JP2003195525A - Method for making lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of stably making a lithographic printing plate free from precipitation of an IR absorbing dye in a plate face protective liquid even if a long-term treatment and thereby free from contamination during printing. <P>SOLUTION: The method for making the lithographic printing plate is carried out by exposing an IR ray-sensitive lithographic printing plate having an image forming layer containing an IR absorbing dye to IR rays, and by developing and treating with the plate face protective liquid containing soybean polysaccharides. <P>COPYRIGHT: (C)2003,JPO

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 information on the law, infra-red lithographic printing plate making
Regarding the method. [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. Recent infrared laser exposure type image recording materials
As the coating material has been improved, it has been used in the image forming layer.
For example, infrared absorbing dyes such as cyanine dyes
It is hydrophobic. Such infrared absorbing dyes are
After the development process, hold it in a processing bath for further post-processing.
It is deposited and deposited, which adheres to the plate surface and stains the non-image area.
That is, there is a drawback that printing stains occur. Like this
In particular, infrared in the plate surface protection solution after development processing
There is a need for means to suppress the precipitation of the line absorbing dye. [0004] The present invention provides a long-term treatment.
Even so, the infrared absorbing dye may precipitate in the plate surface protection liquid.
Stable lithographic printing plates with no print stains
The purpose is to provide a plate making method that can be created
And [0005] Means for Solving the Problems The present inventors have solved the above problems.
As a result of earnest research to achieve
Of a photosensitive lithographic printing plate having an image-forming layer containing a coating material
In the plate, treat with plate surface protection solution containing soy polysaccharide
By doing so, the infrared absorbing dye will remain on the plate even after long-term treatment.
It was found that no precipitation occurred in the protective solution, and the present invention was completed.
It came to be completed. Accordingly, the present invention includes an infrared absorbing dye.
Infrared photosensitive lithographic printing plate with image forming layer
After external exposure and development, the plate surface containing soy polysaccharide
A process for making a lithographic printing plate, characterized by treatment with a protective liquid
Is directed to. [0006] DETAILED DESCRIPTION OF THE INVENTION [Plate surface protecting solution] First, the plate making of the present invention
The plate surface protective liquid used in the method will be described. Plate making method of the present invention
The plate surface protection solution used in the method is water-soluble and has film-forming properties.
It consists of an aqueous solution containing bean polysaccharides. Water soluble
Soy polysaccharide is a polysaccharide obtained by extracting raw soybean with water.
Yes, mainly galactose, arabinose, galactus
Contains ronic acid as a constituent. As a commercial product, Soya
Five-S-LN (Fuji Oil Co., Ltd.)
The The average molecular weight of the soybean polysaccharide that can be used in the present invention is 5 to 5.
1 million, and the viscosity (25 ° C.) of the 10% by mass aqueous solution is 5 to 5.
Those having a range of 100 cp are preferably used. Plate protection
The content of soybean polysaccharide in the liquid is preferably 0.3 to 50
It is 0.5 mass%, More preferably, it is 0.5-40 mass%. This
These soy polysaccharides are dissolved in water or warm water to form a uniform aqueous solution.
Use as In the plate surface protection solution, the above-mentioned soy polysaccharides are
It may be mixed with starch such as dextrin or modified starch
Yes. Furthermore, other water-soluble polymer compounds may be added. Example
For example, gum arabic, fibrin derivatives (eg carboxy
Methylcellulose, carboxyethylcellulose, methyl
Cellulose, etc.) and modified products thereof, polyvinyl alcohol
And its derivatives polyvinylpyrrolidone, polyacryl
Amides and their copolymers, vinyl methyl ether / anhydrous
Maleic acid copolymer, vinyl acetate / maleic anhydride copolymer
And styrene / maleic anhydride copolymer, etc.
It is. The plate surface protection liquid is generally in the acidic region pH 3
It is more advantageous to use in the range of -6. Set pH to 3-6
In general, mineral acids, organic acids or
Add and adjust inorganic salts. The amount added is 0.01-2.
% By mass. For example, mineral acids include nitric acid, sulfuric acid, phosphorus
An acid, metaphosphoric acid, etc. are mentioned. Quench as organic acid
Acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid,
Tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, yes
Examples include phosphonic acid. Nitric acid mug as an inorganic salt
Nesium, primary sodium phosphate, secondary sodium phosphate
Nickel sulfate, sodium hexametaphosphate, tri
Examples include sodium polyphosphate. Mineral acid, organic acid or
Is a combination of at least one or more inorganic salts
May be. Adding a surfactant to the plate surface protective liquid
As a result, the surface condition of the coating layer is improved. Usable surface activity
Anionic surfactant and / or nonion as agent
Surfactant is mentioned. For example, anionic surface activity
Agents include fatty acid salts, abietic acid salts, hydroxy
Sialkane sulfonates, alkane sulfonates and
And / or divalent metal salts, dialkylsulfosuccinates
And / or divalent metal salts, linear alkylbenzene sulfo
Phosphates and / or divalent metal salts, branched chain alkylbennes
Zensulfonates and / or divalent metal salts, alkyl
Naphthalene sulfonates, alkylphenoxypolio
Xylethylenepropyl sulfonates, polyoxyethylene
Lenalkylsulfophenyl ether salts, N-methyl
-N-oleyl taurine sodium, N-alkyls
Rufosuccinic acid monoamide disodium salt, petroleum sulfo
Phosphates, sulfated castor oil, sulfated beef tallow oil, fatty acid al
Kill ester sulfate ester salt, alkyl sulfate ester
Salts, polyoxyethylene alkyl ether sulfates
Tellurium salts, fatty acid monoglyceride sulfates,
Reoxyethylene alkylphenyl ether sulfate
Salts, polyoxyethylene styryl phenyl ether
Sulfate ester salts, alkyl phosphate ester salts, polio
Xylethylene alkyl ether phosphates, poly
Oxyethylene alkyl phenyl ether phosphate
Partial saponification of salts and styrene-maleic anhydride copolymer
Products, partial ken of olefin-maleic anhydride copolymer
, Naphthalenesulfonate formalin condensates, etc.
Is mentioned. Among these, dialkyl sulfosucci
Acid salts and / or divalent metal salts, alkyl sulfates
Particularly preferred are salts and alkylnaphthalene sulfonates.
Used. Further, as nonionic surfactants,
Reoxyethylene alkyl ethers, polyoxyethylene
Lenalkylphenyl ethers, polyoxyethylene
Polystyryl phenyl ether, polyoxyethylene poly
Lioxypropylene alkyl ether, glycerin fat
Acid partial esters, sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial esters, propire
Glycol mono fatty acid ester, sucrose fatty acid partial ester
Steal, polyoxyethylene sorbitan fatty acid partial ester
Tells, polyoxyethylene sorbitol fatty acid partial ester
Stealth, polyethylene glycol fatty acid esters,
Polyglycerin fatty acid partial esters, polyoxyethylene
Renated castor oil, polyoxyethylene glycerin fat
Acid partial esters, fatty acid diethanolamides, N,
N-bis-2-hydroxyalkylamines, polyoxy
Siethylene alkylamine, triethanolamine fat
Acid esters, trialkylamine oxides, etc.
It is. Among them, polyoxyethylene alkylphenyl
Ethers, polyoxyethylene-polyoxypropylene
Preferred are block polymers. Fluorine
The same is true for silicon-based anions and nonionic surfactants
Can be used for Two or more of these surfactants
It can also be used together. For example, two or more different types
Combination of anionic surfactants and anionic surfactants
The combined use of a nonionic surfactant is preferred. Use of surfactant
The amount does not need to be particularly limited, but preferably the plate surface protecting agent
0.01 to 20% by mass. In addition to the above-mentioned components, the plate surface protective liquid may be used if necessary.
As a lubricant, ethylene glycol, propylene glycol
, Triethylene glycol, butylene glycol,
Xylene glycol, diethylene glycol, dipropy
Lenglycol, glycerin, trimethylolpropa
Diglycerin and the like are preferably used. These wet
The agent may be used alone or in combination of two or more.
Generally, the wetting agent is used in an amount of 1-25% by weight.
Is preferred. In addition, chelate compounds are added to the plate surface protection solution.
May be. Usually, the plate surface protection solution is commercially available as a concentrate.
When using, dilute it with tap water, well water, etc.
It is. Cal contained in this diluted tap water and well water
Cium ions etc. have a bad influence on printing, and the printed matter is easily stained.
The chelate compound is added.
In addition, the above disadvantages can be eliminated. Preferred key
Examples of rate compounds include Na.₂P₂O₇, Na_FiveP_Three
O_Three, Na_ThreeP_ThreeO₉, Na₂O _FourP (NaO_ThreeP) PO_ThreeNa₂, Mosquito
Polyphosphoric acid such as lugon (sodium polymetaphosphate)
Salt, ethylenediaminetetraacetic acid, its potassium salt,
Sodium salt of dihydroxyethylglycine
Lium salt, its sodium salt; hydroxyimino divinegar
Acid, its potassium salt, its sodium salt;
-Terdiaminetetraacetic acid, its potassium salt, its sodium
Lium salt; diethylenetriaminepentaacetic acid, potassium
Um salt, its sodium salt; triethylenetetramine
Oxaacetic acid, its potassium salt, its sodium salt, hydro
Xylethylethylenediaminetriacetic acid, its potassium
Salt, sodium salt thereof; 1,2-diaminocyclohexa
Tetraacetic acid, its potassium salt, its sodium salt;
1,3-diamino-2-propanoltetraacetic acid, its
Amino poly, such as potassium salt, its sodium salt etc.
Carboxylic acids, nitrilotriacetic acid, its potassium salt,
Sodium salt of 1-hydroxyethane-1,1-difo
Sphonic acid, its potassium salt, its sodium salt; amino
Tri (methylenephosphonic acid), its potassium salt, its
Thorium salt; ethyleneaziminetetra (methylenephospho
Acid), potassium salt thereof, sodium salt thereof;
N-triaminepenta (methylenephosphonic acid), its potash
Um salt, its sodium salt; hexamethylenediamine
Tiger (methylenephosphonic acid), its potassium salt, its
Organic phosphonic acids such as thorium salt, or 2
-Phosphonobutanetricarboxylic acid-1,2,4
Lithium salt, its sodium salt;
Recarboxylic acid-2,3,4, its potassium salt, its sodium
1-phosphonoethanetricarboxylic acid-1,
2, 2, its potassium salt, its sodium salt etc.
Phosphonoalkanetricarboxylic acids
Yes. Instead of sodium and potassium salts of the above chelating agents
Organic amine salts are also effective. These chelating agents
Stablely present in the plate surface protection liquid composition and does not impair printability
Things are chosen. Addition amount to plate surface protection liquid at the time of use
0.001-1.0 mass% is suitable with respect to it. Add antiseptic, antifoaming agent, etc. to plate surface protection liquid
can do. For example, as a preservative, phenol or
Is its derivative, formalin, imidazole derivative,
Sodium doroacetate, 4-isothiazolin-3-one derivative
Conductor, benzoisothiazolin-3-one, benztria
Zole derivatives, amiding anidine derivatives, quaternary ammo
Induction of nium salts, pyridine, quinoline, guanidine, etc.
Body, diazine, triazole derivatives, oxazole,
And oxazine derivatives. The preferred addition amount is
Amount that is stable against bacteria, mold, yeast, etc.
However, it depends on the type of bacteria, mold and yeast
However, it is 0.01 to 4% by mass with respect to the plate surface protective liquid during use.
Range is preferred and effective against various molds and sterilization
It is preferable to use two or more kinds of preservatives in combination.
Yes. Moreover, as an antifoamer, a silicon antifoamer is preferable.
Among them, emulsification dispersion type and solubilization can be used.
The Preferably it is 0.001 with respect to the plate surface protection liquid at the time of use.
The range of ~ 1.0% by mass is optimal. In addition to the above-mentioned components, the plate surface protective liquid may be used if necessary.
A sensitizer can also be added. For example, turpentine oil,
Xylene, toluene, low heptane, solvent naphth
Sa, kerosene, mineral spirits, boiling point about 120 ℃
Hydrocarbons such as petroleum fractions up to about 250 ° C., for example jib
Tyl phthalate, diheptyl phthalate, di-n-oct
Tyl phthalate, di (2-ethylhexyl) phthalate
, Dinonyl phthalate, didecyl phthalate, dilau
Lid phthalate, butyl benzyl phthalate, etc.
Diester agents such as dioctyl adipate, buty
Luglycol adipate, dioctyl azelate, jib
Tilsebacate, di (2-ethylhexyl) sebacate
, Dioctyl sebacate and other aliphatic dibasic acid esters
Epoxidized trigs such as epoxidized soybean oil
Riselides such as tricresyl phosphate, tri
Octyl phosphate, triskrol ethyl phosphate
Phosphate esters such as benzoate, such as benzyl benzoate
Freezing point of benzoates such as
And a plasticizer having a boiling point of 300 ° C. or higher under 1 atm.
The In addition to these solvents, for example,
Ketones such as rohexanone, such as ethylene dichloro
Halogenated hydrocarbons such as id, such as ethylene glycol
Monomethyl ether, ethylene glycol monofer
Nyl ether, ethylene glycol monobutyl ether
Ethylene glycol ethers such as
Acids include caproic acid, enanthic acid, caprylic acid, and helical
Gonic acid, capric acid, undecyl acid, lauric acid, tri
Decylic acid, myristic acid, pentadecylic acid, palmitic
Acid, heptadecyl acid, stearic acid, nonadecanoic acid,
Lacic acid, behenic acid, lignoceric acid, serotic acid,
Ptacosanoic acid, montanic acid, melissic acid, lacteric acid,
Saturated fatty acids such as isovaleric acid and acrylic acid, crotonic acid,
Isocroton, undecylenic acid, oleic acid, Eleiji
Acid, cetreic acid, nilucic acid, buteticic acid, sorbi
Acid, linoleic acid, linolenic acid, arachidonic acid, propylene
All acid, stearolic acid, sardine acid, taliphosphoric acid, lithium
There are unsaturated fatty acids such as canic acid. More preferably 50 ° C
In which the liquid is a fatty acid, more preferably charcoal
The prime number is 5-25, most preferably the carbon number is 8-2.
1. These sensitizers can be used alone or in combination of two or more.
It can also be used. The preferred range for the amount used is the plate surface
A more preferable range is 0.01 to 10% by mass of the protective liquid.
0.05-5 mass%. The above oil sensitizer is
The plate surface protection liquid is emulsified and dispersed, and contained as its oil phase
May also be solubilized with the help of solubilizers
May be. The various components in the plate surface protection liquid described above
The content is based on the total weight of the plate surface protection liquid during use.
is there. Prepare plate protection solution in concentrated form first.
Is common. Such concentrate is appropriately diluted with water.
Use plate surface protection liquid during use. Plate containing soybean polysaccharides
Surface protection liquid can be used for both solution type and emulsification type.
Easy to design, protects the image area and protects it from non-images
Excellent effect in protecting the hydrophilicity of the image area. Plate protection
The use mode of the liquid is not particularly limited.
It can be used with a dynamic developing machine. Such automatic display
The imager is a post-process that includes processing with a development bath and a plate protection solution.
A device that consists of a physical bath and conveys a photosensitive lithographic printing plate, and each
Consists of processing bath and spray device, etc., exposed
The photosensitive lithographic printing plate is pumped while being transported horizontally.
Process each raised liquid by spraying from the spray nozzle
Is. Recently, a treatment bath filled with treatment solution
A photosensitive lithographic printing plate is placed inside with a liquid guide roll.
There is also known a method of processing by immersion conveyance. like this
In automatic processing, the processing amount and operating time in the processing bath
Depending on the process, replenish each replenisher
In the present invention, processing while replenishing the plate surface protection liquid
can do. The plate surface protection liquid is an automatic gum filling machine.
Even if it uses etc., it can apply | coat uniformly. The present invention
In the processing with the plate surface protective solution, after the development processing step,
It can be done immediately with anhydrous washing, or after development (washing with water
Including process, circulating water wash or small amount of applied water wash
Or treated with a rinsing solution containing a surfactant.
It can be done later. [Photosensitive planographic printing plate] The plate making method of the present invention
Infrared photosensitive lithographic seal containing the infrared absorbing dye to be applied
The printing plate is not particularly limited. Also its exposure
Processing and development processing can be carried out according to conventional methods,
Combined with processing with the above plate surface processing solution, general automatic development
Can be implemented on the machine. In the following, the plate making method of the present invention
Image forming layer containing infrared absorbing dye
Infrared photosensitive lithographic printing plate and plate making method of the present invention
Explains the general alkaline developer used
The The infrared-sensitive lithographic printing plate is printed on a support.
It has an image-forming layer and, if necessary, other layers
The image forming layer includes (A) an infrared absorbing dye, and
(B) optionally containing an alkali-soluble polymer compound
(C) The Al is dissolved in an alkali-soluble polymer compound.
Solubility of potash-soluble polymer compounds in alkaline aqueous solution
And lowering the solubility lowering effect by heating.
May contain less compounds, (D) cyclic acid anhydrides, etc.
Yes. In the case of negative lithographic printing plate precursors,
Is cured to form an image area.
(E) a compound that generates an acid by heat and (F) an acid
It contains a crosslinking agent that crosslinks. Below, each structure
The 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. [0023] 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 with 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. [0037] 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 with 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. [0041] 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 above acidic property.
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. The acid groups (1) to (3) are selected.
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, 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,
Weight average molecular weight is 2000 or more, number average molecular weight is 500
The above are preferable, and the weight average molecular weight is 5000-3.
00000, number average molecular weight is 800-250,000
The dispersity (weight 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,
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 polymer can be obtained 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. As the component (C), the above (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 (I) or (II). [0055] In the general formula (I), 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 (II), 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. Cyclic acid anhydrides such as 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 can be 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 can be 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. 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, the 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. Examples of the anodizing treatment include hydrochloric acid,
Inorganic acids such as sulfuric acid, phosphoric acid, chromic acid, nitric acid, boric acid
Or oxalic acid, sulfamic acid, benzenesulfonic acid, etc.
Of organic acids or their salts in aqueous or non-aqueous solutions.
Aluminum in a single or a combination of two or more electrolytes
It is applied by flowing an electrode using a nium plate as an anode.
Also, as described in US Pat. No. 3,658,662
Silicate electrodeposition 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 (II
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. [0086] Where 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, methyl 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.
Further, 0.05 to 5% by mass is more preferable. Also, immersion temperature
The degree is preferably 20 to 90 ° C, and preferably 25 to 50 ° C.
More preferable. The immersion time is preferably 0.1 second to 20 minutes.
2 seconds to 1 minute is more preferable. Undercoat layer solution
Bases such as monia, triethylamine, potassium hydroxide
PH 1 to acidic substances and acidic substances such as hydrochloric acid and phosphoric acid
It can also be adjusted to a range of 12. Also, tone reproducibility
A yellow dye may be added for the purpose of improvement. Infrared photosensitive lithographic printing plates are infrared lasers
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 Further, the concentration of alkali silicate in the developer is
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 comprising 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. Furthermore, 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)
A surfactant can be added. Surfactant
As non-ionic surfactant, anionic surfactant
Agents, cationic surfactants, amphoteric surfactants
The Nonionic surface activity includes polyoxyethylene
Ruky ethers, polyoxyethylene alkyl pheny
Ethers, polyoxyethylene polystyrylpheny
Ethers, polyoxyethylene polyoxypropylene
Alkyl ethers, glycerin fatty acid partial esters
, Sorbitan fatty acid partial esters, pentaerythri
Tall fatty acid partial esters, propylene glycol
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. Anionic surfactants include, for example, 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 sulfate salts,
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. As the cationic surfactant, for example,
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
-Anionic or amphoteric such as dihydroxyethyl betaine
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. [0105] 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 protection liquid,
Infrared absorbing dye precipitates and deposits in the plate surface protection liquid bath
The flatness which is stable for a long time and has no print stains
A plate printing plate can be made. [0106] 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 [0109] <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 Preparation of developer (SiO₂Preparation of alkaline developing solution containing silica)
Elemental SiO₂And potassium oxide K₂O mixing ratio SiO₂/ K₂
4.0% potassium silicate with O = 1.1, pionine C-
158-G (made by Takemoto Yushi) 0.20%, Pionine D-
1105 (made by Takemoto Yushi) 0.005% and Olfin AK
-02 (Nisshin Chemical Co., Ltd.) Alkaline development containing 0.015%
A 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. Preparation of plate surface protective solution [Plate protection solution 1] Water-soluble soybean polysaccharide (Fuji Oil Co., Ltd.)
Soya Five-S-LN: Analytical value Galactose 43.6
%, Arabinose 22.5%, Galacturonic acid 2.2%, remaining
80% by weight of protein (4.7%) and cream dextrin
(Roasted dextrin) 170 mass parts pure water 728.8 mass
Dissolved in the part. In that aqueous solution is an anionic surfactant
Alkyl (mainly dodecyl) diphenyl ether dis
Lufonate (trade name: Sandet BL Sanyo Chemical Co., Ltd.)
10 parts by weight, di (2-ethylhexyl) sulfosuccinic acid
3 parts by mass of salt (Lapisol B-80 manufactured by NOF Corporation),
0.2 parts by mass of methyl benzoate, 4-isothiazoline-3-
1.0 part by weight of on-derivative, 3.0 parts by weight of phosphoric acid (85%),
Plate surface protection by adding 5.0 parts by weight of magnesium sulfate and dissolving
A liquid was prepared. Dilute this plate surface protection solution 1: 1 with water.
The working solution was used. [Plate surface protecting liquid 2] Water-soluble soybean polysaccharide (plate
(Same as that used for the surface protection liquid)
Dissolve 170 parts by mass of mudextrin in 673.8 parts by mass of pure water.
I understood. 5.0 mass of primary ammonium phosphate in the aqueous solution
Parts, 3 parts by mass of phosphoric acid, 0.2 parts by mass of methyl benzoate, 4-
Add 1.0 part by mass of isothiazolin-3-one derivative and dissolve
The aqueous phase was prepared by cracking. DOP (Dioctylphthalate)
G) 10 parts by mass, 5.0 parts by mass of benzyl alcohol, interface
Di (2-ethylhexyl) sulfosuccinic acid as activator
25 mass of salt (Lapisol B-80 manufactured by Nippon Oil & Fats Co., Ltd.)
Parts, polyoxyethylene nonylphenol ether
Margen # 903 Kao Co., Ltd., HLB = 7.8) 12 quality
Amount part, sorbitan monooleate (nonion OP-80 days
Mix and dissolve 3 parts by mass of this oil and fat Co., Ltd. to prepare an oil phase.
It was. Stir the water phase at 500 rpm to 600 rpm and a small amount of oil phase
Drip each one, and emulsify through a homogenizer after completion of the addition.
A mold plate surface protection solution was obtained. Make this plate surface protection solution 1: 1 with water.
Diluted to make a working solution. [Comparative plate surface protective liquid 1]
Prepared in a similar procedure but with the following composition: Pure water 72
8.8 g, cream dextrin 170 g, Arabia
Gum 80g, Sandet BL 10g, Rapisol B80
3 g, methyl benzoate 0.2 g, 4-isothiazoline-3-
ON derivative 1.0g, phosphoric acid (85%) 3.0g, sulfuric acid
Magnesium 5.0g. This plate surface protection solution is 1: 1 with water.
Diluted into a working solution. [Comparative Plate Surface Protection Liquid 2] The above-mentioned plate surface protection liquid
Prepared in a similar procedure to 2, but with the following composition: (water
Phase) Pure water 673.8g, Cream dextrin 170
g, gum arabic 80 g, primary ammonium phosphate 5
g, phosphoric acid (85%) 3 g, methyl benzoate 0.2 g,
4-isothiazolin-3-one derivative 1.0 g, (oil phase) D
OP 10g, benzyl alcohol 5.0g, Lapizo
Le B-80 25.0 g, Emargen # 903 12.0 g,
Nion OP-80 3.0g. Make this plate surface protection solution 1: 1 with water.
Diluted to make a working solution. [0118] Examples 1 to 8 and Comparative Examples 1 to 8 Photosensitivities prepared above
Plate making using a lithographic printing plate, developer, and plate surface protection solution.
It was. Exposure, development processing, printing conditions and evaluation are as follows:
did. Output 500m to the lithographic printing plate precursor obtained above
W, wavelength 830 nm, beam diameter 17 μm (1 / e²Half of
Exposure using a conductor laser at a main scanning speed of 5 m / second,
Maintained at 25 ° C. After exposure, the planographic printing plate precursor
Automatic display filled with Lucari developing solution and various plate surface protection solutions
According to the imager PS900NP (manufactured by Fuji Photo Film Co., Ltd.)
Developed at a development temperature of 30 ° C. for 12 seconds,
A lithographic printing plate was obtained through the treatment according to 1. [Evaluation] The processing amount in the plate surface protection liquid bath was 50 m.
²/ Day or 150m²/ Day, the plate after each throughput
Precipitation / precipitation of foreign matters in the protective liquid bath was visually observed. Continued
The resulting lithographic printing plate is Man Roland
GEOS G made by Dainippon Ink Co., Ltd.
Print using red (S) and check for ink stains on non-image areas
Evaluated visually. In Table 1 below, the plate surface protection solution used in each example,
The amount of treatment in the plate surface protective liquid bath and the result of evaluation are shown. Na
In Examples 1 to 4 and Comparative Examples 1 to 4, the development processing is performed using Si.
O₂Example 5
-8 and Comparative Examples 5-8 are non-reducing sugar-containing alkali developing treatments
This was carried out using a scientific solution. [0120] [Table 1]

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 treated with a plate surface protective solution containing soybean polysaccharide. A process for making a lithographic printing plate characterized by