and m ′ represents 1
Represents an integer of -4, and n represents 0 or an integer of 1-4. ) Specific examples of the compound represented by the above formula (I)
Aminotri (methylenephosphonic acid) and its salts
For example, DQ2 manufactured by Nihon Monsanto Co., Ltd.
000 (aminotri (methylenephosphonic acid)), DQ2
006 (aminotri (methylenephosphonic acid), 5Na
Salt). The compound represented by the above formula (II) is 1-hydride.
Roxyethane-1,1-diphosphonic acid and its salts,
For example, DQ201 manufactured by Nihon Monsanto Co., Ltd.
0 (1-hydroxyethane-1,1-diphosphonic acid), DQ2
016 (1-hydroxyethane-1,1-diphosphonic acid) · 4
Na salt). A compound represented by the above formula (III) and
Ethylenediaminetetra (methylenephosphone
Acid), hexamethylenediaminetetra (methylenephospho)
Acid), diethylenetriaminepenta (methylenephospho)
Acid) and their salts. With those commercial products
For example, Nippon Monsanto Co., Ltd. DQ2041 (Echi
Range amine tetra (methylenephosphonic acid)), DQ2
042 (ethylenediaminetetra (methylenephosphone
Acid) ・ 5NH_FourSalt), DQ2044 (ethylenediamine)
Tetra (methylenephosphonic acid), 5K salt), DQ205
1 (hexamethylenediaminetetra (methylenephosphone
Acid)), DQ2052 (hexamethylenediaminetetra)
(Methylenephosphonic acid) ・ 6NH_FourSalt), DQ2054
(Hexamethylenediaminetetra (methylenephosphone
Acid) · 6K salt), DQ2060 (diethylenetriamine)
Penta (methylenephosphonic acid)), DQ2066 (die
Tylene triamine penta (methylene phosphonic acid), 5N
a salt). [Washing water] The above organic phosphonic acids are washed with water.
The concentration of the product will be the total mass of the washing water.
Based on 10^-Five10 mass% is suitable, preferably
10^-Four-10 ^-1% By weight, more preferably 10^-3-10
^-2% By mass. In addition, preservatives may be included in the washing water
Often, the preservatives used are fiber, wood processing, food,
Known products used in the fields of medicine, cosmetics, agricultural chemicals, etc.
Can be used. For example, quaternary ammonium salt, monovalent pheno
Derivatives, dihydric phenol derivatives, polyhydric phenol derivatives
Conductor, imidazole derivative, pyrazolopyrimidine derivative
Body, monovalent naphthol, carbonates, sulfone derivative
Body, organotin compounds, cyclopentane derivatives, phenyl
Derivatives, phenol ether derivatives, phenol esthetics
Derivatives, hydroxylamine derivatives, nitrile derivatives
Body, naphthalene, pyrrole derivative, quinoline derivative,
Benzothiazole derivatives, secondary amines, 1,3,5 tones
Liazine derivatives, thiadiazole derivatives, anilide derivatives
Body, pyrrole derivative, halogen derivative, dihydric alcohol
Derivatives, dithiols, cyanate derivatives, thiocarbami
Doic acid derivatives, diamine derivatives, isothiazole derivatives,
Monohydric alcohol, saturated aldehyde, unsaturated monocarboxylic
Acid, saturated ether, unsaturated ether, Lactones, amino acid derivatives, hydantoy
, Cyanuric acid derivatives, guanidine derivatives, pyridine
Derivatives, saturated monocarboxylic acids, benzenecarboxylic acid derivatives
Body, hydroxycarboxylic acid derivative, biphenyl, hydro
Xamic acid derivatives, aromatic alcohols, halogenophenols
Derivatives, benzenecarboxylic acid derivatives, mercaptocal
Bonic acid derivatives, quaternary ammonium salt derivatives, trifer
Nylmethane derivatives, hinokitiol, furan derivatives,
Nzofuran derivatives, acridine derivatives, isoquinoline derivatives
Conductor, arsine derivative, thiocarbamic acid derivative, phosphorus
Acid ester, halogenobenzene derivative, quinone derivative,
Benzenesulfonic acid derivatives, monoamine derivatives, organic polymers
Acid esters, piperazine derivatives, phenazine derivatives,
Pyrimidine derivatives, thiophanate derivatives, imidazoles
Derivatives, isoxazole derivatives, ammonium salt derivatives
Known preservatives in conductors and the like can be used. As a particularly preferred preservative, pyridinethiol
Salt of ole-1-oxide, salicylic acid and salts thereof,
1,3,5-trishydroxyethylhexahydro-S
-Triazine, 1,3,5-trishydroxymethyl
Xahydro-S-triazine, 1,2-benzisothia
Zolin-3-one, 5-chloro-2-methyl-4-iso
Thiazoline-3-one, 2-bromo-2-nitro-1,
3-propanediol is mentioned. Preferred addition amount
Is stable against bacteria, mold, yeast, etc.
Depending on the type of bacteria, mold and yeast
However, the range of 0.001 to 10% by mass with respect to the washing water is
It is preferable and effective against various molds and bacteria.
Thus, it is preferable to use two or more kinds of preservatives in combination. [Rinse solution] Rinse the organic phosphonic acids
When used in a liquid, the concentration is determined by the quality of the rinse liquid.
10 based on quantity^-Five-10 mass% is suitable and preferred
Or 10^-Four-10^-1% By weight, more preferably 10^-3~
10^-2% By mass. In addition to the above compounds,
Including surfactant, pH adjuster, lipophilic substance,
Preservatives, antifungal agents, antifoaming agents, etc.
Yes. As the surfactant that is the main component of the rinse liquid,
Nionic surfactant, cationic surfactant, amphoteric surfactant
Agents and nonionic surfactants. Anion world
Surfactants include fatty acid salts, abietic acid salts, hydride
Roxyalkane sulfonates, alkane sulfonates
, Α-olefin sulfonates, dialkyl sulfos
Succinates, alkyl diphenyl ether disulfones
Acid salts, linear alkylbenzene sulfonates, branched chain
Alkylbenzene sulfonates, alkyl naphthalene
Sulfonates, alkylphenoxy polyoxyethylene
Propyl sulfonates, polyoxyethylene alkyl
Rusulfophenyl ether salts, N-methyl-N-ole
Irtaurine sodium, N-alkylsulfosucci
Acid monoamide disodium salt, aminocarboxylate
Kind, Petroleum sulfonates, sulfated castor oil, sulfur
Oxidized beef tallow oil, sulfate ester of fatty acid alkyl ester
, Alkyl sulfate esters, polyoxyethylene
Rukiruether sulfates, fatty acid monoglycerides
Desulfuric acid ester salts, polyoxyethylene alkylphenol
Nyl ether sulfates, polyoxyethylenes
Tyryl phenyl ether sulfate, alkyl phosphorus
Acid ester salts, polyoxyethylene alkyl ether
Phosphate ester salts, polyoxyethylene alkylpheny
Ruether phosphate esters, styrene-anhydrous maleic acid
Partial saponification products of acid copolymers, olefin-maleic anhydride
Partially saponified products of acid copolymers, naphthalenesulfonic acid
And salt formalin condensates. Among these
Dialkyl sulfosuccinates, alkyl sulfates
Salts and alkylnaphthalene sulfonates and α-
Olefin sulfonates, alkyl diphenyl ether
Rudisulfonates are particularly preferably used. Kachi
On-surfactants include alkylamine salts, quaternary
Ammonium salts and the like are used. Examples of amphoteric surfactants include alkylcarbo.
Xybetaines, alkylimidazolines, alkylamines
Minocarboxylic acids and the like are used. Nonionic surfactant
As polyoxyethylene alkyl ethers,
Reoxyethylene alkylphenyl ethers, polio
Xylethylene polystyryl phenyl ether, polyoxy
Siethylene polyoxypropylene alkyl ether, group
Lysine fatty acid partial ester, sorbitan fatty acid part
Esters, pentaerythritol fatty acid partial esters
, Propylene glycol mono fatty acid ester, sucrose
Fatty acid partial ester, polyoxyethylene sorbitan fat
Fatty acid partial esters, polyoxyethylene sorbitol
Fatty acid partial esters, polyethylene glycol fatty acid
Esters, polyglycerol fatty acid partial esters, Polyoxyethylenated castor oil, polio
Xylethyleneglycerin fatty acid partial esters, fatty acids
Diethanolamides, N, N-bis-2-hydroxy
Alkylamines, polyoxyethylene alkylamino
, Triethanolamine fatty acid ester, trialkyl
Molecular weight of ruamine oxide and polypropylene glycol
200-5000, trimethylolpropane, glycerin
Or sorbitol polyoxyethylene or polyoxy
Cypropylene adducts, acetylene glycol series, etc.
I can get lost. Also, fluorine and silicon nonionic surface activity
Agents can be used as well. The surfactant is two types
These can be used together. Use amount must be limited
However, the preferred range is based on the total mass of the rinse solution.
Accordingly, 0.01 to 20% by mass is appropriate, and preferably 0.0 to 20% by mass.
05 to 10% by mass. The rinse liquid used in the present invention also has a constitution.
Copolymer containing a monomer unit having a sulfonic acid group as a component
A polymer can be included. Component of the copolymer
A monomer unit having a sulfonic acid group (hereinafter referred to as mono
The “sulfonic acid group” of the mer unit (a) is sulfo
Not only the acid group (—SO 3 H) itself, but also sulfone
Carbonate groups such as alkali metal salts, ammonium salts, and
Also means and includes water-soluble amine salts. mono
The monomer constituting the monomer unit (a) is p-styrene.
Sulfonic acid, 2-acrylamido-2-methylpropa
Sulfonic acid, ethylene sulfonic acid, 2-chloroethylene
Sulfonic acid, ethylene disulfonic acid, 1-propene
1-sulfonic acid, 1-propene-2-sulfonic acid, 2-
Methyl-1,3-propene disulfonic acid, 1-butene-
1-sulfonic acid, 1-pentene-1-sulfonic acid, 1-
Hexene-1-sulfonic acid, 2-phenylethylenesulfuric acid
Phosphonic acid, 1-methyl-2-phenylethylenesulfone
Acid, 3-chloroallylsulfonic acid, allylsulfonic acid,
3-chloro-2-butenesulfonic acid, 3-chlorometac
Rylsulfonic acid, methallylsulfone, 3-methyl
2-butene-2-sulfonic acid, 3-phenylallyls
Sulfonic acid, 3-phenylmethallylsulfonic acid, 2-vinyl
Nylyl sulfonic acid, 2-chloro-4-styrenes
Sulfonic acid, vinyltoluenesulfonic acid, α-methylstyrene
Rensulfonic acid, and alkali metal salts thereof,
Examples include monium salts and water-soluble amine salts. These are appropriate
One type or two or more types are selected. Particularly preferred monomers
The monomer constituting the unit (a) is p-styrene sulfone
Acid, 2-acrylamido-2-methylpropanesulfone
Acid, ethylene sulfonic acid and its sodium salt, potassium
Umm salt. In the copolymer, the monomer unit (a)
The content is suitably 5 to 95 mol%. Monomer unit
When the amount of (a) is less than 5 mol%, the copolymer is
Less soluble in finishing liquid, more than 95 mol%
The effect of suppressing the precipitation of photosensitive components is insufficient.
Yes. In the copolymer, a monomer other than the monomer unit (a)
As the mer unit, the alkyl residue has 1 to 10 carbon atoms.
Alkyl acrylates and carbons of alkyl residues
From alkyl methacrylates having 4 to 10 atoms
A monomer unit selected from the group consisting of
(b)). Monomer constituting the monomer unit (b)
Specific examples include methyl acrylate and ethyl acrylate.
Rate, n-propyl acrylate, isopropyl acetate
Relate, n-butyl acrylate, isobutyl acrylate
Rate, n-amyl acrylate, isoamyl acrylate
, N-hexyl acrylate, 2-ethylhexyl
Acrylate, n-octyl acrylate, n-decyl
Acrylate, n-butyl methacrylate, methyl meta
Chlorate, ethyl methacrylate, isobutyl methacrylate
Relate, n-amyl methacrylate, 2-ethylhex
Sil methacrylate, n-octyl methacrylate, n
-Decyl methacrylate etc., these monomers
Can be used alone or in combination of two or more
The Monomers constituting the particularly preferred monomer unit (b)
As methyl acrylate, ethyl acrylate
Can be mentioned. In the copolymer, the monomer unit (b)
The content is suitably in the range of 5 to 95 mol%. monomer
When the amount of unit (b) is less than 5 mol%,
The effect of suppressing the precipitation of water is not sufficient, from 95 mol%
If the amount is too large, the copolymer is difficult to dissolve in the finishing solution.
Become. The copolymer is a monomer other than the monomer unit (a).
Monomers as listed below as monomer units
A monomer unit (c) composed of
Styrene, o-methylstyrene, m-methylstyrene, p-me
Tylstyrene, 2,4-dimethylstyrene, 2,5-dimethyls
Tylene, 3,4-dimethylstyrene, 3,5-dimethylstyrene
2,4,5-trimethylstyrene, 2,4,6-trimethylstyrene
Len, o-ethylstyrene, o-sec-butylstyrene, o-te
rt-Butylstyrene, p-fluorostyrene, 2,5-diflu
O-styrene, o-chlorostyrene, m-chlorostyrene,
p-chlorostyrene, 2,4-dichlorostyrene, 2,5-dichloro
Rostyrene, 2,6-dichlorostyrene, 3,4-dichlorostyrene
Len, p-bromostyrene, p-cyanostyrene, acrylo
Nitrile, methacrylonitrile, methyl methacrylate
, Ethyl methacrylate, acrylamide, N-sec-B
Tilacrylamide, N-tert-butylacrylamide,
N, N-dibutylacrylamide, N-tert-butylmethacrylate
Luamide etc. These are one or a combination of two or more
Can be used. Among these, the preferred method is
There are chill methacrylate and ethyl methacrylate. Up
The copolymer contains 90 moles of such monomer units (c).
%, Preferably up to about 70 mol%.
The Specific examples include monomer unit (a) and monomer unit.
(b) is 10 to 30 mol% and 10 to 30 mol%, respectively.
In the range, and the remainder is the monomer unit (c)
A copolymer is mentioned. The molecular weight of the copolymer is 1,000 to 50,
000 is suitable, preferably 3,000 to 20,000
It is. Such a copolymer is produced by a conventionally known method.
For example, copolymerization by solution polymerization method
And neutralize the acid residues of the copolymer produced as desired.
It can also be collected. In this solution polymerization method,
For example, isopropyl alcohol which can dissolve monomers of ordinary raw materials
The presence of a polymerization initiator in a nitrogen atmosphere in a solvent such as coal
Copolymerize in the presence. The same as usual latex synthesis.
In this way, the raw material monomer is emulsified in water in a surfactant.
Let the milk with a polymerization initiator such as potassium persulfate.
May be obtained as an aqueous dispersion obtained by chemical polymerization.
You may extract | collect as a solid substance. The above weight in the rinse solution
The combined content is 0.005 based on the total mass of the rinse solution.
-10 mass% is suitable. Less than 0.005 mass%
And the effect of suppressing the precipitation of the photosensitive component is not sufficient.
If the amount is more than 0% by mass, the foaming property of the rinse liquid becomes high, and the mark
Tends to adversely affect printability. Finishing liquids such as rinse liquids are generally used.
In particular, it should be used in the range of pH 3-12, which is lower than the developer.
Are advantageous. Common for pH 3-12
Add mineral acid, organic acid or inorganic salt to the finishing solution.
Add and adjust. The amount added is 0.01 to 2% by weight.
For example, as mineral acids, nitric acid, sulfuric acid, phosphoric acid, metaphosphoric acid, etc.
Is mentioned. Organic acids include citric acid, acetic acid, succinic acid,
Malonic acid, p-toluenesulfonic acid, tartaric acid, apple
Acid, lactic acid, levulinic acid, phytic acid, organic phosphonic acid,
In addition, amino acids such as glycine, α-alanine and β-alanine
Noic acid and the like. Magnesium nitrate as an inorganic salt
, Primary sodium phosphate, secondary sodium phosphate, sulfur
Nickel oxide, sodium hexametaphosphate, tripolyphosphate
Sodium acid etc. are mentioned. Mineral acid, organic acid or inorganic
You may use together at least 1 sort or 2 sorts of salt etc.
Yes. The rinse liquid should be included in the washing water described above.
The same preservatives and antifungal agents can be included. So
Is added in an amount of 0.001-1 based on the total mass of the rinse liquid
A range of 0% by weight is suitable. The rinsing liquid also contains a lipophilic substance.
You can also keep it. As a result, the image portion of the planographic printing plate
Develops higher ink sensitivity and develops ink
(After development, to make the image easier to see, and to improve the oil sensitivity of the image
Emulsion type ink (usually black)
Can be easily placed on the image)
When performing plate surface protection liquid treatment after treatment with aqueous solution,
A decrease in the oil sensitivity of the image area can be strongly suppressed. Like
New lipophilic substances include oleic acid, lanolinic acid,
Valeric acid, nonyl acid, capric acid, myristic acid, palmi
Organic carvone having 5 to 25 carbon atoms such as chic acid
Acids, castor oil, etc. are included. These lipophilic substances are simply
Can be used alone or in combination of two or more
The The lipophilic substance to be included in the rinse liquid
0.005 to 10% by mass, more preferably 0.05 to
It is in the range of 5% by mass. It is also possible to add an antifoaming agent
In particular, silicon antifoaming agents are preferred. Emulsified content in it
Both a dispersion type and a solubilized type can be used. Preferably
0.001 to 1.0% by mass with respect to the rinsing liquid at the time of use
The range is optimal. [Plate surface protective solution] The organic phosphonic acids are applied to the plate surface.
When used in the protective liquid, the concentration of the plate surface protective liquid
10 based on total mass^-Five10 mass% is suitable,
Preferably 10^-Four-10^-1% By weight, more preferably 10
^-3-10^-2% By mass. Plate protection liquid is generally concentrated liquid
A mode in which the product is prepared and diluted with water at the time of use.
May be used in The concentration at this time is the plate protection
It is appropriate that each component of the agent does not cause separation or precipitation.
The Content and addition amount of various components of the plate surface protection liquid here
Unless otherwise stated, the concentration at the time of use, that is, at the time of use is
Sure. The plate surface protective liquid contains a surfactant.
To improve the quality of the coated surface and ink fillability.
You can. Examples of such surfactants are listed above.
Use the same surfactant as the component of
can do. Limit the amount of surfactant used
It is not necessary, but preferably 0.0% of the total mass of the plate surface protective liquid.
1 to 20% by mass. In addition to the plate surface protection liquid, a water-soluble polymer is used.
Compound, pH adjuster, wetting agent, preservative, nitric acid as required
Including salts, sulfates, chelating compounds, antifoaming agents, etc.
You can. The plate surface protection liquid is a water-soluble polymer compound.
Basically, about 15-20% aqueous solution of gum arabic
Often used. Various water besides gum arabic
Soluble resin is used as the main component of the plate surface protection liquid. example
Dextrin, stellabic, structan, al
Guinates, polyacrylates, hydroxyethyl acetate
Rulose, polyvinylpyrrolidone, polyacrylamid
, Methylcellulose, hydroxypropyl cellulose
, Hydroxymethylcellulose, carboxyalkyl
Cellulose salt, water-soluble polysaccharide extracted from soybean okara
And pullulan or a pullulan derivative,
Livinyl alcohol is also preferred. Furthermore, as a modified starch derivative,
Roasted starch such as sugar, enzyme dextrin and shear
Enzyme-modified dextrins such as dinger dextrin, possible
Oxidized starch, modified pregelatinized starch
Pregelatinized starch such as unmodified pregelatinized starch, phosphorus
Acid starch, fat starch, sulfate starch, nitrate starch, xanthogen
Esterified starch such as acid starch and carbamic acid starch,
Ruboxyalkyl starch, hydroxyalkyl starch,
Foalkyl starch, cyanoethyl starch, allyl starch,
Starch, carbamylethyl starch, dialkylamino
Etherified starch such as starch, methylol cross-linked starch, hydro
Xylalkyl cross-linked starch, phosphoric acid cross-linked starch, dicarboxylic acid bridge
Crosslinked starch such as bridge starch, starch polyacrylamide copolymerization
Body, starch polyacrylic acid copolymer, starch polyvinyl acetate
Copolymer, starch polyacrylonitrile copolymer, Khaochi
Starch-based polyacrylate copolymer, Chaotic starch vinyl polymer copolymer,
Starch polystyrene maleic acid copolymer, starch polyethylene
Oxide copolymer, starch polypropylene copolymer, etc.
The starch graft polymer is preferred. Natural polymer compound
As a thing, potato starch, potato starch, tapioca
Starches such as starch, wheat starch and cornstarch
Jinan, Laminaran, Umi Saw Mannan, Funari, Ai
Algae such as rich moss, agar and sodium alginate
Derived from potatoes, Trolley, Mannan, Quinn
Sused, Pectin, Tragacanth gum, Karaya gum,
Xanthine gum, guarbin gum, locust binga
Plant mucous, carob gum, benzoin gum, etc.
Homopolysaccharides such as dextran, glucan, levan, etc.
Hetropolysaccharides such as succinoglucan and santangum
Microbial mucilage, glue, gelatin, casein and co
Proteins such as Lagen are preferred. In the plate surface protection liquid,
Use one or more water-soluble polymer compounds in combination.
You can also. The content of these compounds depends on the quality of the plate surface protection liquid.
3-30 mass% is appropriate based on the amount, more preferred
Or 4 to 25% by weight. The plate surface protective liquid used in the present invention also contains
The components described above as components to be included in the liquid
Containing a monomer unit having a sulfonic acid group
Can be included. Polymerization in the plate surface protection liquid
The content of the body is 0.005 based on the total mass of the plate surface protection liquid.
-10 mass% is suitable. Less than 0.005 mass%
And the effect of suppressing the precipitation of the photosensitive component is not sufficient.
When the content is more than 0% by mass, the foaming property of the plate surface protection liquid becomes high,
There is a tendency to adversely affect printability. The plate surface protection solution has an acidic range of pH 2.5-5.
It is generally advantageous to use a range. pH 2.5-5
In order to adjust to pH, as pH adjuster, inorganic acid, organic acid
It is also appropriate to add salts thereof. Inside
Also, mineral acids, organic acids or inorganic salts are used. Addition amount
Is generally 0.01-based on the total mass of the plate surface protective liquid
3% by weight is suitable. For example, mineral acids include nitric acid, sulfur
An acid, phosphoric acid, metaphosphoric acid, etc. are mentioned. As an organic acid
Is citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfuric acid
Phosphonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phyti
Examples include acid and organic phosphonic acid. As an inorganic salt
Primary sodium phosphate, secondary sodium phosphate, hexa
Sodium metaphosphate, sodium tripolyphosphate, etc.
Can be mentioned. One of these mineral acids, organic acids or inorganic salts
You may use individually or in combination of 2 or more types. As the wetting agent, ethylene glycol, plastic
Lopylene glycol, triethylene glycol, butylene
Glycol, hexylene glycol, diethylene glycol
Coal, dipropylene glycol, glycerin, trime
Tyrolpropane, diglycerin, etc. are preferably used
The These wetting agents may be used alone, but two or more
You may use together. In general, the wetting agent is the total amount of the plate surface protection liquid.
Used in an amount of 1-5% by weight based on the weight. As the preservative and antifungal agent, the above-mentioned washing water,
Include the same components listed above
be able to. Preferred addition amount is bacteria, mold, yeast, etc.
In contrast, the amount is stable and effective, and
Plate protection during use, depending on the type of bi and yeast
A range of 0.01 to 4% by mass relative to the liquid is preferable,
2 or more types to be effective against various molds and sterilization
It is preferable to use a preservative in combination. As nitrate and sulfate, magnesium nitrate
Sodium nitrate, potassium nitrate, ammonium nitrate
Sodium sulfate, potassium sulfate, ammonium sulfate
, Sodium hydrogen sulfate, nickel sulfate, etc.
The The content of these salts is based on the total mass of the plate surface protection liquid.
And about 0.1 to 5% by mass. Usually, the plate surface protective liquid is a concentrated liquid for economic reasons.
And diluted by adding tap water, well water, etc.
used. In tap water, well water, etc. used for this dilution
The calcium ions present have an adverse effect on printing, and the printed matter
May cause dirt. So this inconvenience
Chelate compounds can be added to prevent
The Preferred chelate compounds include, for example, ethyl
Diaminetetraacetic acid, its potassium salt, its sodium
Salt; diethylenetriaminepentaacetic acid, potassium
Salt, its sodium salt; triethylenetetramine hexa
Acetic acid, its potassium salt, its sodium salt, hydroxy
Ethylethylenediaminetriacetic acid, its potassium salt,
Sodium salt of nitrilotriacetic acid, its sodium salt
Phosphonoalkanetricarboxylic acids such as
Can be. Sodium salt of the above chelating agent, potassium
Organic amine salts are also effective instead of um salts. These keys
The rate agent is stably present in the plate surface protective liquid composition, and printability is improved.
Those that do not inhibit are selected. As an addition amount, it is a plate when used
0.001 to 1.0 mass% is appropriate with respect to the surface protective liquid.
The As a defoaming agent, a general silicon-based self
Emulsification type, emulsification type, surfactant nonionic HL
Compounds such as 5 or less of B can be used. Above all
Silicon antifoaming agents are preferred. Among them, emulsified dispersion type and possible
Any of the solubilized types can be used. Antifoam content is good
More preferably, it is 0.001 to 1.
A range of 0% by mass is appropriate, 0.005 to 0.5% by mass.
The% range is optimal. In the plate surface protective liquid, in addition to the above components, a sensitizing agent is used.
Can also be added. For example, poorly water soluble and boiling point 160
Use an organic solvent at ℃ or higher. As its preferred compound
For example, dibutyl phthalate, diheptyl phthalate
, Di-n-octyl phthalate, di (2-ethylhexyl)
Syl) phthalate, dinonyl phthalate, didecyl phthalate
Rate, dilauryl phthalate, butyl benzyl phthalate
Phthalic acid diester agents such as dioctyl
Dipetate, butyl glycol adipate, dioctylua
Zelate, dibutyl sebacate, di (2-ethylhexyl)
2) Aliphatics such as sebacate and dioctyl sebacate
Epoxides such as basic acid esters such as epoxidized soybean oil
Xylated triglycerides such as tricresylphosphine
, Trioctyl phosphate, Triskrol
Phosphate esters such as tylphosphate, eg benzo
Freezing point of benzoic acid esters such as benzyl fragrate
Plastics with a boiling point of 300 ° C or higher at 1 atm or below at 15 ° C
Agent is included. Other alcohols include 2-octa
Nord, 2-ethylhexanol, nonanol, n-de
Canol, undecanol, n-dodecanol, trime
Tyrnonyl alcohol, tetradecanol, benzyl alcohol
And lecoles. Ethylene as glycol type
Glycol isoamyl ether, ethylene glycol
Monophenyl ether, ethylene glycol benzyl ether
-Teleethylene glycol hexyl ether, octile
Glycol and the like. Boiling point for hydrocarbons
Aromatic and aliphatic compounds of petroleum fractions above 160 ° C
Wallan etc. are mentioned. The conditions for selecting the above compounds are as follows.
Environmental safety, especially odor. Of these solvents
The amount used is 0.01 to 1 based on the total mass of the plate surface protective liquid.
0% by mass is appropriate, more preferably 0.05 to 5.0.
%. These solvents are used alone or in combination of two or more.
You can also The above oil sensitizers protect the plate surface
Leave the liquid as an emulsified dispersion and let it contain as its oil phase
It can also be solubilized with the help of solubilizers
Good. The remainder of the plate surface protection liquid is water. The plate making method of the present invention comprises a plate surface processing solution after development.
Washing water containing the above organic phosphonic acid compounds,
Use at least one of rinse solution and plate surface protection solution
The Therefore, as a processing step after development processing, washing water is used.
Treatment only, rinse treatment only, plate surface protection solution
Washing water only → Rinse liquid → Plate surface protection liquid, Rinse water →
Rinse solution, rinse solution → plate surface protection solution, washing water → plate surface protection solution
Select from various processes, etc.
As at least one of water, rinsing liquid or plate surface protecting liquid,
As described above, “having two or more phosphonic acid groups
A plate surface treatment liquid containing a “compound” can be used. The processing method using the plate surface processing solution is a conventional method.
Follow the method, for example, using an automatic processor
Can do. In recent years, for printing plates in the plate making and printing industries
Automatic processing machines are widely used to streamline and standardize plate making operations
It is often used. This automatic processor generally has a developing unit and
Consists of a post-processing unit that transports printing plate material and each process
Consists of a liquid bath and a spray device.
Each processing solution pumped up by the pump is sputtered while being transported flat.
The developing process is performed by spraying from the lay nozzle. Ma
Recently, a submerged guide in a processing liquid bath filled with processing liquid.
Process the printing plate by dipping and transporting it with a roll
The method is also known. In such automatic processing
Replenish each plate surface processing solution according to the processing amount, operating time, etc.
Processing can be performed while replenishing the liquid. Also substantial
So-called disposable processing, which is processed with each unused processing solution
It is also possible to adopt a method. A general processing method will be described below. Flat plate
The washing water in the washing process for printing plates is used repeatedly.
Fresh water for each lithographic printing plate
It may be used, and part of the circulating flush water
It may be used while supplementing with. Wash water repeatedly
For example, JP-A-2
Of an automatic processor as described in Japanese Patent No. 2569
Fill the rinsing tank with a predetermined amount of rinsing water.
Add various ingredients weighed by law, or
Various types of water measured by appropriate methods using a predetermined amount of water
The method of mixing the ingredients and then charging them into the washing tank
Is mentioned. Use flush water repeatedly as above
If rinsed, rinse solution used in the process after washing
Or developer components in washing water recycled to the plate surface protection solution
Replenish the flush tank with fresh water to reduce contamination
May be. In such a case, make various kinds of fresh water.
Needless to say, add
Fill the storage tank with fresh water and fill it with water
Add various ingredients weighed in a proper way, or
Is measured in advance with a predetermined amount of water and appropriate method
To mix the various ingredients and then charge them to the storage tank
Etc. Or the storage tank is a floater tube
If the model automatically keeps the water level constant by reason,
A method of adding a certain amount of various components to the storage tank at intervals
There is also. The washing water used is one of the planographic printing plates.
Adding fresh ingredients to the wash water when the plate is fresh water
For example, JP-A-2-3065 or Japanese Patent Application No.
Automatic current as described in Japanese Patent Publication No. 5-746723
Fill the storage tank of the machine's flush water with a predetermined amount of water,
How to add various ingredients weighed by appropriate methods
Or a predetermined amount of water and appropriate method
Mix the various components weighed in accordance with, and then to the storage tank
The method to prepare is mentioned. Or the storage tank
If the model automatically keeps the water level constant by rotor management
For example, a certain amount of various components are stored in the storage tank every certain period.
The method of adding is also effective. Flushing water with various ingredients added
As a method of washing the planographic printing plate with water, for example, water
Immerse the lithographic printing plate in a bath filled with washing water, preferably
A method of removing by stirring, alone or on a lithographic printing plate
Washing water on the plate through pipes with multiple narrow openings
There are ways to supply. When using an automatic processor
The latter method is advantageous. The washing water in this case is PS version
The appropriate amount is supplied in a timely manner as it passes through the water washing section.
It is preferred that The preferred amount of water to wash is 5 to 300 cc
/ M ²But more preferably 10 to 100 cc / m²,
Particularly preferably 20 to 80 cc / m²It is. 5cc / m²Not yet
If it is full, the lithographic printing plate will be insufficiently washed with water, 300cc / m.
²Exceeding this is not preferable because the amount of wastewater increases. Washed with water
The planographic printing plate has less washing water remaining on the plate surface.
Preferably squeezed, and the squeeze method and
It is possible to squeeze the developer.
When using a developing machine, a method using an elastic roller pair
Is preferred. Finishing used in the plate making method of the present invention
The pH of the solution is different from that of the alkaline developer.
Contains an appropriate amount of pH adjuster for control
It is preferable to leave it in place, and it contains an appropriate pH adjuster.
Replenish the finishing replenisher with pH
You can also Finishing replenisher used for this
Is the same liquid as the finishing liquid.
Liquids with different dilution ratios and liquids with completely different formulations may be used. Present
A water washing process between image processing and finishing liquid processing
It is recommended that the developer on the planographic printing plate be washed with water.
It is preferable for increasing the processing capacity of the slushing liquid. Above and
Preferred developers on lithographic printing plates after squeezing
And the remaining amount of washing water is 20 ml / m²The following is preferable, yo
More preferably 10 ml / m²And most preferably
5ml / m²It is as follows. Finished with finishing solution
A method for immersing a lithographic printing plate in a finishing solution,
How to apply the finishing liquid with a roller, many nozzles
Finishing liquid is ejected from the PS plate or roller
Various methods such as spraying on the
Plate making process by repeatedly using the singing solution
Significantly reduce the amount of finishing solution used per PS plate
It is possible to Finishing liquid on lithographic printing plate
The amount used in the processing method supplied to
It is preferably at least 40 liters / minute. More preferred
3 to 20 liters / minute. Also, a lot of noz
High agitation on lithographic printing plates
The method of processing in the clean state is to leave residual adhesion on the lithographic printing plate.
What can be washed with the finishing solution
Moreover, since the finishing liquid is made uniform,
Is preferred. The replenishment of the finishing solution is alkali development.
Control the rinse solution to a predetermined pH against
Developer component for rolling and finishing liquid
Dilute the concentration of the gel to make it difficult to precipitate gel-like insoluble matter
Specifically, the throughput of the PS plate, preferably the processing amount
Performed according to the surface area, PS plate 1m²Against
Or in the range of 1 to 400 cc, more preferably 5 to 200 cc.
Performed in the range of cc. More preferably 5 to 100 cc
It is a range. The replenisher is the finishing solution charged at the beginning
The solution with exactly the same composition and concentration as the above, only the water dilution rate is changed with the same composition.
The obtained liquid or a liquid of another composition may be used. Also, after treatment with washing water or rinsing liquid
Burning treatment may be performed. Burning process is 2
Heat at 00-300 ° C. After heating, as it is
You can proceed as much as you can. After heating, wash with water
It can also be post-treated with a treatment liquid and proceed to the printing process. Infrared absorbing dye to which the plate making method of the present invention is applied
Infrared photosensitive lithographic printing plate containing
It is not something. In addition, exposure processing and development processing are performed in a conventional manner.
Therefore, the treatment with the plate surface treatment liquid can be carried out.
In combination with a general automatic processor
The Infrared absorbing dye to which the plate making method of the present invention is applied
Infrared photosensitive lithographic printing having an image-forming layer containing a colorant
Plate and general alkali used in the plate making method of the present invention
The developing solution will be described. Infrared photosensitive lithographic printing plate
Has an image-forming layer on the support, and if necessary
It has other layers, and the image forming layer is (A) infrared absorbing dye
And (B) an alkali-soluble polymer compound
Optionally (C) compatible with alkali-soluble polymer compounds
Alkaline aqueous solution of the alkali-soluble polymer compound
The solubility in the water is reduced and the solubility is increased by heating.
Compounds that have a lowering effect, such as (D) cyclic acid anhydrides
You may contain. In the case of negative planographic printing plate precursors
In the image forming layer, the exposed portion is cured to become an image portion.
(E) a compound that generates an acid by heat, and (F)
And a crosslinking agent that crosslinks with an acid. Less than
Next, each component will be briefly described. -(A) Infrared absorbing dye- The infrared absorbing dye used in the image forming layer absorbs infrared light.
There is no particular limitation as long as it is a dye that generates heat and generates heat.
Various dyes known as absorbing dyes can be used
The Infrared absorbing dyes include commercially available dyes or literature (eg
For example, “Dye Handbook”, edited by the Society of Synthetic Organic Chemistry, Showa 45
For example, azo dyeing
Materials, metal complex azo dyes, pyrazolone azo dyes, naphtho
Non dye, anthraquinone dye, phthalocyanine dye,
Carbonium dye, quinoneimine dye, methine dye,
Anine dyes, squarylium pigments, pyrylium salts, metals
And dyes such as thiolate complexes. Of these dyes
Among them, those that absorb infrared light or near infrared light are infrared.
Suitable for use with lasers that emit light or near infrared light
Is particularly preferable. Absorbs such infrared light or near infrared light.
Examples of dyes to be collected include, for example, JP-A-58-125246.
JP, 59-84356, JP 59-2028
No. 29, cyanine described in JP-A-60-78787, etc.
Dye, JP-A-58-173696, JP-A-58-18
1690, Japanese Patent Laid-Open No. 58-194595, etc.
Chin dye, JP-A-58-112793, JP-A-58-
224793, JP-A-59-48187, JP-A-5
9-73996, JP-A-60-52940, JP-A
Naphthoquinone dyes described in JP-A-60-63744, etc.
Squarylium color described in Sho58-112792 etc.
Cyanine described in British Patent 434,875
Dyes described in US Pat. No. 5,380,635
Preferred examples include hydroperimidine squarylium dyes.
It is. Also, as a dye, US Pat. No. 5,156,
Also preferred is a near-infrared absorption sensitizer described in No. 938,
The substitution described in US Pat. No. 3,881,924
Aryl benzo (thio) pyrylium salts,
-142645 (US Pat. No. 4,327,169)
Trimethine thiapyrylium salt described in Japanese Patent Publication No.
-181051, 58-220143, 59-
41363, 59-84248, 59-842
49, 59-146063, 59-14606
The pyrylium compound described in No. 1, JP 59-216 A
146, a cyanine dye described in US Pat. No. 4,28.
Pentamethine thiopylium described in 3,475 specification
To salt etc., Japanese Patent Publication Nos. 5-13514 and 5-19702
The described pyrylium compounds, commercially available products include Epolight I
II-178, Epolight III-130, Epolight III-12
5. Epolight IV-62A (Eporin) is also preferred.
Yes. Further, the formula described in U.S. Pat.
Suitable near infrared absorbing dyes represented by (I) and (II)
Can be mentioned. Of the above, cyanine color
Element, squarylium dye, pyrylium salt, nickelthio
A rate complex is more preferred. More specifically, it is represented by the following general formula (Z).
Can be mentioned. [0056] In the general formula (Z), R^{twenty one}~ R^{twenty four}It
Each independently a hydrogen atom or an optionally substituted carbon
Prime number 1-12 alkyl group, alkenyl group, alkoxy
Group, cycloalkyl group, aryl group, R^{twenty one}When
R^{twenty two}, R^{twenty three}And R^{twenty four}Are bonded together to form a ring structure
May be. R^{twenty one}~ R^{twenty four}As, for example, a hydrogen atom,
Methyl group, ethyl group, phenyl group, dodecyl group, naphthy
Group, vinyl group, allyl group, cyclohexyl group, etc.
These groups may further have a substituent.
Yes. Here, as the substituent, for example, a halogen atom,
Carbonyl group, nitro group, nitrile group, sulfonyl group,
Carboxyl group, carboxylic acid ester, sulfonic acid ester
And the like. Where R^{twenty five}~ R³⁰Are each independently replaced
Represents an alkyl group having 1 to 12 carbon atoms which may have a group.
And R^{twenty five}~ R³⁰For example, methyl group, ethyl
Group, phenyl group, dodecyl group, naphthyl group, vinyl
Groups, allyl groups, cyclohexyl groups, etc., and these
This group may further have a substituent. Where
Examples of the substituent include a halogen atom, a carbonyl group,
Nitro group, nitrile group, sulfonyl group, carboxyl
Groups, carboxylic acid esters, sulfonic acid esters, etc.
It is done. Where R³¹~ R³³Are each independently hydrogen
Atoms, halogen atoms, or carbon atoms that may have a substituent
Represents an alkyl group of 1 to 8;³²R³¹Or
R³³To form a ring structure, and m> 2
If more than one R³²Are linked together to form a ring structure
May be. R³¹~ R³³For example, chlorine source
Child, cyclohexyl group, R³²Cyclo formed by bonding each other
Pentyl ring, cyclohexyl ring, etc., and these
The group may further have a substituent. Where replace
Examples of the group include a halogen atom, a carbonyl group, and a nitrogen group.
Toro group, nitrile group, sulfonyl group, carboxyl group,
Examples include carboxylic acid esters and sulfonic acid esters.
The M represents an integer of 1 to 8, with 1 to 3 being preferred.
Good. Where R³⁴~ R³⁵Are each independently hydrogen
Atoms, halogen atoms, or carbon atoms that may have a substituent
Represents an alkyl group of 1 to 8;³⁴Is R³⁵Combined with
May form a ring structure, and if m> 2,
R³⁴They may be bonded to each other to form a ring structure. Previous
R³⁴~ R³⁵For example, chlorine atom, cyclohex
Sil group, R³⁴Cyclopentyl ring formed by bonding together,
Chlorohexyl ring, etc., and these groups are further substituted.
It may have a substituent. Here, examples of the substituent include
For example, halogen atom, carbonyl group, nitro group, nitrile
Group, sulfonyl group, carboxyl group, carboxylic acid ester
And sulfonic acid esters. M
Represents an integer of 1 to 8, among which 1 to 3 is preferable. Where X^-Represents an anion, for example
Perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triiso
Propylnaphthalenesulfonic acid, 5-nitro-O-toluene
Ensulfonic acid, 5-sulfosalicylic acid, 2,5-dimethyl
Tylbenzenesulfonic acid, 2,4,6-trimethylben
Zensulfonic acid, 2-nitrobenzenesulfonic acid, 3-
Chlorobenzenesulfonic acid, 3-bromobenzenesulfone
Acid, 2-fluorocaprylnaphthalenesulfonic acid,
Decylbenzenesulfonic acid, 1-naphthol-5-sulfur
Phosphonic acid, 2-methoxy-4-hydroxy-5-benzoy
Ru-benzenesulfonic acid, paratoluenesulfonic acid, etc.
Is mentioned. Among them, hexafluorophosphoric acid, triisopro
Pyrnaphthalene sulfonic acid, 2,5-dimethylbenzene
Alkyl aromatic sulfonic acids such as sulfonic acids are preferred. Among the compounds represented by the general formula (Z),
However, specifically, the following compounds are preferably used.
However, the present invention is not limited to these.
Yes.The content of the infrared absorbing dye as described above
The total solid content mass of the image forming layer is 0.01 to 50.
% By mass is preferable, 0.1 to 10% by mass is more preferable,
Furthermore, 0.5-10 mass% is the most preferable. The content is
If it is less than 0.01% by mass, the sensitivity may be lowered.
When the content exceeds 50% by mass, the uniformity of the image forming layer decreases.
However, the durability may deteriorate. -(B) Alkali-soluble polymer compound- Usable alkali-soluble polymer compounds (hereinafter,
Sometimes referred to as “component (B)”. )
(1) to (3) in the main chain and / or side chain structure
Use of an alkaline water soluble polymer compound
Can do. (1) Phenol group (-Ar-OH) (2) Sulfonamide group (—SO₂NH-R) (3) Substituted sulfonamide acid group (hereinafter referred to as “active imide”
It is called "base". ) [-SO₂NHCOR, -SO₂NHSO₂R, -CON
HSO₂R] In the above (1) to (3), Ar may have a substituent.
R represents a divalent aryl linking group, and R has a substituent.
Represents an optionally substituted hydrocarbon group. Specific examples are shown below.
However, the present invention is not limited to these.
Absent. (1) Alkali soluble having a phenol group
Examples of the functional polymer compound include phenol and form.
Condensation polymer with aldehyde, m-cresol and formal
Condensation polymer with aldehyde, p-cresol and formaldehyde
A polycondensation polymer with m- / p-mixed cresol and formua
Condensation polymer with aldehyde, phenol and cresol (m
Any of-, p- or m- / p-mixing may be used. ) And ho
Novolac resin such as condensation polymer with rumaldehyde or
Mention may be made of condensation polymers of rogalol and acetone.
The In addition, monomers with phenol groups in the side chain
There may also be mentioned combined polymer compounds. Polymer having a phenolic hydroxyl group in the side chain
Compounds include unsaturated polymers that can polymerize with phenolic hydroxyl groups.
Consists of low molecular compounds each having one or more sum bonds
Homopolymerization of a polymerizable monomer, or the polymerizable monomer
Polymerization obtained by copolymerizing with other polymerizable monomers
Compound may be mentioned. Monomers having a phenol group in the side chain
As for acrylamido having a phenol group in the side chain.
, Methacrylamide, acrylic ester, methacrylate
Examples of the acid ester include hydroxyester and hydroxystyrene. Specifically, N- (2-hydroxypheny
E) Acrylamide, N- (3-hydroxyphenyl)
Acrylamide, N- (4-hydroxyphenyl) aqua
Rilamide, N- (2-hydroxyphenyl) methacryl
Luamide, N- (3-hydroxyphenyl) methacryl
Amide, N- (4-hydroxyphenyl) methacrylamide
Imide, o-hydroxyphenyl acrylate, m-hydride
Roxyphenyl acrylate, p-hydroxyphenyl
Acrylate, o-hydroxyphenyl methacrylate
, M-hydroxyphenyl methacrylate, p-hydride
Roxyphenyl methacrylate, o-hydroxystyrene
, M-hydroxystyrene, p-hydroxystyrene
2- (2-hydroxyphenyl) ethyl acrylate
2- (3-hydroxyphenyl) ethyl acrylate
2- (4-hydroxyphenyl) ethyl acrylate
2- (2-hydroxyphenyl) ethyl methacrylate
2- (3-hydroxyphenyl) ethyl methacrylate
Rate, 2- (4-hydroxyphenyl) ethyl methacrylate
Preferable examples include relation. Alkali soluble having the phenol group
The mass average molecular weight of the polymer compound is 5.0 × 10²
~ 2.0 × 10^FiveHas a number average molecular weight of 2.0.
× 10 ²~ 1.0 × 10^FiveAre preferred in terms of image-forming properties.
That's right. Moreover, the alkali-soluble high content which has a phenol group
Child compounds can be used alone or in combination of two or more.
You may use together. In the case of combination,
As described in the permit 4123279 specification,
Condensation polymer of t-butylphenol and formaldehyde
And condensation polymerization of octylphenol and formaldehyde
Body as an alkyl group having 3 to 8 carbon atoms
Containing a condensation polymer of phenol and formaldehyde
May be used. These condensation polymers also have a weight average molecular weight.
5.0 × 10²~ 2.0 × 10^FiveThe number average molecular weight is 2.0
× 10²~ 1.0 × 10^FiveAre preferred. (2) Alkali having a sulfonamide group
Examples of soluble polymer compounds include sulfonamides.
Polymerization using a group-containing compound as the main monomer constituent unit
Other than the homopolymer or the monomer constitutional unit
Mention may be made of copolymers obtained by copolymerizing polymerizable monomers.
it can. As a polymerizable monomer having a sulfonamide group
At least one hydrogen on a nitrogen atom in one molecule
Atom-bound sulfonamide group -SO₂ -NH-
Low content having at least one polymerizable unsaturated bond
And monomers composed of a child compound. Above all,
Substituted with a liloyl group, allyl group or vinyloxy group, or
Mono-substituted aminosulfonyl group or substituted sulfonylimino
And a low molecular weight compound having a group. Low molecular weight
Examples of the compound include those represented by the following general formulas (a) to (e).
In the present invention, this is
It is not limited to that. [0070] Where X¹, X²Each independently
Child or NR⁷ Represents. R¹ , R^Four Each independently water
Elementary atom or CH_ThreeRepresents. R², R^Five, R⁹, R¹², R
¹⁶Are each independently an optionally substituted carbon number
1-12 alkylene group, cycloalkylene group, aryl
Represents a ren group or an aralkylene group. R^Three, R⁷, R¹³Is
Each independently a hydrogen atom or an optionally substituted charcoal
Prime number 1-12 alkyl group, cycloalkyl group, aryl
Represents a ru group or an aralkyl group. R⁶, R¹⁷The
1 to 12 carbon atoms which may each independently have a substituent
Alkyl group, cycloalkyl group, aryl group, arral
Represents a kill group. R⁸, R^Ten, R¹⁴Each independently water
Elementary atom or CH_ThreeRepresents. R¹¹, R¹⁵Are independent
1 to 12 carbon atoms which may have a single bond or a substituent
An alkylene group, a cycloalkylene group, an arylene group, or
Represents an aralkylene group. Y¹, Y²Are each independently
Represents a bond or CO. Among them, m-aminosulfonylphenyl meta
Acrylate, N- (p-aminosulfonylphenyl)
Tacrylamide, N- (p-aminosulfonylpheny
E) Acrylamide and the like can be preferably used. (3) Alkali soluble having an active imide group
Examples of the functional polymer compound include an active imide group
A polymer whose main monomer constituent unit is
Can be. Mainly compounds with active imide groups
As a polymer as a monomer constituent unit, in one molecule,
An active imide group represented by the following formula and a polymerizable unsaturated bond
Mono-comprising low molecular weight compounds each having one or more
Homopolymerization of the monomer, or other polymerizable monomers
List polymer compounds obtained by copolymerization of mer
Can do. [0074] As such a compound, specifically,
N- (p-toluenesulfonyl) methacrylamide, N
-(P-toluenesulfonyl) acrylamide and the like are preferable
Can be listed. In addition to the above,
A polymerizable monomer having a nor group, a sulfonamide group
Polymerizable monomer having an active imide group
High that polymerizes any two or more of functional monomers
Molecular compound or two or more kinds of these polymerizable monomers
Obtained by copolymerizing with other polymerizable monomers
Also preferred are molecular compounds. Polymerizable monomer having a phenol group (M
1) a polymerizable monomer having a sulfonamide group (M
2) and / or polymerizable monomer having an active imide group
Mixing ratio when copolymerizing (M3) (M1: M2 and
(Or M3; mass ratio) is 50:50 to 5:95.
Is preferable, and 40:60 to 10:90 is more preferable. The alkali-soluble polymer compound has the acidity.
Monomer having any one selected from groups (1) to (3)
-Consists of constituent units and constituent units of other polymerizable monomers.
In the case of a copolymer formed, the acid is contained in the copolymer.
Mono having any one selected from sex groups (1) to (3)
It is preferable to contain 10 mol% or more of the monomer structural unit.
It is more preferable to contain 0 mol% or more. The monomer structure
If the content of the constituent unit is less than 10 mol%, sufficient
Negligible solubility is not obtained and development latitude is narrow.
Sometimes. As a method for synthesizing the copolymer, conventionally,
More known graft copolymerization, block copolymerization, run
A dam copolymerization method or the like can be used. Selected from the acidic groups (1) to (3)
Polymerizable monomer comprising monomer having a difference
Copolymerized with Examples of other polymerizable monomers include
For example, list the monomers listed in (a) to (1) below.
However, the present invention is not limited to these.
Not. (A) 2-hydroxyethyl acrylate or
Is an aliphatic hydroxide such as 2-hydroxyethyl methacrylate
Group-containing acrylic esters, methacrylic acid ester
Le. (B) Methyl acrylate, ethyl acrylate, acrylic
Propyl butyl, butyl acrylate, amyl acrylate, amyl
Hexyl acrylate, octyl acrylate, acrylic acid base
Nylyl, 2-chloroethyl acrylate, glycidyl
Chlorate, N-dimethylaminoethyl acrylate, etc.
Alkyl acrylates. (C) Methyl methacrylate, ethyl methacrylate, meta
Propyl crylate, butyl methacrylate, methacrylic acid
Amyl, hexyl methacrylate, cyclohexyl methacrylate
Xylyl, benzyl methacrylate, 2-methacrylic acid
Loroethyl, glycidyl methacrylate, N-dimethyl
Alkyl methacrylate such as aminoethyl methacrylate
G. (D) Acrylamide and methacrylamid
, N-methylolacrylamide, N-ethylacryl
Luamide, N-hexyl methacrylamide, N-cyclo
Hexyl acrylate amide, N-hydroxyethyl acrylate
Luamide, N-phenylacrylamide, N-nitrof
Phenyl acrylamide, N-ethyl-N-phenyl acrylate
Acrylamide such as rilamide, or methacrylamid
De. (E) Ethyl vinyl ether, 2-chloroethyl vinyl
Ether, hydroxyethyl vinyl ether, propyl
Vinyl ether, butyl vinyl ether, octyl vinyl
Vinyl ethers such as ruether and phenyl vinyl ether
Le. (F) Vinyl acetate, vinyl chloroacetate, vinyl
Vinyl esters such as nilbutyrate and vinyl benzoate
Kind. (G) Styrene, α-methylstyrene, methylstyrene
Chloromethylstyrene and styrenes. (H) methyl vinyl ketone, ethyl vinyl
Luketone, propyl vinyl ketone, phenyl vinyl keto
Vinyl ketones such as (I) ethylene, propylene, isobutylene, butadiene
And olefins such as isoprene. (J) N-vinyl pyrrolidone, N-vinyl carbazo
, 4-vinylpyridine, acrylonitrile, methacrylate
Ronitrile etc. (K) maleimide, N-acryloylacrylamide,
N-acetylmethacrylamide, N-propionylmeta
Kurylamide, N- (p-chlorobenzoyl) methacryl
Unsaturated imides such as luamide. (L) Acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as taconic acid. As the alkaline water-soluble polymer compound
Regardless of homopolymer or copolymer, in terms of film strength,
Mass average molecular weight is 2000 or more, number average molecular weight is 500
The above are preferable, and the mass average molecular weight is 5000-3.
00000, number average molecular weight is 800-250,000
The dispersity (mass average molecular weight / number average molecular weight) is 1.1 to 1.1.
10 is more preferable. The alkali-soluble
The polymer compound is phenol-formaldehyde resin,
If it is a cresol-aldehyde resin, etc.
The average molecular weight is 500-20000, and the number average molecular weight
Is preferably 200 to 10,000. Inclusion of the alkaline water-soluble polymer compound
As an amount, it is 30 to the total solid mass of the image forming layer.
99% by mass is preferable, and 40 to 95% by mass is more preferable.
50 to 90% by mass is most preferable. The content is
If it is less than 30% by mass, the durability of the image forming layer is lowered.
If it exceeds 99% by mass, sensitivity and durability will be
May decrease. In addition, the polymer compound is one kind
You can use only a kind or a combination of two or more
Yes. -(C) the alkali-soluble polymer compound
The alkali-soluble polymer compound
While reducing the solubility in aqueous solution,
Compounds with reduced solubility-reducing action This component (C) is a hydrogen bonding functional group present in the molecule.
By the function of the group, the (B) alkali-soluble polymer compound
Uniform coating solution for image forming layer with good compatibility with the product
And an alkali-soluble polymer compound
The interaction of the alkali-soluble polymer compound
Has a function to suppress lukali solubility (solubility control action)
Compound. Also, alkali-soluble polymers can be formed by heating.
The solubility-inhibiting effect on the compound disappears, but this red
When the external line absorbent itself is a compound that decomposes by heating
Has enough energy for decomposition, laser power and irradiation
Alkali-soluble if not given due to conditions such as time
To sufficiently reduce the solubility-inhibiting action of polymer compounds
May not be possible and sensitivity may be reduced. For this reason,
The thermal decomposition temperature of component (C) is preferably 150 ° C or higher.
Good. (C) Component (B) Alkali
Considering the interaction with the soluble polymer compound, for example,
Sulfone compounds, ammonium salts, phosphonium salts,
Mutual with the alkali-soluble polymer compound such as a midi compound
It can be appropriately selected from compounds that can act.
(C) component and said (B) alkali-soluble polymer compound
As a compounding ratio (C / B), generally 1/99 to 25 /
75 is preferred. -(D) Cyclic acid anhydride- Even if a cyclic acid anhydride is used for the lithographic printing plate precursor,
Good. The cyclic acid anhydride has carboxylic acid anhydride in its structure.
Having a bond conjugated to the carbonyl group of the product
The decomposition rate is controlled by increasing the stability of
The acid is decomposed at an appropriate rate in That
Therefore, deterioration of developability during storage is suppressed, and developability is reduced for a long time.
Can be kept constant. As the cyclic acid anhydride, the following general
Examples include compounds represented by formula (IV) or (V). [0088] In the general formula (IV), R⁴¹, R⁴²Each
A hydrogen atom or a carbon atom optionally having a substituent
Number 1-12 alkyl group, alkenyl group, alkoxy
Group, cycloalkyl group, aryl group, carbonyl group,
Ruboxy group or carboxylic acid ester is represented. In addition,
R⁴¹, R⁴²May be linked to each other to form a ring structure.
R⁴¹, R⁴²As, for example, a hydrogen atom or a carbon atom
Unsubstituted alkyl group having 1 to 12 members, aryl group, alkyl
Preferred examples include a kenyl group and a cycloalkyl group.
Physically, hydrogen atom, methyl group, ethyl group, phenyl group,
Dodecyl, naphthyl, vinyl, allyl, cyclo
Hexyl groups, etc., and these groups are further substituted
It may have a group. R⁴¹, R⁴²Are connected to each other
When forming a structure, the cyclic group includes, for example,
Nylene group, naphthylene group, cyclohexene group, cyclope
Nten group and the like. Examples of the substituent include
Halogen atom, hydroxy group, carbonyl group, sulfo
Acid esters, nitro groups, nitrile groups, etc.
The In the general formula (V), R⁴³, R⁴⁴, R⁴⁵, R⁴⁶
Are independently hydrogen atom, hydroxy group, chlorine, etc.
A halogen atom, a nitro group, a nitrile group, or a substituent
An optionally substituted alkyl group having 1 to 12 carbon atoms,
Lucenyl group, alkoxy group, cycloalkyl group, aryl
Group, carbonyl group, carboxy group or carboxylic acid
Represents an ester group and the like. R⁴³, R⁴⁴, R⁴⁵, R⁴⁶When
For example, a hydrogen atom, a halogen atom, or 1 carbon atom
~ 12 unsubstituted alkyl, alkenyl, carbon atoms
Preferred examples thereof include an aryl group of 6 to 12, specifically
Has methyl, vinyl, phenyl, allyl, etc.
Can be mentioned. These groups may have further substituents
Good. Examples of the substituent include a halogen atom and a hydride.
Roxy group, carbonyl group, sulfonate ester, nitro
Group, nitrile group, carboxy group and the like. As a cyclic acid anhydride, for example, phthalic anhydride
Acid, 3,4,5,6-tetrahydrophthalic anhydride, teto
Lachlorophthalic anhydride, 3-hydroxyphthalic anhydride,
3-methylphthalic anhydride, 3-phenylphthalic anhydride,
Trimellitic anhydride, pyromellitic anhydride, maleic anhydride
Acid, phenylmaleic anhydride, dimethyl maleic anhydride
Acid, dichloromaleic anhydride, chloromaleic anhydride, etc.
Are preferred. As content of cyclic acid anhydride
Is 0.5 to 20 mass based on the total solid content of the image forming layer
% Is preferable, 1 to 15% by mass is more preferable, and 1 to 1
0% by mass is most preferred. The content is less than 0.5% by mass
If it is, the effect of maintaining developability may be insufficient,
If it exceeds 20% by mass, an image may not be formed. The following constitutes the recording layer of the negative lithographic printing plate
It is an ingredient to do. -(E) Compound that generates acid by heat- If the image forming material is negative, it generates acid when heated.
A compound (hereinafter referred to as “acid generator”) is used in combination. this
Acid generator decomposes by heating to 100 ° C or higher
As a result, the number of compounds generating acid is increased. As the acid generated,
Strong acid with a pKa of 2 or less, such as sulfonic acid and hydrochloric acid
Is preferred. Examples of the acid generator include iodonium salts,
Sulfonium salt, phosphonium salt, diazonium salt, etc.
Preferable examples include onium salts. In particular,
U.S. Pat. No. 4,708,925 and JP-A-7-20629
And the compounds described in No. 1
Iodonium salt, sulfonate
Umum salts and diazonium salts are preferred. As the diazonium salt, US Pat.
The diazonium salt compound described in 3,867,147,
Diazo described in US Pat. No. 2,632,703
Ni compounds, JP-A-1-102456, JP-A-1-
The diazo resin described in each publication of No. 102457 is also suitable.
I can make it. U.S. Pat. No. 5,135,83
No. 8, the benzine described in US Pat. No. 5,200,544
Rusulfonates, JP-A-2-100054, JP-A-2-
2-100055 and JP-A-8-9444
Sulfonic acid esters and disulfonyl compounds are also preferred
Yes. Others described in JP-A-7-271029
Also preferred are rualkyl-substituted S-triazines. The acid
The amount of the generator added is the total solid mass of the image forming layer.
The content is preferably 0.01 to 50% by mass, and 0.1 to 40% by mass.
Is more preferable, and 0.5 to 30% by mass is most preferable. -(F) Crosslinking agent cross-linked by acid- When the lithographic printing plate precursor is negative, it is crosslinked with acid.
A cross-linking agent (hereinafter sometimes simply referred to as “cross-linking agent”)
Combined. Examples of the crosslinking agent include the following:
You can. (I) placed at an alkoxymethyl group or a hydroxymethyl group
Substituted aromatic compounds (Ii) N-hydroxymethyl group, N-alkoxymethyl
Group or N-acyloxymethyl group-containing compound (iii) Epoxy compound Further, those described in JP-A-11-254850
And phenol derivatives. The amount of the crosslinking agent added is the image forming layer.
5 to 80 mass% is preferable with respect to the total solid content mass of 10
-75 mass% is more preferable, and 20-70 mass% is the most
preferable. Use the phenol derivative as a crosslinking agent
The amount of the phenol derivative added is image type
5 to 70% by mass is preferred based on the total solid content of the composition
10 to 50% by mass is more preferable. Various combinations above
For details of the product, see Japanese Patent Laid-Open No. 2000-267265.
Is described in the report. -Other components- If necessary, the image forming layer of the lithographic printing plate precursor
Various additives can be added. For example, sensitivity
For the purpose of improving cyclic acid anhydrides, phenols,
Combined use of known additives such as organic acids and sulfonyl compounds
You can also Examples of the cyclic acid anhydride include US
Tetrahydro described in allowed 4,115,128 specification
Phthalic anhydride, hexahydrophthalic anhydride, 3,6-d
Oxy-Δ^Four-Tetrahydrophthalic anhydride, α-fu
Phenyl maleic anhydride, succinic anhydride,
And toic acid. As phenols,
Enol A, p-nitrophenol, p-ethoxyphene
Nord, 2,4,4'-Trihydroxybenzopheno
2,3,4-trihydroxybenzophenone, 4-
Hydroxybenzophenone, 4,4 ', 4 "-trihydr
Roxytriphenylmethane, 4,4 ', 3 ", 4" -te
Trahydroxy-3,5,3 ', 5'-tetramethylto
Examples include rephenylmethane. Examples of the organic acids include JP-A-60-8.
No. 8942, JP-A-2-96755, etc.
Sulfonic acids, sulfinic acids, alkyls
Sulfuric acids, phosphonic acids, phosphate esters and cal
Bonic acids, etc., specifically p-toluenesulfo
Acid, dodecylbenzenesulfonic acid, p-toluenesulfuric acid
Finic acid, ethyl sulfate, phenylphosphonic acid, phenyl
Phosphinic acid, phenyl phosphate, diphenyl phosphate,
Benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalate
Acid, 4-cyclohexene-2,2-dicarboxylic acid, L
Caric acid, lauric acid, n-undecanoic acid, ascorbic acid
Etc. Examples of sulfonyl compounds include
Bishydroxyphenylsulfone, methylphenyls
Luhon, diphenyldisulfone and the like can be mentioned. Above
Other cyclic acid anhydrides, phenols, organic acids or sulfo
The amount of nil compounds added is the total solid content of the image forming layer.
0.05 to 20 mass% is preferable with respect to mass, and 0.1 to 1
5% by mass is more preferable, and 0.1 to 10% by mass is most preferable.
That's right. Further, the stability of the processability with respect to the development conditions is improved.
For the purpose of expanding, JP-A-62-251740, JP-A-6-251740
Nonionic surface activity described in Japanese Patent Laid-Open No. 3-208514
Agent, JP-A-59-121044, JP-A-4-1314
Amphoteric surfactant described in No. 9 publication, etc., EP950517
Siloxane compounds such as those described in
As described in Kaihei 11-288093
Fluorine-containing monomer copolymer can be added
The Examples of nonionic surfactants include sorbitant
Restearate, sorbitan monopalmitate, sorbi
Tantrioleate, stearic acid monoglyceride, poly
Such as oxyethylene nonylphenyl ether
The Examples of amphoteric surfactants include alkyldi (amido).
Noethyl) glycine, alkylpolyaminoethylglyci
Hydrochloride, 2-alkyl-N-carboxyethyl-N-
Hydroxyethylimidazolinium betaine, N-teto
Radecyl-N, N-betaine type (for example, trade name: AMOR
Gen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. Shiroki
Sun compounds include dimethylsiloxane and polyal
Preference is given to block copolymers of xylene oxide, specific examples
As a product of Chisso Corporation, DBE-224, DBE-6
21, DBE-712, DBP-732, DBP-53
4. Polyalkylene such as Tego Glide 100 made by Tego, Germany
Mention may be made of oxide-modified silicones. Above
Use amount of nonionic surfactant or amphoteric surfactant
Is 0.05 to 15 quality relative to the total solid mass of the image forming layer.
% By weight is preferable, and 0.1 to 5% by weight is more preferable. In the image forming layer, after heating by exposure,
As a print-out agent or image colorant to obtain a visible image immediately
All dyes and pigments can be added. The baking-out agent
As an example, an acid is generated by heating by exposure.
And a combination of an organic dye capable of forming a salt
It is. Specifically, Japanese Patent Laid-Open No. 50-36209, Japanese Patent Laid-Open No.
O-Naphthoquinone described in each publication of No. 53-8128
Diazide-4-sulfonic acid halide and salt-forming organic dye
Combination with materials, JP-A 53-36223, JP-A 54
JP-A-74728, JP-A-60-3626, JP-A-61
143748, JP-A 61-151644 and special
Trihalomes described in Japanese Laid-Open Patent Publication Nos. 63-58440
A combination of a chill compound and a salt-forming organic dye.
The As the trihalomethyl compound, an oxazole type
There are compounds and triazine compounds, both of which are stable over time
Excellent printability and a clear printout image. The image coloring
Examples of the agent include, in addition to the salt-forming organic dye, other
For example, oil-soluble dyes, bases
A suitable dye is preferably used. Specifically, oil yellow # 101, orange
Il Yellow # 103, Oil Pink # 312, Oil
Green BG, Oil Blue BOS, Oil Blue # 6
03, Oil Black BY, Oil Black BS, Oy
Le Black T-505 (above, Orient Chemical Industry
Co., Ltd.), Victoria Pure Blue, Crystal Buy
Olet (C.I. 42555), methyl violet
(C.I. 42535), ethyl violet, loader
Min B (C.I. 145170B), Malachite Glee
(C.I. 42000), methylene blue (C.I.
52015). In addition, JP-A-6
The dye described in JP-A-2-293247 is particularly preferred.
Yes. The amount of the various dyes added is the total solidity of the image forming layer.
The content is preferably 0.01 to 10% by mass with respect to the mass of the part, 0.1
-3 mass% is more preferable. If necessary, the coating film is flexible.
For the purpose of imparting, a plasticizer can be added. OK
Examples of plasticizers include butylphthalyl and polyethylene group.
Recall, tributyl citrate, diethyl phthalate,
Dibutyl tartrate, dihexyl phthalate, dioctyl phthalate
Chill, tricresyl phosphate, tributyl phosphate, phosphoric acid
Trioctyl, tetrahydrofurfuryl oleate, a
Such as oligomers and polymers of crylic acid or methacrylic acid
And so on. If necessary, the following various additives are added.
Can be added. For example, onium salt, o-kino
Diazide compounds, aromatic sulfone compounds, aromatic sulfones
In pyrolytic and undecomposed state, such as phosphonate compounds
Substantially reduces the solubility of alkaline water-soluble polymer compounds
A compound to be reduced can be used in combination. Addition of the compound
Is to improve the ability to prevent dissolution of the image area in the developer.
preferable. Examples of the onium salt include diazonium.
Salt, ammonium salt, phosphonium salt, iodonium
Salt, sulfonium salt, selenonium salt, arsonium salt
Etc. Among them, for example, S.I.Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al,
Polymer, 21, 423 (1980), JP-A-5-158230
The diazonium salts described in the publication, US Pat. No. 4,069,
No. 055, No. 4,069,056, JP-A-3-140
Ammonium salt described in No. 140, D. C. Necker et a
l, Macromolecules, 17, 2468 (1984), C. S. Wen et a
l, The Proc. Conf. Rad. Curing ASIA, p478 Tokyo, O
ct (1988), U.S. Pat. No. 4,069,055, 4,
Phosphonium salts described in No. 069,056, J. V. Criv
elloet et al. Macromolecules, 10 (6), 1307 (1977),
Chem. & Eng. News, Nov. 28, p.31 (1988), European patent
No. 104,143, US Pat. No. 339,049,
No. 410,201, JP-A-2-150848, JP-A-2-150848
An iodonium salt described in JP-A-2-296514, J. V. Crivello et al, Polymer J. 17, 7
3 (1985), J. V. Crivello et al, J. Org. Chem., 43,
3055 (1978), W.R, Watt et al, J. Polymer Sci., Po
lymerChem. Ed., 22, 1789 (1984), J. V. Crivello et
 al, Polymer bull., 14, 279 (1985), J. V. Crivello
 et al, Macromolecules, 14 (5), 1141 (1981), J.V.Cr
ivello et al, J. Polymer Sci., Polymer Chem. Ed.,
17. 2877 (1979), European Patent No. 370,693, 2
33,567, 297,443, 297,44
2, U.S. Pat. Nos. 4,933,377 and 3,90
2,114, 410,201, 399,049
No. 4,760,013, No. 4,734,444
No. 2,833,827, German Patent No. 2,904
626, 3,604,580, 3,604,5
The sulfonium salt according to No. 81, J. V. Crivello et al, Macromolecules,
10 (6), 1307 (1977), J.V.Crivelloet al, J. Polymer
 Sci., Polymer Chem. Ed., 17, 1047 (1979)
Selenonium salt, C. S. Wen et al, The Proc. Conf. R
ad. Curing ASIA, p.478, Tokyo, Oct (1988)
Examples include arsonium salts. Of the above, diazo
Nilium salts are preferred, and above all, JP-A-5-158230.
More preferred are those described in Japanese Patent Publication. The counter ion of the onium salt is tetrafluoride.
Boric acid, hexafluorophosphoric acid, triisopropylnaphthalene
Sulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfo
Acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfuric acid
Phosphonic acid, 3-bromobenzenesulfonic acid, 2-fluoro
Capryl naphthalene sulfonic acid, dodecyl benzene sul
Phosphonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy
Ci-4-hydroxy-5-benzoyl-benzenesulfo
Acid, paratoluenesulfonic acid, etc.
it can. Among them, hexafluorophosphate, triisopropyl na
Phthalenesulfonic acid, 2,5-dimethylbenzenesulfone
Alkyl aromatic sulfonic acids such as acids are preferred. As the o-quinonediazide compound,
Compound having at least one o-quinonediazide group
And those that increase alkali solubility by thermal decomposition.
In addition, compounds having various structures can be used. O
-Quinonediazide has the ability to inhibit the dissolution of the binder by thermal decomposition.
And o-quinonediazide itself is alkali-soluble
Lithographic printing plate precursor due to both effects
Help solve. O-quinonediazide compounds as described above and
For example, J. et al. By Korser, “Light Sensitivity”
Systems (John Wiley & Sons. Inc.) 33rd
The compounds described on pages 9 to 352 can be used.
Various aromatic polyhydroxy compounds or aromatic amino acids
Of sulfonic acid of o-quinonediazide reacted with nitro compounds
Esters or sulfonic acid amides are preferred. Also, JP
Benzoquinone described in JP-A-43-28403
(1,2) -diazide sulfonic acid chloride or the United States
Patent No. 3,046,120, No. 3,188,210
Benzoquinone- (1,2) -diazidosulfo
Acid chloride or naphthoquinone- (1,2) -diazi
Do-5-sulfonic acid chloride and phenol formal
Also preferred are esters with dehydrated resins. Further, naphthoquinone- (1,2) -dia
Zido-4-sulfonic acid chloride and phenol formua
Rudehydr resin or cresol-formaldehyde tree
Esters with fat, naphthoquinone- (1,2) -diazide
-4-sulfonic acid chloride and pyrogallol-acetone
Also preferred are esters with resins. In addition, for example, JP-A-4
7-5303, JP 48-63802, JP 4
8-63803, JP-A-48-96575, JP-A
49-38701, JP-A-48-13354, Japanese Patent
Sho 41-11222, Shoko 45-9610, Shoko
Sho 49-17482, U.S. Pat. No. 2,797,213
No.3, No.3,454,400, No.3,544,32
No. 3, No. 3,573,917, No. 3,674,4
No. 95, No. 3,785,825, British Patent Nos. 1, 2
No. 27,602, No. 1,251,345, No. 1,
No. 267,005, No. 1,329,888, No.
No. 1,330,932, German Patent No. 854,890
Those described in the above are also useful. These compounds alone
But you can combine several types and use them as a mixture.
Yes. The onium salt, o-quinonediazide compound, aroma
As the addition amount of the aromatic sulfonate, etc., the image forming layer
0.1 to 50% by mass is preferable based on the total solid content mass of
0.5-30 mass% is more preferable, 0.5-20 mass% is
Most preferred. In addition, for image discrimination
For the purpose of strengthening and strengthening the resistance to scratches on the surface
As described in Kai 2000-187318
And a perfluoroalkyl group having 3 to 20 carbon atoms in the molecule.
Polymerization of (meth) acrylate monomer having 2 or 3
It is preferable to use a polymer as a component in combination. Addition amount
Therefore, 0.1 to 10 quality with respect to the total solid content mass of the image forming layer.
% By weight is preferred, more preferably 0.5 to 5% by weight.
The In addition, for the purpose of imparting resistance to scratches, the surface
It is also possible to add compounds that lower the static friction coefficient of
The Specifically, in US Pat. No. 6,117,913
Estes of long chain alkyl carboxylic acids as disclosed
And the like. Preferred as its addition amount
The reason is that 0.1 to 10 quality with respect to the total solid content of the image forming layer.
%, More preferably 0.5 to 5% by mass. Ma
In addition, various dissolution inhibitors are used for the purpose of adjusting the solubility of the image forming layer.
An antagonizer may be included. As a dissolution inhibitor, JP-A-11
Disulfonation as described in JP-A-119418
A compound or a sulfone compound is preferably used.
Use 4,4'-bishydroxyphenylsulfone
Is preferred. The preferred amount of addition is image formation.
0.05 to 20% by mass with respect to the total solid mass of the layer,
More preferably, it is 0.5-10 mass%. Photosensitive lithographic plate to which the plate making method of the present invention can be applied
As a specific example of a printing plate, Japanese Patent Application No. 2000-378507
An image forming layer as disclosed in US Pat.
Also included is a lithographic printing plate precursor as a layer. That is, this positive type
The thermosensitive layer has a laminated structure and is close to the surface (exposed surface).
Provided on the heat sensitive layer and the side close to the support
And a lower layer containing an alkali-soluble polymer compound
It is characterized by that. One or both of the heat-sensitive layer and the lower layer
(A) Infrared absorbing dye, (B) Alkali available
Soluble polymer compound, (C) alkali-soluble polymer compound and
Alkaline water of the alkali-soluble polymer compound to be compatible
While reducing the solubility in the solution, heating the solution
Contains compounds that reduce the degradability, and other ingredients
You can have it. Alkali soluble used in the lower layer
As a functional polymer compound, acrylic resin has a buffering action.
Alkali development based on organic compounds and bases
Because it can maintain good solubility of the lower layer in the liquid, development
This is preferable from the viewpoint of image formation. Furthermore this acrylic
A resin having a sulfoamide group is particularly preferred.
Yes. Alkali soluble polymer used in heat sensitive layer
As a compound, strong hydrogen bonding occurs in the unexposed area,
In the exposed part, some hydrogen bonds are easily released
From the point of view, a resin having a phenolic hydroxyl group is desired.
Yes. More preferred is a novolac resin. Infrared absorption
Dyes can be added not only to the heat-sensitive layer but also to the lower layer.
Yes. Add the infrared absorbing dye to the lower layer to feel the lower layer
It can function as a thermal layer. Infrared absorption in the lower layer
When adding dye, it is the same as that in the upper thermal layer.
You can use the same or different items.
Yes. Other additives may be included only in the lower layer,
It may be contained only in the heat sensitive layer, and further contained in both layers.
It may be allowed. An image forming layer of the planographic printing plate precursor (the above two-layer structure)
In addition, the above components are dissolved in a solvent to give appropriate support.
It can be applied on the carrier. Examples of solvents include
Tylene dichloride, cyclohexanone, methyl ethyl
Ketone, methanol, ethanol, propanol, ethyl
Lenglycol monomethyl ether, 1-methoxy-2
-Propanol, 2-methoxyethyl acetate, 1-
Methoxy-2-propyl acetate, dimethoxyethane
, Methyl lactate, ethyl lactate, N, N-dimethylacetate
Amides, N, N-dimethylformamide, tetramethyl
Urea, N-methylpyrrolidone, dimethylsulfoxy
, Sulfolane, α-butyrolactone, toluene, etc.
Although it is mentioned, it is not limited to these. Above
A solvent may be individual or may mix 2 or more types. When the image forming layer has a two-layer structure, a heat-sensitive layer
Alkali-soluble polymer compound used in
Those with different solubility to Lucari soluble polymer
Is preferred. In other words, after applying the lower layer,
When applying the upper heat-sensitive layer adjacent to this, the top layer
As a coating solvent, dissolve the underlying alkali-soluble polymer compound.
If a solvent that can be dissolved is used, mixing at the layer interface can be ignored.
In extreme cases, it is not a layered layer, but a uniform single layer.
May end up. For this purpose, apply the upper heat-sensitive layer
The solvent used to do this is soluble in alkali contained in the lower layer.
A poor solvent for the polymer compound is preferred. The above in the solvent when the image forming layer is applied
In general, the total solid concentration of the components is preferably 1 to 10% by mass.
That's right. In addition, an image that is applied and dried on a support
The dry coating amount (solid content) of the formed layer is generally 0.5.
~ 5.0g / m²Is preferred. In the case of a two-layer structure,
The heat sensitive layer is 0.05 to 1.0 g / m.²The lower layer is 0.
3 to 3.0 g / m²It is preferable that Small application amount
As it disappears, the apparent sensitivity increases, but the image shape
The film properties of the stratification are reduced. A method of coating on a support and
Therefore, it can be appropriately selected from various known methods,
For example, bar coater coating, spin coating, spray coating, coating
-Ten coating, dip coating, air knife coating, gray
Coating, roll coating and the like. Image form
In the coating solution for stratification, it is surface active for the purpose of improving coatability.
Agents such as those described in JP-A-62-170950.
A nitrogen-based surfactant can be added. Its attendant
The addition amount is 0.0 with respect to the total solid mass of the image forming layer.
1-1 mass% is preferable, 0.05-0.5 mass% is more preferable.
Good. -Support- As a support for a lithographic printing plate precursor, for example, pure aluminum
Aluminum plate, aluminum alloy plate, aluminum laminate
Or vapor deposited plastic film
It is. The surface of the aluminum plate is grained, silicate
, Potassium fluoride zirconate, phosphate, etc.
Tables for penetration into aqueous solution or anodizing treatment
It is preferable that surface treatment is performed. US patents
After graining as described in No. 2,714,066
Aluminum soaked in sodium silicate aqueous solution
Aluminum plate described in Japanese Patent Publication No. 47-5125
After anodizing the copper plate, the alkali metal silicate water
An aluminum plate immersed in a solution is also preferable. As the anodizing treatment, for example, phosphorus
Inorganic acids such as acid, chromic acid, nitric acid, boric acid or soot
Acids, organic acids such as sulfamic acid or their salts in water
Liquid or non-aqueous solution alone or in combination of two or more
In the electrolyte, let the electrode flow with the aluminum plate as the anode.
It is given by doing. US Pat. No. 3,658,
The silicate electrodeposition described in the 662 specification is also effective. Also, US Pat. No. 4,087,341
Book, Japanese Examined Patent Publication No. 46-27481, Japanese Unexamined Patent Publication No. 52-3
The support body which gave the electrolytic grain of 0503 gazette
Those subjected to the anodizing treatment are also useful. US special
Grained as described in allowed 3,834,998 specification
After that, it was chemically etched and further anodized.
Luminium plates are also useful. These treatments are performed on the support surface.
In addition to making the surface hydrophilic, it is provided on the support.
To prevent harmful reactions with the image forming layer
For various purposes such as improving the adhesion to the formed image
Applied. The lithographic printing plate precursor is at least on a support.
It is provided by laminating image forming layers, but if necessary
An undercoat layer can be provided on the support. Undercoat
Examples of the components used in the above include various organic compounds,
For example, carboxymethylcellulose, dextrin, a
Amino such as rabia gum and 2-aminoethylphosphonic acid
A phosphonic acid having a group;
Phenylphosphonic acid, naphthylphosphonic acid, alkylphosphine
Phosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and
And organic phosphonic acids such as ethylenediphosphonic acid; substituents
Which may have phenyl phosphate, naphthyl phosphate,
Organic phosphoric acids such as alkyl phosphoric acid and glycerophosphoric acid;
Optionally substituted phenylphosphinic acid, naphth
Tylphosphinic acid, alkylphosphinic acid and glycero
Organic phosphinic acids such as phosphinic acid; glycine and β-
Amino acids such as alanine; salt of triethanolamine
Hydrochlorides of amines with hydroxyl groups such as acid salts
Is mentioned. The organic compounds may be used alone
Alternatively, two or more kinds may be mixed and used. In addition,
It is also a preferred embodiment to undercoat a diazonium salt.
The The undercoat layer has the following general formula (V
A small number of organic polymer compounds having the structural unit represented by I)
An organic undercoat layer containing at least one kind is also preferred. [0119] In the formula, R⁵¹Is a hydrogen atom, a halogen atom or
Represents an alkyl group, R⁵²And R⁵³Each independently water
Elementary atom, hydroxyl group, halogen atom, alkyl group, substituted al
Kill group, aryl group, substituted aryl group, -OR⁵⁴, -C
OOR⁵⁵, -CONHR⁵⁶, -COR⁵⁷Or -CN
And R⁵²And R⁵³Bond together to form a ring structure
May be. Where R⁵⁴~ R⁵⁷Are each independently
Represents an aryl group or an aryl group. X is a hydrogen atom, a metal atom,
-NR⁵⁸R⁵⁹R⁶⁰R⁶¹Represents. Where R⁵⁸~ R ⁶¹Is it
Each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an
Represents a reel group or a substituted aryl group, R⁵⁸And R⁵⁹Is
May be bonded to each other to form a ring structure. m is 1 to 3
Represents a number. The dry coating amount of the undercoat layer is 2 to 200 m
g / m²Is preferably 5 to 100 mg / m²Is more preferred
Yes. The dry coating amount is 2 mg / m²Less than enough
Membrane properties may not be obtained. On the other hand, 200mg / m²The
Even if it is applied in excess, no further effect can be obtained.
Yes. The undercoat layer can be provided by the following method.
Yes. That is, water or methanol, ethanol, methyl ether
For organic solvents such as tilketone or mixed solvents
A solution for the undercoat layer in which the organic compound is dissolved is aluminized.
A method of coating and drying on a support such as a um plate,
Water or methanol, ethanol, ethyl ethyl ketone
In any organic solvent or a mixed solvent thereof,
An undercoat layer solution in which an object is dissolved, an aluminum plate, etc.
So that the organic compound is adsorbed, and then
It is a method of cleaning and drying with water or the like. In the former method, the organic compound of 0.00
It is preferable to use an undercoat layer solution having a concentration of 5 to 10% by mass.
Good. On the other hand, in the latter method, the undercoat layer solution
The concentration of the organic compound is preferably 0.01 to 20% by mass.
And more preferably 0.05 to 5% by mass. Also, the immersion temperature and
20 to 90 ° C is preferable, and 25 to 50 ° C is more preferable.
Good. The immersion time is preferably 0.1 second to 20 minutes,
2 seconds to 1 minute is more preferable. Undercoat layer solution is ammonia
Basic substances such as a, triethylamine, potassium hydroxide
PH 1-12 using quality substances, acidic substances such as hydrochloric acid and phosphoric acid
It is also possible to adjust to the range. Also, tone reproducibility improvement
A yellow dye can be added for the purpose. The infrared photosensitive lithographic printing plate is an infrared laser.
In addition to recording with an ultraviolet lamp,
Thermal recording with a thermal head or the like is also possible. Above
As an infrared laser, red with a wavelength of 700-1200 nm
Lasers that emit external radiation are preferred, and infrared in the same wavelength range
Solid lasers or semiconductor lasers that emit radiation are more preferred
Good. [Alkali development processing solution] Plate making method of the present invention
Alkaline developing solution (hereinafter simply referred to as “development”)
Also called “liquid”. ) Is an alkaline aqueous solution.
It can be appropriately selected from known alkaline aqueous solutions
The As the alkaline aqueous solution, alkali silicate or
Examples include a developer comprising a non-reducing sugar and a base.
The thing of H12.5-13.5 is preferable. Silica alk
As for Li, it shows alkalinity when dissolved in water
For example, sodium silicate, potassium silicate,
Alkali metal silicates such as lithium silicate, silicate
Examples include monium. One alkali silicate
However, two or more kinds may be used in combination. The alkaline aqueous solution is a silicate component.
Some silicon oxide SiO₂And alkali oxide M₂O (M is a
Represents a Lucari metal or ammonium group. Mixing ratio with
The developability can be easily adjusted by adjusting the rate and density.
You can. Among the alkaline aqueous solutions, the oxidation catalyst
Ion SiO₂And alkali oxide M₂Mixing ratio with O (Si
O₂/ M₂O: molar ratio) of 0.5 to 3.0 is preferable,
The thing of 1.0-2.0 is more preferable. SiO₂/ M₂O
If is less than 0.5, the alkali strength will increase.
General purpose aluminum as a support for lithographic printing plate precursors
It may cause harmful effects such as etching a plate.
If it exceeds 3.0, developability may decrease.
The Also, the alkali silicate concentration in the developer
1 to 10% by mass with respect to the mass of the aqueous alkali solution
Is preferable, 3 to 8% by mass is more preferable, and 4 to 7% by mass.
% Is most preferred. If this concentration is less than 1% by weight,
Image quality and processing capacity may be reduced. Over 10% by mass
It tends to form precipitates and crystals,
Gelling easily during neutralization, hindering waste liquid treatment
There are times. In a developer composed of a non-reducing sugar and a base
Non-reducing sugars have free aldehyde groups and ketone groups.
Means a non-reducing saccharide because
Trehalose-type oligosaccharides bound by a person, saccharide reducing groups and non-
Glycosides linked to sugars, sugars reduced by hydrogenation of sugars
Classified as alcohol. In the present invention, both of these
It can be used suitably. Trehalose type oligosaccharide
Examples include sucrose and trehalose,
Examples of the glycoside include alkyl glycosides and phenols.
For example, le glycosides and mustard oil glycosides. Sugar Arco
For example, D, L-arabit, rebit,
Xylit, D, L-Sorbit, D, L-Mannic
D, L-exit, D, L-talit, slippery
And allozul sit. Furthermore, disaccharide
Of maltitol and oligosaccharides obtained by hydrogenation
Preferred examples include reduced form (reduced water candy) obtained by addition.
Can be. Among the above, as non-reducing sugar, sugar alcohol
And saccharose are preferred, and in particular, D-sol
Bit, saccharose, and reduced water candy in moderate pH range
It is more preferable in that it has a buffering action. These non-reducing sugars
It can be used alone or in combination of two or more.
The proportion occupied is preferably 0.1 to 30% by mass.
-20 mass% is more preferable. To the alkali silicate or non-reducing sugar
As appropriate, an alkali agent as a base is appropriately selected from conventionally known substances.
You can select and combine them. As the alkaline agent
For example, sodium hydroxide, potassium hydroxide, hydroxide
Lithium iodide, trisodium phosphate, tripotassium phosphate,
Triammonium phosphate, disodium phosphate, diphosphate
Potassium, diammonium phosphate, sodium carbonate, charcoal
Potassium acid, ammonium carbonate, sodium bicarbonate,
Potassium bicarbonate, ammonium bicarbonate, sodium borate
No such as lithium, potassium borate, ammonium borate
Alkaline agent, potassium citrate, tripotassium citrate
And sodium citrate. Further, monomethylamine and dimethylamino
, Trimethylamine, monoethylamine, diethylamine
Min, triethylamine, monoisopropylamine, di
Isopropylamine, triisopropylamine, n-butyl
Tylamine, monoethanolamine, diethanolamine
, Triethanolamine, monoisopropanolamine
, Diisopropanolamine, ethyleneimine, ethyl
Organic alkali agents such as range amine and pyridine are also suitable.
Can be mentioned. These alkaline agents are used alone
Alternatively, two or more kinds may be used in combination. Above all water
Sodium oxide and potassium hydroxide are preferred. The reason
Adjusts the amount of non-reducing sugar added
This is because the pH can be adjusted in a high pH range.
In addition, trisodium phosphate, tripotassium phosphate, sodium carbonate
Thorium, potassium carbonate, etc. have their own buffering effect.
Therefore, it is preferable. As described above, the alkali developing solution is a kettle.
A developer containing an alkali oxalate or non-reducing sugar and a base
Although used as its cation component, Li⁺, N
a⁺, K⁺, NH_Four ⁺Are used.
In systems containing a large amount of cation,
High transparency and excellent developability, but also dissolves up to the image area.
Causes image defects. Therefore, to increase the alkali concentration,
There is a certain limit and it will not cause defects in the image area.
And no image forming layer (residual film) remains in the non-image area.
For complete processing, it is necessary to set delicate liquid conditions.
requested. However, as the cation component,
By using a cation with a large on-radius,
It can suppress the permeability of the developer into the layer,
Without reducing the potash density, that is, developability, the image area
The dissolution inhibiting effect can also be improved. The click
Examples of the on-component include the alkali metal cation and
In addition to monium ions, other cations can be used.
Yes. In the above alkaline aqueous solution (developer)
It is necessary to add a surfactant. Surface activity
Nonionic surfactants and anionic surfactants
Include surfactants, cationic surfactants, and amphoteric surfactants
It is. Nonionic surfactants include polyoxyethylene
Alkyl ethers, polyoxyethylene alkylphenol
Nyl ethers, polyoxyethylene polystyryl fe
Nyl ethers, polyoxyethylene polyoxypropy
Len alkyl ethers, glycerin fatty acid partial esthetics
, Sorbitan fatty acid partial esters, pentaerythris
Litol fatty acid partial esters, propylene glycol
Mono fatty acid esters, Sucrose fatty acid partial esters, polyoxy
Ethylene sorbitan fatty acid partial esters, polyoxy
Ethylene sorbitol fatty acid partial esters, polyethylene
Lenglycol fatty acid esters, polyglycerin fat
Acid partial esters, polyoxyethylenated castor oils,
Polyoxyethylene glycerin fatty acid partial esters,
Fatty acid diethanolamides, N, N-bis-2-hydride
Roxyalkylamines, polyoxyethylene alkyl
Amine, triethanolamine fatty acid ester, tria
Suitable examples include alkylamine oxide. Examples of the anionic surfactant include fat.
Acid salts, abietic acid salts, hydroxyalkanesulfo
Phosphates, alkane sulfonates, dialkyl sulfos
Succinate esters, α-olefin sulfonates, direct
Chain alkylbenzene sulfonates, branched chain alkylbenzenes
Sulfonates, alkyl naphthalene sulfonic acids
Salts, alkylphenoxypolyoxyethylenepropyl
Sulfonates, polyoxyethylene alkylsulfof
Phenyl ether salts, N-methyl-N-oleyl tauri
Sodium salt, N-alkylsulfosuccinic acid monoamide
Disodium salt, petroleum sulfonates, sulfated beef oil,
Sulfuric acid ester salts of fatty acid alkyl esters, alkyl
Sulfate esters, polyoxyethylene alkyl ether
Sulfates, Fatty acid monoglyceride sulfates,
Polyoxyethylene alkylphenyl ether sulfate
Tellurium salts, polyoxyethylene styryl phenyl ether
Sulfate esters, alkyl phosphate esters,
Lioxyethylene alkyl ether phosphate ester salt
, Polyoxyethylene alkylphenyl ether phosphorus
Acid ester salts of styrene / maleic anhydride copolymer
Of partially saponified products, olefin / maleic anhydride copolymer
Partially saponified products, naphthalenesulfonate formalin condensation
Preferred examples include materials. Examples of the cationic surfactant include a
Rukylamine salts, tetrabutylammonium bromide
Quaternary ammonium salts such as polyoxyethylene alcohol
Killamine salts, polyethylene polyamine derivatives, etc.
Can be mentioned. Examples of amphoteric surfactants include carboxy
Sibetaines, alkylaminocarboxylic acids, sulfobe
Tines, amino sulfates, imidazolines, etc.
Is mentioned. Among the above surfactants, “polyoxy
The term “ethylene” refers to polyoxymethylene,
Polyoxya such as xylene, polyoxybutylene
It can also be read as Rukiren,
Included in surfactants. Surfactant concentration in developer
The degree is preferably 0.001 to 10% by mass,
5 to 1% by mass is more preferable, and 0.01 to 0.5% by mass is the most preferable.
Is also preferable. Further development performance is included in the alkaline developing solution.
For the purpose of enhancing the
Yes. For example, N described in JP-A-58-75152
Neutral salts such as aCl, KCl, KBr, JP-A-58-1
EDTA, NTA, etc. described in Japanese Patent No. 90952
As described in JP-A-59-121336.
o (NH_Three)₆] Cl_ThreeCoCl₂・ 6H₂O, etc.
Body, an alkylna described in JP-A-50-51324
Sodium phthalene sulfonate, n-tetradecyl-N, N
^ Anions such as dihydroxyethyl betaine or amphoteric
Surfactant, U.S. Pat. No. 4,374,920
Nonionic fields such as tetramethyldecynediol as described
Surfactant, p- described in JP-A-55-95946
Methyl chloride of dimethylaminomethyl polystyrene
Cationic polymers such as quaternary compounds,
Vinylbenzyltrimethyl described in No. 142528
Copolymerization of ammonium chloride and sodium acrylate.
Amphoteric polymer electrolytes such as those disclosed in JP-A-57-192951
Reducing inorganic salts such as sodium sulfite described in Japanese Patent No.
Such as lithium chloride described in JP-A-58-59444
Inorganic lithium compounds, disclosed in JP 59-75255 A
Organometallic surfactants containing the described organic Si, Ti, etc.,
Organoboron compounds described in JP-A-59-84241
, Tetraalkyls described in EP101010
Quaternary ammonium salts such as ammonium oxide
Can be mentioned. [0138] The image forming layer containing an infrared absorbing dye
Infrared photosensitive lithographic printing plate having the plate making method of the present invention
Therefore, by treating with a specific plate surface treatment liquid, infrared
Line absorbing dye precipitates and precipitates in washing bath and finishing bath
Do not give a defect to the formed image area.
A lithographic printing plate with a sharp, sharp image
The In addition, a lithographic printing plate free from stains in printing can be obtained. [0139] The present invention will now be described in detail with reference to examples.
However, the present invention is not limited to these. In addition,
“%” In the examples represents “mass%”. <Preparation of lithographic printing plate precursor> 0.3 mm thick aluminum
Degreasing the board (material 1050) by washing with trichlorethylene
Nylon brush and 400 mesh pumice-water
Using a suspension, this surface should be grained and washed thoroughly with water.
It was. After washing, this aluminum plate is treated with 25% hydroxide at 45 ° C.
Etching is performed by dipping in an aqueous solution of sodium fluoride for 9 seconds.
After washing with water, immerse in 20% nitric acid aqueous solution for 20 seconds.
It was pickled and washed again with water. Etching of the grained surface at this time
About 3g / m ²Met. Next, this aluminum plate was charged with 7% sulfuric acid.
Current density 15A / dm as a solution ²3g of direct current
/ M²After the anodic oxide coating was provided, it was washed with water and dried. This
10 seconds with a 2.5% aqueous solution of sodium silicate at 30 ° C.
After processing, apply the following undercoat layer coating solution,
The support was obtained by drying for 5 seconds. Drying the primer layer after drying
The coating amount is 15 mg / m²Met. <Coating liquid for undercoat layer> The following copolymer P (molecular weight 28000) 0.3 g Methanol 100g 1g of water [0142] <Synthesis of specific copolymer> Synthesis example (specific copolymer 1) 500ml three-neck equipped with stirrer, condenser and dropping funnel
In a flask, 31.0 g (0.36 mol) of methacrylic acid,
39.1 g (0.36 mol) ethyl chloroformate and aceto
Add 200ml of trinitrile and mix while cooling in an ice-water bath
The thing was stirred. To this mixture was added triethylamine 36.4.
g (0.36 mol) by dropping funnel over about 1 hour
It was dripped. After the dripping is complete, remove the ice-water bath and remove at room temperature 3
The mixture was stirred for 0 minutes. The reaction mixture is mixed with p-aminobenzene.
Nesesulfonamide 51.7g (0.30mol) was added.
Agitate the mixture for 1 hour while warming to 70 ° C in an oil bath.
It was. After completion of the reaction, the mixture is poured into 1 liter of water.
Stir with stirring and stir the resulting mixture for 30 minutes
It was. The mixture is filtered to remove the precipitate, which is
After slurrying with 500 ml, the slurry is filtered,
The obtained solid is dried to give N- (p-aminosulfur
A white solid of (phenylphenyl) methacrylamide was obtained.
(Yield 46.9 g) Next, a stirrer, a cooling pipe and a dropping funnel are provided.
N- (p-aminosulfonylphenol) was added to a 20 ml three-necked flask.
Nyl) methacrylamide 4.61 g, (0.0192 mole)
), 2.94 g (0.0258 mol) of ethyl methacrylate.
), 0.80 g (0.015 mol) of acrylonitrile
And 20 g of N, N-dimethylacetamide in a hot water bath
The mixture was stirred while heating to 65 ° C. This mixture
Add 0.15 g of “V-65” (Wako Pure Chemical Industries, Ltd.) to the product
And stirring the mixture for 2 hours under a nitrogen stream while maintaining at 65 ° C
did. This reaction mixture is further mixed with N- (p-aminosulfonyl).
Phenyl) methacrylamide 4.61 g, methacrylic acid
2.94 g of ethyl, 0.80 g of acrylonitrile, N, N-
Dimethylacetamide and 0.15 g of “V-65”
The compound was added dropwise through a dropping funnel over 2 hours. End of dripping
After completion, the mixture obtained was further stirred at 65 ° C. for 2 hours.
It was. After completion of the reaction, 40 g of methanol is added to the mixture and cooled.
And the resulting mixture is stirred into 2 liters of water.
And stirred the mixture for 30 minutes,
15g white by removing by filtration and drying
A solid was obtained. Gel permeation chromatography
The weight average molecular weight of this particular copolymer (polis
Tylene standard) was 53,000.
It was. On the obtained support, the following image forming layer coating solution
The dry coating amount is 1.8 g / m²Apply to be
Thus, a positive type lithographic printing plate precursor was obtained. <Coating liquid for image forming layer>   0.4 g of the above specific copolymer 1 [component (B)]   m, p-cresol novolak [component (B)] 0.6 g   (M / p ratio = 6/4, weight average molecular weight 8000,     0.5% unreacted cresol)   Cyanine dye A [(A + C) component] 0.1 g   Phthalic anhydride [component (D)] 0.05 g   0.002 g of p-toluenesulfonic acid   Ethyl violet 0.02g   (Counterion: 6-hydroxy-β-naphthalenesulfonic acid)   Naphthoquinone 1,2-diazide-5-sulfonylcroid and     0.01 g esterified with pyrogallol-acetone resin   Fluorosurfactant 0.05g   (Product name: Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)   Methyl ethyl ketone 8g   1-methoxy-2-propanol 4g (SiO 2₂Preparation of alkaline developer solution
(Made by) silicon oxide SiO₂And potassium oxide K₂Mixing ratio of O
SiO₂/ K₂4.0% potassium silicate with an O of 1.1,
Ionine C-158-G (manufactured by Takemoto Yushi) 0.20%
Ionin D-1105 (made by Takemoto Yushi) 0.005% and
Olfin AK-02 (Nisshin Chemical) containing 0.015%
A Lucari developing solution was prepared. (Preparation of alkali developing solution containing non-reducing sugar) Non-reducing sugar
-Sorbit / Potassium Oxide Combining Base and Base
K₂Potassium salt made of O 5.0%, Pionine C-1
58-G (made by Takemoto Yushi) 0.20%, Pionein D-1
105 (made by Takemoto Yushi) 0.005% and Olfin AK-0
2 (Nissin Chemical) 0.015% Alkaline Development
A liquid was prepared. Output 5 to the lithographic printing plate precursor obtained above
00 mW, wavelength 830 nm, beam diameter 17 μm (1 /
e²) Main scanning speed of 5 m / sec using semiconductor laser
And then kept at 25 ° C. [0148] Examples 1-12 and Comparative Examples 1-12 This lithographic printing plate
The original plate is made of the above SiO₂Full of alkaline developer solution
Automatic processor PS900NP (Fuji Photo Film)
Developed at a development temperature of 30 ° C. for 12 seconds.
did. After the development process is completed, the water washing process and rinse process
After treatment with plate protection liquid (desensitization treatment)
A plate printing plate was obtained. Washing water and water used in Examples 1-12
Each of the aqueous solution and the plate surface protective solution is composed of the following compounds A to F:
Either one was added. A: Aminotri (methylenephosphonic acid), 5Na salt (day
DQ2006 from Monsanto Co., Ltd.) B: 1-hydroxyethane-1,1-diphosphonic acid, 4Na salt
(Japan Monsanto Co., Ltd. DQ2016) C: Ethylenediaminetetra (methylenephosphonic acid)
5K salt (DQ2044 manufactured by Nippon Monsanto Co., Ltd.) D: Hexamethylenediaminetetra (methylenephosphone
Acid) · 6K salt (DQ2054 manufactured by Monsanto Japan) E: Diethylenetriaminepenta (methylenephosphone
Acid) (DQ2060, Monsanto Japan) F: Diethylenetriaminepenta (methylenephosphone
Acid) ・ 5Na salt (DQ206 manufactured by Monsanto Japan)
6) Washing water: any of compounds A to F in tap water
To which is added. Rinse solution: Rinse solution stock solution with the following composition (unit: mass%)
Add any of compounds A to F and dilute 8 times
did. Rinse solution stock solution   Sodium dodecyl diphenyl ether disulfonate 2.00% by mass   Dioctylsulfosuccinate sodium salt 2.00   Phosphoric acid (85%) 5.00   Sodium hydroxide 2.00   Emulsion type silicone antifoaming agent 0.01   Copolymer A (see formula below, molecular weight 10,000) 0.50 [0150] [Chemical 1]   5-Chloro-2-methyl-4-isothiazolin-3-one 0.02   2-Bromo-2-nitro-1,3-propanediol 0.02 The total amount is made 100% by mass with water. Plate surface protective solution: The following composition (unit: mass%)
To which any of compounds A to F is added. Gum arabic 1.8% by mass Enzyme-modified potato starch 8.3 Enzyme-modified onion starch 3.7 Phosphorylated waxy onion starch 1.8 Dioctylsulfosuccinate sodium salt 0.91 Copolymer A (see formula above) 0.05 Primary ammonium phosphate 0.27 Phosphoric acid (85%) 0.37 EDTA-tetrasodium salt 0.27 Ethylene glycol 1.8 Benzyl alcohol 2.3 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 2-Bromo-2-nitro-1,3-propanediol 0.02 Citric acid 0.3 Emulsion type silicone antifoaming agent 0.02 The total amount is made 100% by mass with water. In the comparative example, each plate surface treatment liquid is added to the top.
The composition used does not contain any of compounds A to F.
I used it. Plate processing process after development in each example, plate processing
Organic phosphonic acid compound contained in the liquid, and its added amount (during use)
Table 1 summarizes the concentrations. Plate processing process
100m per day²After 1 month at the processing amount, wash with water
In bath, rinse bath, desensitizing bath (plate protection solution bath)
The presence or absence of precipitation was observed. The results are shown in Table 1.
○, where no precipitation was observed,
Indicated as x. [0153] Examples 13-24 and Comparative Examples 13-24 As developers
Other than using non-reducing sugar-containing alkaline developer
As in Examples 1-12 and Comparative Examples 1-12, a lithographic printing plate was prepared.
Manufacturing, washing bath, rinsing bath, desensitizing bath (plate surface protection liquid
The presence or absence of precipitation in the bath) was observed. Details in each example
Table 2 shows the results. [0154] [Table 1] [0155] [Table 2]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AB03 AC08 AD01 AD03 CB14                       CB15 CB29 CB52 CC20 FA03                       FA17 FA28                 2H096 AA07 BA16 BA20 EA04 GA08                       HA02 JA04                 2H114 AA04 AA24 BA01 BA10 DA21                       DA28 DA34 DA52 DA53 DA59                       EA01 EA02 EA05 EA08 GA01

Claims (1)

What is claimed is: 1. An infrared-sensitive lithographic printing plate having an image-forming layer containing an infrared-absorbing dye is exposed to infrared light, developed, and then processed with a plate surface treatment solution. A plate making method, wherein the plate surface treatment liquid contains a compound having two or more phosphonic acid groups.