JP2003295467A - Method for treating lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating a heat sensitive lithographic printing plate by which a printing plate is stably treated without having deposition of scum from a heat sensitive layer component even for long-term continuous treatment or without having failure in ink deposition or contamination of the base while little sludge is produced. <P>SOLUTION: The method for treating a plate is carried out by image-wisely exposing a lithographic printing plate having a heat sensitive layer on a supporting body and then developing the plate by using an alkali developer containing an alkali metal silicate and containing an alkali-soluble resin by 0.02 to 0.1 mass%. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a flat plate having a heat sensitive layer.
The present invention relates to a method for processing a printing plate. [0002] 2. Description of the Related Art Plate making process of lithographic printing plate for infrared laser
Then, the thermosensitive layer component is dissolved in the developer in the developing bath, and then
It is common to perform washing and gumming with an automatic processor.
is there. As the plate throughput increases, thermal stratification occurs in the development bath.
Concentration of the water increases, and the heat sensitive layer component becomes debris.
Or settles on the plate.
To adhere to the ink and cause ink imperfections or soiling.
Often happened and was a problem. Solve this problem
To do this, use a highly alkaline developer and
It has also been proposed to use a development replenisher with high potency.
However, the development stability is sufficiently high due to the large change in alkali activity.
Not a minute, especially in long-running processing
Was big. Various surfactants are also being investigated.
But it was not enough. [0003] Accordingly, it is an object of the present invention.
The heat-sensitive layer components are
There is no adhesion of scum that comes, ink imperfection imperfection and ground dirt etc.
It generates no sludge and is stable.
A processing method for lithographic printing plates for infrared lasers
There is to serve. [0004] The inventor has solved the above problems.
As a result of diligent research to solve the problem, lithographic printing plates with image exposure
Containing an alkali metal silicate and a certain amount of
By processing with a developer containing potash-soluble resin,
There is no adhesion of ink, resulting in poor ink deposition or scumming.
And found that it can be processed stably without
It was. That is, the present invention relates to a lithographic plate having a heat-sensitive layer on a support.
After image exposure of printing plate, alkaline developer and developer replenisher
In the processing method used for development processing,
The alkali developer contains an alkali metal silicate
And 0.02 to 0.1% by mass of an alkali-soluble resin.
Concerning processing method of planographic printing plate characterized by containing
The By the method of the present invention, the residue dispersibility is improved.
Can reduce the reattachment of scum, but this is red
Included in the unexposed area of the heat-sensitive layer of the lithographic printing plate for external laser
By increasing the affinity between the resin used and the developer
it is conceivable that. [0005] BEST MODE FOR CARRYING OUT THE INVENTION
Details on the processing method of printing plate (hereinafter referred to as PS plate)
Explain in detail. Used in the processing method of the present invention
Lucari developer contains at least one alcohol at the start of development.
Contains potassium metal silicate and alkali-soluble resin
It is characterized by containing 0.02 to 0.1% by mass. Book
In addition to the above essential components, the alkaline developer in the invention may be further modified.
May optionally contain other bases, surfactants, and the like. [Alkali metal silicate] Silica of alkali metal
Examples of the salt include sodium silicate, potassium silicate,
There are lithium silicates, either alone or in combination
Can be used. At this time, it is a component of the silicate
Silicon oxide SiO₂And alkali oxide M₂O (M is alkali
Represents a metal or ammonium group. Mixing ratio with
And the density can be adjusted easily.
Yes. Silicon oxide SiO₂And alkali oxide M₂With O
Mixing ratio (SiO₂/ M₂O: molar ratio) is 0.5 to 3.0
Is preferable, and 1.0 to 2.0 is more preferable
Yes. The developer and replenisher used in the present invention are alkali metals.
It is possible to use an alkali agent (base) other than silicate of
Yes. Examples include potassium hydroxide and sodium hydroxide.
, Lithium hydroxide, sodium secondary or tertiary phosphate
Or ammonium salt, sodium metasilicate, sodium carbonate
Inorganic alkaline agents such as lithium and ammonia, mono, di, and
Or trimethylamine, mono, di, or triethyla
Min, mono or diisopropylamine, n-butylamin
Min, mono, di, or triethanolamine, mono,
Di- or triisopropanolamine, ethylene
Organic amine compounds such as ethylene and ethylenediimine are used.
It is. Content of these alkaline agents in the developer
Is 0.005 to 10% by mass, preferably 0.05 to
5% by mass. [Alkali-soluble resin] In the present invention,
Lucari developer is 0.02-0.1 quality at the start of development
Contains an amount of alkali-soluble resin. Alkali soluble
Examples of the resin include novolak resin, hydroxyl group and carbon.
Vinyl resin having an alkali-soluble group such as a boxyl group
Is mentioned. In addition, the heat-sensitive layer of the lithographic printing plate to be developed
The same alkali as the alkali-soluble resin contained therein
More preferably, a soluble resin is used. Tree like this
By using fat, the developability of the components in the heat sensitive layer and
Dispersibility is increased, and it is considered that there is a higher effect of the present invention.
It is done. Novolac resins include phenols and
Obtained by condensation of aldehyde or ketone in the presence of an acid catalyst
Examples of the phenols include:
Phenol, o-cresol, m-cresol, p
-Cresol, 3,5-xylenol, 2,4-xylenol
, 2,5-xylenol, carvacrol, thymol,
Catechol, resorcin, hydroquinone, pyrogallow
And prologlucin, etc.
Formaldehyde, benzaldehyde, acetal
Dehydr, crotonaldehyde, furfural, etc.
It is. Among these, preferred are formaldehyde and
And benzaldehyde. As ketones,
And methyl ethyl ketone. The above phenolic compounds may be used alone or in combination
Condensed with formaldehyde or ketone in combination
A resin can be obtained. Of these, preferred novola
The resin is phenol, m-cresol, o-creso
At least one selected from the group and p-cresol
Resin obtained by copolycondensation with formaldehyde
For example, phenol-formaldehyde resin, m-
Cresol / formaldehyde resin, o-cresol /
Formaldehyde resin, phenol, p-cresol,
Formaldehyde copolymer resin, m-cresol, p-
Cresol-formaldehyde copolycondensate resin, o-c
Resole / p-cresol / formaldehyde copolycondensation
Body resin, phenol, m-cresol, p-cresol
・ Formaldehyde copolycondensate resin, phenol o-
Cresol / p-cresol / formaldehyde
A coalesced resin is mentioned. In addition, the novolac resin
Phenol, m-cresol, p-cresol, pho
Lumaldehyde resin is preferred. Also, pyrogallol
Acetone resin is also preferred. In the present invention, the above-mentioned novo
The rack resin may be used alone or in combination of two or more
You may use it. The molecular weight of the novolak resin (polystyrene)
As a standard), the weight average molecular weight Mw is 2.0 × 10
^Three~ 2.0 × 10^FourAnd the number average molecular weight Mn is 7.0 × 10
²~ 5.0 × 10^ThreeIs preferably a value within the range of
Further, preferably, Mw is 3.0 × 10.^Three~ 6.0 × 1
0^Three, Mn is 7.7 × 10²~ 1.2 × 10^ThreeIn the range of
Value. Measurement of molecular weight of novolak resin in the present invention
GPC (gel permeation chromatography)
-Method). The above novolac resin is used alone
It may be used in combination of two or more. Alkali-soluble such as hydroxyl group and carboxyl group
Examples of vinyl resins having a functional group include
Polymer comprising at least one structural unit of formula (A)-(F)
Is mentioned. [0011] [Chemical 1] In the general formulas (A) to (F), R
^AAnd R^BAre each a hydrogen atom, an alkyl group or a carbo
Represents a xyl group, preferably a hydrogen atom. R^CIs water
Represents an elementary atom, a halogen atom or an alkyl group, preferably
Is a hydrogen atom or an alkyl group such as a methyl group or an ethyl group
The R^D, R^EIs a hydrogen atom, an alkyl group, an aryl group or
Represents an aralkyl group, preferably a hydrogen atom. A¹
Links a nitrogen or oxygen atom to an aromatic carbon atom
M represents an optionally substituted alkylene group, m
Represents an integer of 0 to 10, and B¹Has a substituent
Good phenylene group or naphthylene which may have a substituent
Represents a group. The above phenolic hydroxyl acid used in the present invention
As a vinyl polymer having a group, a copolymer type structure is used.
And those having the general formulas (A) to (F) are preferred.
As monomers to be copolymerized with the structural units indicated by
For example, ethylene, propylene, isobutylene,
Ethylenically unsaturated olefins such as butadiene and isoprene
Such as styrene, α-methylstyrene, p-me
Styrenes such as chilled styrene and p-chlorostyrene, eg
For example, acrylic acids such as acrylic acid and methacrylic acid, examples
For example, itaconic acid, maleic acid, maleic anhydride, etc.
Saturated aliphatic dicarboxylic acids such as methacrylic acid
, Ethyl acrylate, acrylic acid-n-butyl, acrylic
Isobutyl acrylate, dodecyl acrylate, acrylic acid
2-chloroethyl, phenyl acrylate, α-chloroa
Methyl crylate, methyl methacrylate, methacrylate
Α-methylene aliphatic mono, such as chill and ethyl methacrylate
Esters of carboxylic acids, such as acrylonitrile,
Nitriles such as methacrylonitrile, such as acryl
Amides such as luamide, such as acrylic anilide, p
-Chloroacrylanilide, m-nitroacrylanilide
And anilides such as m-methoxyacrylanilide, eg
For example, vinyl acetate, vinyl propionate, vinyl benzoate
Vinyl esters such as nyl, vinyl acetate,
Ruvinyl ether, ethyl vinyl ether, isobutyl
Vinyl ether, β-chloroethyl vinyl ether, etc.
Vinyl ethers, vinyl chloride, vinylidene chloride
Vinylidene cyanide such as 1-methyl-1-me
Toxiethylene, 1,1-dimethoxyethylene, 1,2-di
Methoxyethylene, 1,1-dimethoxycarbonyl ethyl
And ethylene derivatives such as 1-methyl-1-nitroethylene
Such as N-vinylpyrrole, N-vinylcarbazol
, N-vinylindole, N-vinylpyrrolidene, N-
There are N-vinyl monomers such as vinyl pyrrolidone. this
These vinyl monomers have a structure in which the unsaturated double bond is cleaved.
It exists in a polymer compound. Of the above monomers, aliphatic monocarboxylic acids
The esters and nitriles are excellent for the purpose of the present invention.
The performance is preferable. These monomers are used in the present invention.
Either block or random in the polymer used
It may be combined in such a state. Alkali-soluble resin
0.02 to 0.02 in alkaline developer at the start of development
0.1% by mass, preferably 0.02 to 0.09% by mass
Have it. If the amount of alkali-soluble resin is too small,
There is no effect of preventing sludge
Causes sludge. [Surfactant] In the developer in the present invention,
Developability and dispersion of development residue and printing plate image area
Various surface activity as needed to improve the ink affinity
Agents and organic solvents can be added. As a preferred surfactant
Is anionic, cationic, nonionic and amphoteric
A surface active agent is mentioned. As a preferable example of the surfactant
Polyoxyethylene alkyl ethers, polyoxyethylene
Siethylene alkyl phenyl ethers, polyoxye
Tylene polystyryl phenyl ethers, polyoxye
Tylene polyoxypropylene alkyl ethers, grease
Serine fatty acid partial esters, sorbitan fatty acid partial esters
Stealth, pentaerythritol fatty acid partial ester
, Propylene glycol mono fatty acid esters, sho
Sugar fatty acid partial esters, polyoxyethylene sorbita
Fatty acid partial esters, polyoxyethylene sorbite
Fatty acid partial esters, polyethylene glycol fat
Fatty acid esters, polyglycerol fatty acid partial esters
, Polyoxyethylenated castor oil, polyoxyethylene
Lengglycerin fatty acid partial esters, fatty acid dietano
Uramides, N, N-bis-2-hydroxyalkyl
Amines, polyoxyethylene alkylamine, trie
Tanolamine fatty acid ester, trialkylamine ester
Nonionic surfactants such as xoxides, Fatty acid salts, abietic acid salts, hydroxy
Sialkane sulfonates, alkane sulfonates,
Dialkylsulfosuccinic acid ester salts, linear alkyl bases
Sulfonates, branched alkylbenzene sulfone
Phosphates, alkylnaphthalene sulfonates, alkyls
Ruphenoxy polyoxyethylene propyl sulfonate
Polyoxyethylene alkyl sulfophenyl ether
Salt, sodium N-methyl-N-oleyl taurate
Salt, N-alkylsulfosuccinic acid monoamide disodium salt
Salt, petroleum sulfonate, sulfated beef oil, fatty acid alkyl
Sulfates of alkyl esters, alkyl sulfates
Salts, polyoxyethylene alkyl ether sulfate ester
Salt, fatty acid monoglyceride sulfate, poly
Oxyethylene alkyl phenyl ether sulfate
Salts, polyoxyethylene styryl phenyl ether sulfate
Acid ester salts, alkyl phosphate ester salts, polio
Xylethylene alkyl ether phosphates
Reoxyethylene alkylphenyl ether phosphate
Tellurium salt, styrene / maleic anhydride copolymer partially saponified
And partial saponification of olefin / maleic anhydride copolymer
Compounds, naphthalenesulfonate formalin condensates, etc.
Which anionic surfactant, alkylamine salts, tetra
Quaternary ammonium salts such as butylammonium bromide
, Polyoxyethylene alkylamine salts, polyethylene
Cationic surfactants such as lenpolyamine derivatives,
Ruboxybetaines, aminocarboxylic acids, sulfobeta
Ins, aminosulfuric acid esters, imidazolines, etc.
Examples include amphoteric surfactants. Of the surfactants listed above
Among them, polyoxyethylene is polyoxymethyl
Len, polyoxypropylene, polyoxybutylene, etc.
Can also be read as polyoxyalkylene
These surfactants are also included. A more preferred surfactant is perfume in the molecule.
A fluorosurfactant containing a fluoroalkyl group
The Such fluorosurfactants include perfluoro
Alkyl carboxylates, perfluoroalkyl sulfones
Acids such as acid salts and perfluoroalkyl phosphates
ON type, amphoteric type such as perfluoroalkylbetaine,
Such as perfluoroalkyltrimethylammonium salt
Cationic and perfluoroalkylamine oxides
Perfluoroalkylethylene oxide adduct,
-Fluoroalkyl group and hydrophilic group-containing oligomer,
Perfluoroalkyl group and lipophilic group-containing oligomer
-Perfluoroalkyl group, hydrophilic group and lipophilic group
Containing oligomer, perfluoroalkyl group and lipophilicity
Nonionic types such as group-containing urethanes can be mentioned. above
Surfactants can be used alone or in combination of two or more.
0.001 to 10 mass in the developer
%, More preferably in the range of 0.01 to 5% by mass
It is. [Development Stabilizer] In the developer of the present invention,
Various development stabilizers can be added. It
As a preferred example thereof, JP-A-6-282079 is disclosed.
Polyethylene glycol adduct of the sugar alcohol described,
Tetrabutyl ammonium hydroxide, etc.
Rukylammonium salt, tetrabutylphosphonium bromide
Phosphonium salts such as mido and diphenyliodoni
Preferred examples include iodonium salts such as umchloride.
It is mentioned. Further, JP-A-50-51324
The anionic or amphoteric surfactants described, or
Water-soluble cationizers described in JP-A-55-95946
Kupolymer, described in JP-A-56-142528
There are water-soluble amphoteric polymer electrolytes. Further, JP
With alkylene glycol of JP 59-84241
Added organoboron compounds, JP-A-60-111246
Of polyoxyethylene and polyoxypropylene
Non-block polymerization type water-soluble surfactant, JP-A-60-1
No. 29750 polyoxyethylene polyoxyp
Alkylenediamine compounds substituted with lopyrene,
A weight average molecular weight of 300 described in JP-A-61-215554
The above polyethylene glycol, JP-A-63-1758
Fluorine-containing surface activity having a cationic group of No. 58
Agent, acid or alcohol disclosed in JP-A-2-39157
Water obtained by adding 4 mol or more of ethylene oxide to
Soluble ethylene oxide adduct and water-soluble polyalkyl
And the like, and the like. [Organic solvent] In addition, the developer may be further present if necessary.
Mechanical solvent is added. Such organic solvents include water.
A solubility of about 10% by mass or less is suitable.
Preferably, it is selected from those having 5% by mass or less. For example, 1
-Phenylethanol, 2-phenylethanol, 3-
Phenyl-1-propanol, 4-phenyl-1-buta
Nord, 4-phenyl-2-butanol, 2-phenyl
-1-butanol, 2-phenoxyethanol, 2-be
Nyloxyethanol, o-methoxybenzyl alcohol
, M-methoxybenzyl alcohol, p-methoxy
Benzyl alcohol, benzyl alcohol, cyclohex
Sanol, 2-methylcyclohexanol, 3-methyl
Cyclohexanol and 4-methylcyclohexano
, N-phenylethanolamine and N-phenyl
Examples include diethanolamine. Organic
The content of the agent is 0.1 to 5% by mass relative to the total weight of the liquid used
It is. The amount used is closely related to the amount of surfactant used.
As the amount of organic solvent increases, the amount of surfactant increases
It is preferable to increase. This is a small amount of surfactant
If a large amount of organic solvent is used, the organic solvent is completely dissolved.
Therefore, it can not be expected to ensure good developability.
This is because that. [Reducing agent] Development used in the present invention
A reducing agent can be further added to the liquid. This is a print version
To prevent soiling, especially photosensitive diazonium
When developing negative photosensitive lithographic printing plates containing salt compounds
It is valid. Preferred organic reducing agents include thiosalicy
Phosphoric acid, hydroquinone, metol, methoxyquinone,
Phenol compounds such as zolcine and 2-methylresorcin
Products such as phenylenediamine and phenylhydrazine
Min compound. Further preferred inorganic reducing agents and
Sulfurous acid, bisulfite, phosphorous acid, phosphorous acid water
Acid, phosphorous acid dihydrogen, thiosulfuric acid and dithionite
Sodium salt, potassium salt, ammonium salt of inorganic acid such as
And salt. Of these reducing agents
The sulfite is particularly excellent in the antifouling effect. This
These reducing agents are preferably used in the developer at the time of use.
It is contained in the range of 0.05 to 5% by mass. [Organic carboxylic acid] Developer in the present invention
In addition, an organic carboxylic acid can be added. Like
Organic carboxylic acids are aliphatic carbos having 6 to 20 carbon atoms.
Acids and aromatic carboxylic acids. Aliphatic carboxylic acid
Specific examples of caproic acid, enanthylic acid,
Prillic acid, lauric acid, myristic acid, palmitic acid
And stearic acid, with carbon number being particularly preferred
8-12 alkanoic acids. Also double bond in carbon chain
Unsaturated fatty acids having a branched carbon chain
But you can. Aromatic carboxylic acids include benzene rings and naphth
A carboxyl group is substituted on the thalene ring, anthracene ring, etc.
Specifically, o-chlorobenzoic acid, p
-Chlorobenzoic acid, o-hydroxybenzoic acid, p-hydride
Loxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid
Perfic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydride
Loxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,
3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid
Perfic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3
-Hydroxy-2-naphthoic acid, 2-hydroxy-1-
Naphthoic acid, 1-naphthoic acid, 2-naphthoic acid, etc.
However, hydroxynaphthoic acid is particularly effective. Above fat
Aromatic and aromatic carboxylic acids are
Used as a lithium, potassium or ammonium salt
It is preferable. Organic carvone of developer used in the present invention
The acid content is not particularly limited, but is lower than 0.1% by mass.
The effect is not sufficient, and at 10% by mass or more
Not only can the improvement of the above effect be improved, but also another additive is used in combination.
May interfere with dissolution. Therefore, a preferred accessory
The added amount is 0.1 to 10% by mass with respect to the developer at the time of use.
More preferably, it is 0.5-4 mass%. [Others] The developer in the present invention further includes
If necessary, preservatives, colorants, thickeners, antifoaming agents and
And a hard water softener. Soft water softening
Examples of the agent include polyphosphoric acid and its sodium salt,
Potassium and ammonium salts, ethylenediamine
Traacetic acid, diethylenetriaminepentaacetic acid, triethyl
Lentetamine hexaacetic acid, hydroxyethylethylene
Diamine triacetic acid, nitrilotriacetic acid, 1,2-diamy
Nocyclohexanetetraacetic acid and 1,3-diamino-
Aminopolycarboxylic such as 2-propanoltetraacetic acid
Acids and their sodium, potassium and anions
Monium salt, aminotri (methylenephosphonic acid), ethyl
Range amine tetra (methylene phosphonic acid), diethyl
Triaminepenta (methylenephosphonic acid), triethyl
Lentetamine hexa (methylene phosphonic acid), hydro
Xylethylethylenediaminetri (methylenephosphone
Acid) and 1-hydroxyethane-1,1-diphosphone
Acids and their sodium, potassium and ammoni salts
Um salts can be mentioned. Such a water softener has a chelating power.
And the optimum value depending on the hardness and amount of hard water used
However, if you show the general amount of use, development during use
0.01-5 mass% in a liquid, More preferably, 0.01-0.
It is in the range of 5% by mass. In addition amounts less than this range
The intended purpose is not fully achieved, and the amount added is within this range.
If there are many, there will be an adverse effect on the image area such as color loss.
The The remaining component of the developer is water. Used in the present invention
The developer used is less water than it is used.
So that it is diluted with water before use.
It is advantageous for transportation. In this case, the concentration is
It is appropriate that the minute does not cause separation or precipitation. (PS plate) Processed by the processing method of the present invention.
The PS plate is a positive that forms an image with an infrared laser.
A lithographic printing plate having a heat-sensitive layer of a mold or a negative type. First, to a lithographic printing plate having a positive type heat-sensitive layer
explain about. Positive type to which the treatment method of the present invention can be applied
A lithographic printing plate with a heat sensitive layer contains infrared absorbing dyes, etc.
If the planographic printing plate has a heat-sensitive layer
However, the following is a typical configuration.
explain. A lithographic printing plate having a positive thermosensitive layer
It has an image-forming layer that is a heat-sensitive layer on top, and if necessary
The image forming layer has (A) infrared absorption.
A dye, and (B) an alkali-soluble polymer compound
Optionally (C) a phase with an alkali-soluble polymer compound
Alkaline water-soluble of the alkali-soluble polymer compound
Reduces solubility in liquid and dissolves by heating
Compounds with reduced activity lowering properties, (D) cyclic acid anhydrides, etc.
It may contain. Below is a brief description of each component
explain. -(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, 582-22014, 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 (G).
Can be mentioned. [0030] [Chemical 2]In the general formula (G), 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, m> 2.
If more than one R³²Are bonded 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. In general formula (G), X^-Represents anions
For example, perchloric acid, tetrafluoroboric acid, phosphorus hexafluoride
Acid, triisopropylnaphthalenesulfonic acid, 5-nitrate
B-O-toluenesulfonic acid, 5-sulfosalicylic acid,
2,5-dimethylbenzenesulfonic acid, 2,4,6-to
Limethylbenzenesulfonic acid, 2-nitrobenzenesulfur
Phosphonic acid, 3-chlorobenzenesulfonic acid, 3-bromobe
Nzen sulfonic acid, 2-fluorocapryl naphthalene
Sulfonic acid, dodecylbenzenesulfonic acid, 1-naphtho
5-Sulphonic acid, 2-methoxy-4-hydroxy-
5-Benzoyl-benzenesulfonic acid and paratoluene
A sulfonic acid etc. are mentioned. Among them, hexafluorophosphoric acid,
Triisopropylnaphthalenesulfonic acid, 2,5-dimethyl
Alkyl aromatic sulfonic acids such as tilbenzene sulfonic acid
Is preferred. Among the compounds represented by the general formula (G),
However, specifically, the following compounds are preferably used.
However, the present invention is not limited to these.
Yes. [Chemical 3]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. [0044] [Formula 4] In the general formulas (a) to (e), X¹, X²The
Each independently an oxygen atom or NR⁷Represents. R¹, R^FourIs
Each independently a hydrogen atom or CH_ThreeRepresents. R², R^Five,
R⁹, R¹², R¹⁶Each independently has a substituent.
An alkylene group having 1 to 12 carbon atoms, cycloalkyl
Rene group, arylene group or aralkylene group is represented.
R^Three, R⁷, R¹³Each independently represents a hydrogen atom or a substituent.
An optionally substituted alkyl group having 1 to 12 carbon atoms, cyclo
Represents an alkyl group, an aryl group or an aralkyl group; Ma
R⁶, R¹⁷Each independently has a substituent.
C1-C12 alkyl group, cycloalkyl
Represents a group, an aryl group, or an aralkyl group. R⁸, R^{1 0}, R
¹⁴Are each independently a hydrogen atom or CH_ThreeRepresents.
R¹¹, R¹⁵Each independently has a single bond or a substituent.
An optionally substituted alkylene group having 1 to 12 carbon atoms, cycloa
Represents a ruxylene group, an arylene group or an aralkylene group;
Y¹, Y²Each independently represents a single 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. 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. [0048] [Chemical formula 5] 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 is
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, the monomers listed in the following (a) to (l)
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
Ketone, propyl vinyl ketone, phenyl vinyl ketone
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 preferred, 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 number average molecular weight is 500 to 20000
Is preferably 200 to 10,000. Including 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 further used for the image forming layer,
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
The compound represented by Formula (H) or (I) is mentioned. [0062] [Chemical 6] In the general formula (H), 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 (I), 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. -Other components- Various additions may be added to the image forming layer as necessary.
An agent can be added. For example, improve sensitivity
For purposes, cyclic acid anhydrides, phenols, organic acids,
Known additives such as sulfonyl compounds can be used in combination.
Yes. Examples of the cyclic acid anhydride include US Pat. No. 4,11.
Tetrahydroanhydrophthalic acid as described in US Pat. No. 5,128
Acid, hexahydrophthalic anhydride, 3,6-endooxy
-Δ^Four-Tetrahydrophthalic anhydride, α-phenyl anhydride
Maleic acid, succinic anhydride, promellitic anhydride, etc.
Can be mentioned. As phenols, bisphenol
A, p-nitrophenol, p-ethoxyphenol,
2,4,4'-trihydroxybenzophenone, 2,
3,4-trihydroxybenzophenone, 4-hydroxy
Cibenzophenone, 4,4 ', 4 "-trihydroxyto
Riphenylmethane, 4,4 ', 3 ", 4" -tetrahydr
Roxy-3,5,3 ', 5'-tetramethyltripheny
For example, rumethane. 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. In addition, the stability of processability with respect to development conditions
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. Further, 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), US 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%. A planographic printing plate tool having the positive heat-sensitive layer.
An example is disclosed in Japanese Patent Application No. 2000-378507.
The image forming layer is a two-layer positive heat-sensitive layer.
An example is a printing plate precursor. In other words, this positive thermal layer
It has a layer structure and is provided at a position close to the surface (exposed surface).
Heat sensitive layer and alkali provided on the side close to the support
And a lower layer containing a soluble polymer compound.
It is a sign. The heat-sensitive layer and the lower layer, or one of the above,
(A) Infrared absorbing dye, (B) alkali-soluble polymer
Compound (C) Alkali-soluble polymer compound
Dissolution of the alkali-soluble polymer compound in an aqueous alkali solution
Reduces solubility and reduces solubility by heating
Contain compounds that reduce usage, and other ingredients
it can. Alkali-soluble polymer used for lower layer
As a compound, acrylic resin is an organic material with a buffering action.
For alkaline developer containing compound and base as main components
Since the solubility of the lower layer can be maintained well, the image shape during development
It is preferable from the viewpoint of composition. Furthermore, as this acrylic resin
Those having a sulfoamide group are particularly preferred. Also feeling
As an alkali-soluble polymer compound used in the thermal layer
Causes strong hydrogen bonding in the unexposed areas and
Because some hydrogen bonds are easily released
A resin having a phenolic hydroxyl group is desirable. More preferred
Or a novolac resin. Infrared absorbing dye is heat sensitive
It can be added not only to the layer but also to the lower layer. In the lower layer
By adding an infrared absorbing dye, the lower layer can be used as a heat-sensitive layer.
Can be made to function. Add infrared absorbing dye to the lower layer
The same thing as in the upper thermal layer.
You may use and a different thing may be used. Other
Additives may be included only in the lower layer, or only in the heat sensitive layer
You may make it contain, and you may make it contain in both layers further. Image forming layer of the lithographic 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 having the positive thermosensitive layer
Is a dimensionally stable plate with the required strength and durability
For example, paper, plastic (for example, poly
Ethylene, polypropylene, polystyrene, etc.)
Paper, metal plates (eg, aluminum,
Lead, copper, etc.), plastic film (eg, diacetic acid
Roulose, cellulose triacetate, cellulose propionate
, Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate
, Polyethylene terephthalate, polyethylene, polyethylene
Restyrene, polypropylene, polycarbonate, poly
Vinyl acetal, etc.) and the above metals are laminates
Or vapor-deposited paper or plastic fill
Etc. are included. As the support, polyester fiber
Rum or aluminum plate is preferred, among which
Aluminum plates that have good qualities and are relatively inexpensive are particularly preferred.
Good. Suitable aluminum plates include pure aluminum plates and
Alloys mainly containing aluminum and trace amounts of foreign elements
It is a plate, and aluminum is laminated or evaporated.
It may be a plastic film. Aluminum alloy
Foreign elements contained in gold include silicon, iron, manganese, copper,
Magnesium, chromium, zinc, bismuth, nickel, titanium
There are tongues. The content of foreign elements in the alloy is at most 10 quality
% Or less. Particularly suitable aluminum is pure aluminum
Nitrogen, but completely pure aluminum is scouring technology
Containing slightly different elements because it is difficult to manufacture
But you can. Thus, the composition of the aluminum plate is specified
Aluminum that has been publicly known and publicly used
A nickel plate can be used as appropriate. aluminum
The thickness of the plate is about 0.1 mm to 0.6 mm, preferably
0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.
3 mm. Prior to roughening the aluminum plate,
If desired, for example, the surface activity to remove surface rolling oil
Degreasing treatment with an organic agent, organic solvent or alkaline aqueous solution
Is done. The roughening treatment of the surface of the aluminum plate
This can be done in various ways, for example mechanically roughening
A method for electrochemically dissolving and roughening a surface; and
It is carried out by a method of selectively dissolving the surface chemically.
Mechanical methods include ball polishing, brush polishing,
Use known methods such as last polishing and buffing.
You can. As an electrochemical roughening method, hydrochloric acid is used.
Alternatively, there is a method that uses alternating current or direct current in a nitric acid electrolyte.
The Also disclosed in Japanese Patent Laid-Open No. 54-63902
You can also use a combination of both
Yes. In the present invention, the support is made of hydrochloric acid electrolytic coarse.
It is preferable to perform surface treatment. Hydrochloric acid electrolytic roughening treatment
Is an electrochemical roughening treatment in an aqueous solution mainly composed of hydrochloric acid.
Means alternating current, high frequency exchange in aqueous hydrochloric acid
There is a method of performing electrolysis by current, triangular wave alternating current or direct current.
Generally, an aluminum plate in an aqueous solution containing hydrochloric acid
Electrochemically roughened by applying alternating current to the electrode facing
Process. The concentration of the hydrochloric acid compound is 1.0 g / liter
To the saturation limit, preferably 5 to
The range is 100 g / liter, and more preferably 5 to 5 g.
The range is 20 g / liter. Preferred compounds are salts
Aluminum chloride, hydrochloric acid, sodium chloride, ammonium chloride
Contains hydrochloric acid ions consisting of um or magnesium chloride
These are used alone or in combination. Ma
It may be combined with other hydrochloric acid ions. further
20-150 g / lit of aluminum salt in hydrochloric acid electrolyte
It is preferable to mix them in the amount of water. If necessary,
Add sulfuric acid, phosphoric acid, boric acid, ammonium salt, etc.
There is no problem. The temperature of electrolytes mainly composed of hydrochloric acid is usually
It is 10-60 degreeC, Preferably it is the range of 30-55 degreeC. In an aqueous solution mainly composed of hydrochloric acid, electrochemical
As an alternating current waveform used for roughening the surface, Japanese Patent Publication No. 48-
A sine wave as described in Japanese Patent No. 28123,
Sine wave alternating current as described in Japanese Patent No. -25381
Which is phase controlled by a star, Japanese Patent Laid-Open No. 52-58602
There is a special waveform etc.
In particular, it is preferable to use a rectangular wave alternating current with a duty ratio of 1: 1.
That's right. In addition to AC, JP-A-51-42605,
Using direct current as described in Kaihei 1-141094
You can also. AC voltage is used in an aqueous solution mainly composed of hydrochloric acid.
In the electrochemical surface roughening treatment,
Degree is 10-200A / dm²Is preferable, and the amount of electricity is
1-1000C / dm²Is preferably in the range of 10 to 800
C / dm²The range of is more preferable. The frequency is 50Hz or more
Is preferable, and the range of 60 to 500 Hz is more preferable.
In the above hydrochloric acid electrolytic surface roughening treatment, other surface roughening treatment, for example,
You may combine the method of roughening mechanically. The aluminum plate roughened in this way
If necessary, alkali etching treatment and neutralization treatment
After being made, the water retention and wear resistance of the surface are increased as desired.
Therefore, an anodizing process is performed. Aluminum plate yang
The electrolyte used for the extreme oxidation treatment is porous oxide skin
A variety of electrolytes can be used to form the membrane,
Acid, phosphoric acid, succinic acid, chromic acid or their mixed acids are used
I can. Among them, anodizing with sulfuric acid is mentioned.
The The concentration of those electrolytes depends on the type of electrolyte.
It is decided. The conditions for anodizing depend on the electrolyte used.
Since it varies, it cannot be specified unconditionally.
The solution has a concentration of 1 to 80% by mass, the liquid temperature is 5 to 70 ° C,
Flow density 5-60A / dm², Voltage 1-100V, electrolysis time 1
A range of 0 second to 5 minutes is appropriate. Of anodized film
The amount is 1.0g / m²If it is less, the printing durability is insufficient.
Or the non-image area of the lithographic printing plate is easily scratched,
So-called “scratch stain” in which ink adheres to the scratched part during printing
Is likely to occur. After anodizing, aluminum
The surface of the um is subjected to a hydrophilic treatment if necessary. Hydrophilization treatment
In theory, US Pat. No. 2,714,066,
3,181,461, 3,280,734 and
Arcas as disclosed in 3,902,734
Remetal silicate (for example, sodium silicate aqueous solution) method
There is. In this method, the support is sodium silicate.
Dipping in an aqueous solution or electrolytic treatment. other
Fluorination disclosed in Japanese Patent Publication No. 36-22063
Potassium zirconate and US Pat. No. 3,276,868
No. 4,153,461 No. 4,689,27
Treated with polyvinylphosphonic acid as disclosed in No. 2
Or the like. A lithographic printing plate having a positive thermosensitive layer is supported.
It is provided by laminating an image forming layer on the body, but it is necessary
Accordingly, an undercoat layer can be provided on the support. under
Examples of components used in the coating layer include various organic compounds.
For example, carboxymethylcellulose, dextri
, Gum arabic, 2-aminoethylphosphonic acid, etc.
Phosphonic acids having an amino group;
Good phenylphosphonic acid, naphthylphosphonic acid, alkyl
Ruphosphonic acid, glycerophosphonic acid, methylene diphospho
Organic phosphonic acids such as acid and ethylene diphosphonic acid;
Optionally substituted phenylphosphoric acid, naphthylyl
Organic acids such as acid, alkyl phosphate and glycerophosphate
Acid; phenylphosphine optionally having substituent (s)
Acids, naphthylphosphinic acids, alkylphosphinic acids and
Organic phosphinic acids such as glycerophosphinic acid;
And amino acids such as β-alanine;
Salts of amines with hydroxyl groups, such as hydrochloride of min
Examples include acid salts. The organic compound is one kind alone
You may use, and 2 or more types may be mixed and used for it. Ma
It is also preferable to undercoat the diazonium salt described above.
It is a mode. The undercoat layer has the following general formula:
(J) of an organic polymer compound having a structural unit represented by
An organic undercoat layer containing at least one kind is also preferred. [0094] [Chemical 7] In the general formula (J), R⁵¹Is a hydrogen atom, halogene
R atom or an alkyl group, R⁵²And R⁵³Is that
Independently hydrogen atom, hydroxyl group, halogen atom, alkyl
Group, substituted alkyl group, aryl group, substituted aryl group,-
OR⁵⁴, -COOR⁵⁵, -CONHR⁵⁶, -COR⁵⁷or
Represents -CN and R⁵²And R⁵³Are linked to each other
A structure may be formed. Where R⁵⁴~ R⁵⁷Each
Independently represents an alkyl group or an aryl group. X is hydrogen source
Child, metal atom, -NR⁵⁸R⁵⁹R⁶⁰R⁶¹Represents. Where R
⁵⁸~ R⁶¹Each independently represents a hydrogen atom, an alkyl group, or a substituent
Represents an alkyl group, an aryl group or a substituted aryl group, and R
⁵⁸And R⁵⁹May be bonded to each other to form a ring structure.
m represents an integer of 1 to 3. As dry coating amount of undercoat layer
2 to 200 mg / m²5-100 mg /
m²Is more preferable. The dry coating amount is 2 mg / m²Less than
If it is, sufficient film properties may not be obtained. Meanwhile 20
0 mg / m²Even if it is applied beyond
I can't. The undercoat layer is provided by the following method.
Can do. That is, water or methanol, ethanol, methyl
Organic solvents such as ruethyl ketone or mixed solutions
A solution for the undercoat layer in which the organic compound is dissolved in the agent.
Method of coating and drying on a support such as a minium plate
And water or methanol, ethanol, ethyl ethyl keto
The organic solvent such as
An aluminum plate is added to the undercoat layer solution in which the compound is dissolved.
So that the organic compound is adsorbed,
This is a method of cleaning and drying with post-water or the like. In the former method, 0.000 of the organic compound is used.
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. The lithographic printing plate having the positive heat-sensitive layer is red.
Can be recorded with an external laser. Infrared ray
The laser emits infrared light with a wavelength of 700-1200 nm
Laser is preferred and emits infrared light in the same wavelength range
A solid laser or a semiconductor laser is more preferable. Next, a negative to which the processing method of the present invention is applied.
A lithographic printing plate having a mold type thermosensitive layer will be described. The present invention
The method of
Ga type lithographic printing plate precursor, that is, infrared laser irradiation part is cured
Planographic printing with a negative heat-sensitive layer that forms the image area
Any version can be applied.
The As one of such negative heat-sensitive layers, a photopolymerization layer is used.
Can be mentioned. In the photopolymerization layer, (A) an infrared absorber and
(B) generated with a radical generator (radical polymerization initiator)
(C)
A dical polymerizable compound, preferably (D)
Contains a polymer. Red absorbed by infrared absorber
The outside wire is converted into heat, and the heat generated at this time makes onium
Radical polymerization initiators such as salts decompose and generate radicals
The The radical polymerizable compound contains at least one ethylene.
With an unsaturated double bond and a terminal ethylenically unsaturated bond
A compound having at least one, preferably two or more
The polymerization reaction is chained by the generated radicals.
It occurs and hardens. In addition, as another embodiment of the negative type heat-sensitive layer,
An acid cross-linking layer may be mentioned. (E) Light or heat
A compound that generates an acid by the following (hereinafter referred to as an acid generator)
And (F) a compound that crosslinks with the generated acid (hereinafter referred to as a bridge).
Called a bridging agent), and further containing these
Can react with crosslinker in the presence of acid to form layer
(G) An alkali-soluble polymer is included. In this acid cross-linked layer
In this case, the acid generator is decomposed by light irradiation or heating.
The generated acid promotes the function of the cross-linking agent, and there are cross-linking agents
Or a strong cross-linking structure between the cross-linking agent and the binder polymer.
Structure is formed, which reduces alkali solubility
And becomes insoluble in the developer. At this time, the infrared laser energy
In order to use energy efficiently, (A)
An infrared absorber is blended. Used for the heat-sensitive layer of negative-type planographic printing plate precursors
Each compound is described below. [(A) Infrared Absorber] The infrared absorber is the absorbed infrared.
It has the function of converting the wire into heat. Heat generated at this time
Causes radical generators and acid generators to decompose and radicals
And acid. Infrared absorption used in the present invention
The agent has an absorption maximum from 760 nm to 1200 nm.
Dye or pigment. Examples of the dye include commercially available dyes such as “dye”.
"Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1968)
Known materials described in the literature can be used. concrete
For example, paragraph number of JP-A-10-39509
Names described in issue [0050] to [0051]
You can. Especially preferred among these dyes
Cyanine dye, squarylium dye, pyrylium
Examples thereof include salts and nickel thiolate complexes. In addition,
Anine dyes are preferable, and are represented by the following general formula (K).
Most preferred are cyanine dyes. [0103] [Chemical 8] In general formula (K), X¹Is a halogen atom,
Or X²-L¹Indicates. Where X²Is an oxygen atom or
Represents a sulfur atom and L¹Is charcoal having 1 to 12 carbon atoms
A hydrogen fluoride group is shown. R¹And R²Each independently
A hydrocarbon group having 1 to 12 atoms is shown. Of heat-sensitive layer coating liquid
From storage stability, R¹And R²Is more than 2 carbon atoms
Is preferably a hydrocarbon group, and R¹And R²
Are bonded to each other to form a 5-membered or 6-membered ring
It is particularly preferred. Ar¹, Ar²Are the same
May be different and may have a substituent.
Represents a hydrocarbon group. Y¹, Y²Are the same but different
May be sulfur atoms or 12 or more carbon atoms
The lower dialkylmethylene group is shown. R ^Three, R^FourIs that
These may be the same or different and may have a substituent.
A good hydrocarbon group having 20 or less carbon atoms is shown. Like
As a substituent, alkoxy having 12 or less carbon atoms
Group, carboxyl group, and sulfo group. R^Five,
R⁶, R⁷And R⁸Are the same but different
Good, hydrocarbons with hydrogen atoms or carbon atoms of 12 or less
Indicates the basis. From the availability of raw materials, preferably with hydrogen atoms
is there. Z^1-Represents a counter anion. However, R¹
~ R⁸When any of the sulfo groups is substituted,
Z^1-Is not necessary. Preferred Z^1-Store the thermal layer coating solution
From stability, halogen ion, perchlorate ion, tetra
Fluoroborate ion, hexafluorophosphate
Ions and sulfonate ions, particularly preferred
Perchlorate ion, hexafluorophosphate
On and aryl sulfonate ions. In the present invention, it can be suitably used.
Specific examples of cyanine dyes represented by the general formula (K)
Is the paragraph number [0 of Japanese Patent Application No. 11-310623.
017] to [0019]
Can do. As the pigment used in the present invention,
Commercial pigment and color index (CI) handbook,
"Latest pigment handbook" (edited by the Japan Pigment Technology Association, 1977)
Published), "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Published), "Printing Ink Technology" CMC Publishing, published in 1984)
Can be used. As the types of pigments, black pigment, yellow face
, Orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Examples include polymer-bound dyes. Details of these pigments
Is the paragraph number [005] of JP-A-10-39509.
2] to [0054], which are described in detail.
The present invention can also be applied. Of these pigments
Preferred is carbon black. In the negative type heat-sensitive layer, the above-mentioned dyes or
The pigment content is based on the total solid weight of the heat sensitive layer.
0.01-50 mass% is preferable, 0.1-10 mass%
Is more preferable, and in the case of a dye, 0.5 to 10
% By weight is most preferred, and in the case of pigments, 1.0 to 10
Mass% is most preferred. The content is 0.01% by mass
If it is less than 50% by mass, the sensitivity may be lowered.
If it exceeds, the non-image area of the original for lithographic printing will be stained.
This may occur. [(B) Compound generating radical]
Radicals in negative-type heat-sensitive layers for use in light
Examples of compounds that generate onium salts include onium salts,
Physically, iodonium salts, diazonium salts, sulfoni
Umm salt. These onium salts are used as acid generators.
Although it also has a function, it is used in combination with the radical polymerizable compound described later
In doing so, it functions as an initiator for radical polymerization. Book
The onium salt suitably used in the invention is the following general
It is an onium salt represented by the formulas (L) to (N). [0110] [Chemical 9] In the formula (L), Ar¹¹And Ar¹²Respectively
Independently, the number of carbon atoms which may have a substituent is 20 or less.
The lower aryl group is shown. This aryl group has a substituent
Preferred substituents in the case of halogen atom, nitro
B group, alkyl group having 12 or less carbon atoms, carbon atom number
12 or less alkoxy groups or 12 or less carbon atoms
The following aryloxy groups are mentioned. Z^11-Is halogen
Ion, perchlorate ion, tetrafluoroborate ion
, Hexafluorophosphate ion, and sulfone
Represents a counter ion selected from the group consisting of acid ions,
Preferably, perchlorate ion, hexafluorophosphine
Acid ions and aryl sulfonate ions
The In the formula (M), Ar^{twenty one}Has a substituent
And an aryl group having 20 or less carbon atoms. Good
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group having 12 or less atoms, 12 or less carbon atoms
An alkoxy group having 12 or less carbon atoms
Si group, alkylamino group having 12 or less carbon atoms, carbon
Dialkylamino group having 12 or less atoms, 1 carbon atom
2 or less arylamino groups or 12 carbon atoms
The following diarylamino groups are mentioned. Z^{twenty one -}Is Z^11-
Represents a counter ion having the same meaning as. In the formula (N), R³¹, R³²And R³³It
Each may be the same or different and have a substituent.
And a good hydrocarbon group having 20 or less carbon atoms. Like
New substituents include halogen atoms, nitro groups, and carbon atoms.
Alkyl group with 12 or fewer children, 12 or fewer carbon atoms
An alkoxy group or an aryl having 12 or less carbon atoms
An oxy group is mentioned. Z^31-Is Z^11-Counter ion synonymous with
Represents. In the present invention, it can be suitably used.
Specific examples of the onium salt include Japanese Patent Application No. 11-3106.
In paragraph numbers [0030] to [0033] of No. 23 specification
What has been described can be mentioned. The onium salt used in the present invention is:
The maximum absorption wavelength is preferably 400 nm or less,
Furthermore, it is preferable that it is 360 nm or less. like this
By making the absorption wavelength in the ultraviolet region, lithographic printing plate
The original can be handled under white light. These onium salts are used in the entire heat-sensitive layer coating solution.
0.1 to 50% by mass, preferably 0.5 to the solid content
30% by weight, particularly preferably 1-20% by weight
It can be added to the hot layer coating solution. Addition amount is 0.1
If it is less than mass%, the sensitivity will be low, and 50 mass% will be reduced.
If it exceeds, smearing occurs in the non-image area during printing. These
Only one type of nium salt may be used, or two or more types may be used together.
May be used. In addition, these onium salts
It can be added to the same layer, or another layer can be added
May be. [(C) Radical polymerizable compound] Radical
The polymerizable compound has at least one ethylenically unsaturated diisotropy.
A radically polymerizable compound having a heavy bond,
At least one, preferably two or more lentic unsaturated bonds
Selected from the above compounds. Such a group of compounds
It is widely known in the industrial field, and
These can be used without any particular limitation. these
Are for example monomers, prepolymers, ie dimers,
Trimers and oligomers, or mixtures thereof
They have chemical forms such as their copolymers. monomer
And examples of copolymers thereof include unsaturated carboxylic acids
(For example, acrylic acid, methacrylic acid, itaconic acid,
Rotonic acid, isocrotonic acid, maleic acid, etc.)
Examples include esters and amides, preferably unsaturated
Este of carboxylic acid and aliphatic polyhydric alcohol compound
Of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound
Midos are used. In addition, hydroxyl group, amino
Group, mercapto group and other nucleophilic substituents
Bonic acid esters, amides and monofunctional or polyfunctional isoforms
Addition reaction with cyanates, epoxies, monofunctional
Also preferred are dehydration condensation products with polyfunctional carboxylic acids.
Used for. Also, isocyanate groups, epoxy groups, etc.
Unsaturated carboxylic acid esters with various electrophilic substituents
Or amides and monofunctional or polyfunctional alcohols
, Addition reaction with amines and thiols,
Have a detachable substituent such as a halogen group or a tosyloxy group.
Unsaturated carboxylic acid esters or amides
Functional or polyfunctional alcohols, amines and thios
Also suitable are substitution products with diols. Another example
Instead of the above unsaturated carboxylic acid
It is also possible to use compounds that have been replaced with acid, styrene, etc.
Is possible. Aliphatic polyhydric alcohol compounds and unsaturated cal
It is a radical polymerizable compound that is an ester with boronic acid.
Acrylic acid ester, methacrylic acid ester, itacone
Acid ester, crotonic acid ester, isocrotonic acid ester
Specific examples of tellurium and maleate esters are described in Japanese Patent Application No. 11-3.
Paragraph numbers [0037] to [004] of the 10623 specification
2], and these also apply to the present invention.
You can. Examples of other esters include, for example, special
Kosho 46-27926, JP-B 51-47334, JP
Aliphatic alcohols described in JP-A-57-196231
Type esters, JP-A-59-5240, JP-A-59-
5241, aroma described in JP-A-2-226149
Having a family skeleton, JP-A-1-165613
Those containing the amino groups described are also preferably used. In addition, an aliphatic polyvalent amine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylic
Amide, 1,6-hexamethylenebis-acrylamid
1,6-hexamethylenebis-methacrylamide,
Diethylenetriaminetrisacrylamide, Xylile
Bisacrylamide, Xylylenebismethacrylami
There are Examples of other preferred amide monomers
The cyclohexylene described in JP-B-54-21726
The one with the structure can be given. Further, addition reaction of isocyanate and hydroxyl group
Also suitable for urethane-based addition-polymerizable compounds produced using
As a specific example, for example, Japanese Patent Publication No. 4
2 per molecule described in Japanese Patent No. 8-41708
Polyisocyanate having isocyanate groups above
Vinyl compound containing a hydroxyl group represented by the following formula
2 or more polymerizable vinyl groups in one molecule to which a mer is added
And vinyl urethane compounds containing. CH₂= C (R) COOCH₂CH (R ′) OH (Where R and R ′ are H or CH_ThreeIndicates. ) Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent
No. 2-332293 and Japanese Patent Publication No. 2-16765
Urethane acrylates such as those listed,
58-49860, Shoko 56-17654, Shoko
Sho-62-39417 and JP-B-62-39418
Urethanes with ethylene oxide-based skeletons
Compounds are also suitable. Further, JP-A 63-277653, JP
Japanese Utility Model Laid-Open No. 63-260909, Japanese Patent Application Laid-Open No. 1-105238
Amino structures and sulfides in the molecule described in each publication
Radical polymerizable compounds having a structure may be used. Regarding these radically polymerizable compounds,
What kind of structure is used, used alone or in combination
The details of how to use, such as how much is added,
Can be set arbitrarily according to the performance design of typical recording materials.
The For example, it is selected from the following viewpoints. Sensitivity point
In this case, a structure with a high content of unsaturated groups per molecule is preferred.
In many cases, 2 or more functionalities are preferable. Also images
In order to increase the strength of the part, that is, the cured film, trifunctional or higher
The above ones are good, and different functionalities and different polymerizability
A compound having a group (for example, an acrylic ester compound)
, Methacrylate compounds, styrene compounds
Etc.) are used in combination to achieve both photosensitivity and strength
It is also effective to adjust this. From these points of view,
In many cases, the preferred blending ratio of the cal-polymerizable compound is a combination.
5-80% by weight, preferably 20-
75% by mass. Moreover, even if these are used independently, they are 2 types.
You may use together. In addition, radically polymerizable compounds
Is used for the degree of polymerization inhibition to oxygen, resolution,
Appropriate structure from the standpoints of breathability, refractive index change, surface tackiness, etc.
The structure, blending and addition amount can be arbitrarily selected. [(D) Binder polymer] In the present invention,
In addition, the negative heat-sensitive layer uses a binder polymer.
Use. Linear organic polymer as binder polymer
Is preferably used. Such a "linear organic polymer
Any of “-” may be used. Preferably
In order to enable water development or weak alkaline water development,
Linear that is soluble or swellable in water or weak alkaline water
An organic polymer is selected. Linear organic polymers are heat sensitive
Not only as a film-forming agent for forming layers, but also water,
Suitable for use as weak alkaline water or organic solvent developer
Selected and used. For example, water soluble organic polymer
When used, water development becomes possible. Such linear organic poly
As a mer, radical weight having a carboxylic acid group in the side chain is used.
Combined, for example, JP-A 59-44615, JP-B 54-
No. 34327, No. 58-12777, No. 54
25957, JP 54-92723, JP 5
Described in JP-A-9-53836 and JP-A-59-71048.
That is, methacrylic acid copolymer,
Rylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer
Polymer, maleic acid copolymer, partially esterified maleic acid
There are copolymers and the like. Similarly, the side chain has a carboxylic acid group.
There are acidic cellulose derivatives. In addition, it has a hydroxyl group
Useful are polymers with cyclic acid anhydride added to the polymer
It is. Of these, in particular, benzyl groups or ants
(Meth) acrylic having a carboxyl group and a carboxyl group in the side chain
Resin has an excellent balance of film strength, sensitivity, and developability.
It is preferable. Also, Japanese Patent Publication No.7-12004 and Japanese Patent Publication No.7
-120041, JP 7-120042, JP
8-12424, JP 63-287944, JP
Sho 63-287947, JP-A 1-271744,
Acid groups described in Japanese Patent Application No. 10-116232
The urethane-based binder polymer containing
Excellent strength, advantageous in terms of printing durability and low exposure suitability
The In addition to these, a water-soluble linear organic polymer and
Polyvinyl pyrrolidone or polyethylene oxide
Etc. are useful. In order to increase the strength of the cured film,
Lucol soluble nylon and 2,2-bis- (4-hydro
Xylphenyl) -propane and epichlorohydrin poly
Ethers and the like are also useful. Weight average content of the polymer used in the present invention
The amount of the child is preferably 5000 or more, and
Preferably it is in the range of 10,000 to 300,000, and the number average molecular weight is
About 1000 or more is preferable, and more preferable
Or in the range of 2000-250,000. Polydispersity (weight level
(Average molecular weight / number average molecular weight) is preferably 1 or more, and
Preferably it is the range of 1.1-10. These polymers are random polymers,
Any of block polymer, graft polymer, etc.
Is preferably a random polymer. In the present invention
The polymer used can be synthesized by a conventionally known method.
The Used in synthesizing the polymer used in the present invention.
Examples of radical polymerization initiators include azo initiators, peracids
Known compounds such as compound initiators can be used. The binder polymer used in the present invention is
They may be used alone or in combination. These polymers
Is 20 to 95% by mass with respect to the total solid content of the heat-sensitive layer coating solution,
Preferably, it is added to the heat sensitive layer at a ratio of 30 to 90% by mass.
It is. When the added amount was less than 20% by mass, an image was formed.
At this time, the strength of the image portion is insufficient. The amount added is 95% by mass.
If it exceeds, no image is formed. Also radical polymerization
Linear with compounds with possible ethylenically unsaturated double bonds
The organic polymer is in the range of 1/9 to 7/3 by weight.
Is preferred. Next, the components of the acid crosslinking layer will be described.
The The infrared absorber used here is in the photopolymerization layer.
(A) Infrared absorber similar to that described above was used.
Can. The preferred content is the total solid content of the heat sensitive layer.
0.01-50 mass% is preferable with respect to weight, 0.1
10 mass% is more preferable, and in the case of a dye,
0.5 to 10% by weight is most preferable, and in the case of a pigment,
1.0-10 mass% is the most preferable. The content is
If it is less than 0.01% by mass, the sensitivity may decrease.
When it exceeds 50% by mass, it is used as an original for lithographic printing
Dirt may occur in the non-image area. [(E) Acid generator] In this embodiment,
An acid generator that decomposes by heat to generate an acid is 200
Irradiate light in the wavelength region of ~ 500 nm or 100 ° C or higher
It refers to a compound that generates an acid when heated upward.
Examples of the acid generator include a photo-initiator for photo-cationic polymerization, light
Photoinitiator for radical polymerization, photodecolorant for dyes, photochromic
Known for use in chemicals or microresists
Known compounds that can generate acid by thermal decomposition
Products and mixtures thereof. For example, S.M.
I. Schlesinger, Photogr. Sc
i. Eng. , 18, 387 (1974), T.A. S. B
al et al, Polymer, 21, 423 (1
980) and the applicant of the present application previously proposed.
Paragraph number of the issued Japanese Patent Application No. 11-332963
The compounds listed in [0101] to [0103]
Can be mentioned. Among these acid generators, the following general formula
Compounds represented by (O) to (S) are preferred. [0135] Embedded image In the general formulas (O) to (S), R¹, R²,
R^FourAnd R^FiveMay be the same or different and
It represents a hydrocarbon group having 20 or less carbon atoms which may have.
R^ThreeIs a halogen atom or an optionally substituted carbon
A hydrocarbon group having a carbon number of 10 or less or an alkoxy having a carbon number of 10 or less
Represents the Si group. Ar¹, Ar²Can be the same or different
Well, an ant having 20 or less carbon atoms which may have a substituent
Represents an alkyl group. R⁶Is an optionally substituted carbon
This represents a divalent hydrocarbon group having a number of 20 or less. n is 0-4
Represents an integer. In the general formulas (O) to (S), R¹, R²,
R^FourAnd R^FiveIs preferably a hydrocarbon group having 1 to 14 carbon atoms.
Yes. Acid generation represented by the general formulas (O) to (S)
A preferred embodiment of the herbal agent is the patent application previously proposed by the present inventors.
No. 11-320997 paragraph number [0197]
[0222] are described in detail. These compounds
Are disclosed in, for example, Japanese Patent Laid-Open Nos. 2-100054 and 2-1
Can be synthesized by the method described in No. 00005
The (E) Halogenation as an acid generator
Also include onium salts with counterions such as products and sulfonic acids
Among them, represented by the following general formulas (T) to (V)
Iodonium salt, sulfonium salt, diazonium salt
Preferably, those having any structural formula of
it can. [0139] Embedded imageIn the general formulas (T) to (V), X^-Ha
Rogenide ion, ClO_Four ^-, PF₆ ^-, SbF₆ ^-, BF
_Four ^-Or R⁷SO_Three ^-Where R⁷Has a substituent
Represents a hydrocarbon group having 20 or less carbon atoms which may be present. Ar
^Three, Ar^FourEach independently may have a substituent.
Represents an aryl group having 20 or less carbon atoms. R⁸, R⁹, R ^Ten
Is a hydrocarbon having 18 or less carbon atoms which may have a substituent.
Represents a basic group. Such an onium salt is disclosed in JP-A-10-3.
General to paragraph numbers [0010] to [0035] of No. 9509
It is described as a compound of formula (I)-(III). [0141] The amount of the acid generator added is the total solids of the heat sensitive layer.
0.01-50 mass% is preferable with respect to the part weight,
1-25 mass% is more preferable, 0.5-20 mass% is
Most preferred. The addition amount is less than 0.01% by mass
The image may not be obtained, exceeding 50% by mass.
Then, non-images at the time of printing when using the original for lithographic printing
Part may become dirty. The above acid generator is independent
May be used in combination with two or more
Good. [(F) Crosslinking agent] Next, the crosslinking agent will be described.
To do. The following are mentioned as a crosslinking agent. (I) Hydroxymethyl group or alkoxymethyl group
Aromatic compounds substituted with (Ii) N-hydroxymethyl group, N-alkoxymethyl
Group or N-acyloxymethyl group-containing compound (Iii) Epoxy compound The following compounds (i) to (iii) are as follows.
And will be described in detail. (I) the hydroxymethyl group or
As an aromatic compound substituted with an alkoxymethyl group
Is, for example, a hydroxymethyl group, an acetoxymethyl group
Or fragrance poly-substituted with alkoxymethyl groups
Group compounds or heterocyclic compounds. However,
Phenols and aldehydes
Also includes resinous compounds that have been polycondensed under basic conditions
The Polyhydroxy group or alkoxymethyl group
Among the substituted aromatic compounds or heterocyclic compounds,
In the position adjacent to the hydroxy group
Or the compound which has an alkoxymethyl group is preferable. Ma
Aromatic compounds poly-substituted with alkoxymethyl groups
Or in a heterocyclic compound, an alkoxymethyl group is
Compounds having 18 or less carbon atoms are preferred, and the following general formula (1)
The compound represented by (4) is more preferable. [0144] Embedded image [0145] Embedded image In the general formulas (1) to (4), L₁~ L
₈Each independently represents methoxymethyl, ethoxymethyl
H or the like substituted with an alkoxy group having 18 or less carbon atoms such as
A droxymethyl group or an alkoxymethyl group is represented. this
These crosslinking agents have high crosslinking efficiency and can improve printing durability.
Is preferable. (Ii) N-hydroxymethyl group, N-al
Has a coxymethyl group or N-acyloxymethyl group
As the compound to be used, European Patent Publication (hereinafter referred to as “EP-
A ". No. 0,133,216, West German Patent No.
Described in 3,634,671 and 3,711,264
Monomers and oligomers-melamine-formalde
Hyde condensates as well as urea-formaldehyde condensates, EP
-A alkoxy as described in 0,212,482
Examples include substituted compounds. Among them, for example, few
2 free N-hydroxymethyl groups, N-alkoxy
Has a cymethyl group or an N-acyloxymethyl group
Melamine-formaldehyde derivatives are preferred, N-A
Lucoxymethyl derivatives are most preferred. (Iii) As an epoxy compound, one or more
Monomers, dimers, and oligomers with epoxy groups
-Polymeric epoxy compounds include, for example,
Reaction formation of bisphenol A and epichlorohydrin
, Low molecular weight phenol-formaldehyde resin and epi
And a reaction product with chlorohydrin. That
US Patent No. 4,026,705, British Patent No. 1,
It is described and used in each specification of 539,192.
Can be mentioned. As the crosslinking agent, the compounds (i) to (iii)
The amount added when using a compound is the total solid content of the heat-sensitive layer.
5-80 mass% is preferable with respect to weight, 10-75 mass
% Is more preferable, and 20 to 70% by mass is most preferable.
When the addition amount is less than 5% by mass, the obtained image recording
The durability of the heat-sensitive layer of the recording material may be reduced, and 80 quality
If the amount exceeds%, storage stability may be reduced.
The In the present invention, the crosslinking agent (iv)
A phenol derivative represented by the following general formula (5) is also suitable.
Can be used. [0151] Embedded imageIn the general formula (5), Ar¹Is substituted
It represents an aromatic hydrocarbon ring that may have. Obtaining raw materials
In terms of the properties, the aromatic hydrocarbon ring may be benzene.
A ring, a naphthalene ring or an anthracene ring is preferred. Ma
The substituent includes a halogen atom, 12 or more carbon atoms.
Lower hydrocarbon group, alkoxy group having 12 or less carbon atoms, carbon
An alkylthio group, cyano group, nitro group,
A trifluoromethyl group and the like are preferable. Of the above, the sensitivity can be increased.
Ar¹As benzene ring having no substituent,
Phthalene ring, halogen atom, carbon having 6 or less carbon atoms
Hydrogen fluoride group, alkoxy group having 6 or less carbon atoms, 6 or less carbon atoms
Having an alkylthio group or nitro group as a substituent
A benzene ring or a naphthalene ring is more preferable. [(G) Alkali water soluble polymer compound]
Alkaline water-soluble polymer compound that can be used in the crosslinked layer
For example, a novolak resin or side chain with a hydroxyaryl group
The polymer which has is mentioned. With the novolac resin
The phenols and aldehydes under acidic conditions.
The combined resin is mentioned. Among them, for example, phenol and formal
Novolac resin obtained from Dehydr, m-cresol and
Novolac resin, formaldehyde obtained from formaldehyde
Novolac tree derived from resole and formaldehyde
From oil, o-cresol and formaldehyde
Borak resin, octylphenol and formaldehyde
Novolak resin obtained from m- / p-mixed creso
Novolac resin obtained from
Enol / cresol (m-, p-, o- or m- / p
-, M- / o-, o- / p-mixed)
Novolac resin obtained from mixture and formaldehyde
And using phenol and paraformaldehyde as raw materials,
Obtained by reaction under high pressure in a sealed state without using a catalyst
High molecular weight novolak resin with high ortho bond rate is preferred
Yes. The novolac resin has a weight average molecular weight of 800 to
300,000 and a number average molecular weight of 400-60,00
Select a suitable one according to the purpose from zero
Use it. Also, a hydroxyaryl group is added to the side chain.
Also preferred is a polymer having hydroxy in the polymer
As the aryl group, aryl having one or more OH groups bonded thereto
Groups. Examples of the aryl group include fluorine.
Enyl, naphthyl, anthracenyl, phenanthate
Renyl group etc. are mentioned, among others, availability and physical properties
From this viewpoint, a phenyl group or a naphthyl group is preferable. Book
A hydroxyaryl group in the side chain that can be used in the embodiment
As the polymer having, for example, the following general formula (W)
Including any one of the structural units represented by (Z)
Can be mentioned. However, in the present invention
However, it is not limited to these. [0157] Embedded imageIn the general formulas (W) to (Z), R¹¹The hydrogen field
It represents a child or a methyl group. R¹²And R ¹³Is the same but different
May be hydrogen atom, halogen atom, carbon number 10
The following hydrocarbon groups, alkoxy groups having 10 or less carbon atoms, or
An aryloxy group having 10 or less carbon atoms is represented. R¹²
And R¹³Is bonded or condensed to form a benzene ring or cyclohexane ring.
May be formed. R¹⁴Is a single bond or carbon number 20
The following divalent hydrocarbon groups are represented. R¹⁵Is a single bond or charcoal
Represents a divalent hydrocarbon group having a prime number of 20 or less. R¹⁶Is a single
Or a divalent hydrocarbon group having 10 or less carbon atoms. X¹
Single bond, ether bond, thioether bond, esthetic
Represents an alkyl bond or an amide bond. p represents an integer of 1 to 4
The q and r each independently represents an integer of 0 to 3. As these alkali-soluble polymers,
Japanese Patent Application No. 11-320997 previously proposed by the present inventors
Detailed description in the paragraph numbers [0130] to [0163] of the specification
It is. Alkaline water soluble that can be used in this embodiment
Only one kind of polymer compound may be used, or two kinds
You may use it in combination. Alkaline water soluble
The amount of the polymer compound added is based on the total solid content of the heat sensitive layer.
5 to 95% by mass is preferable, and 10 to 95% by mass is more preferable.
20 to 90% by mass is preferable. alkali
When the addition amount of the water-soluble resin is less than 5% by mass, heat sensitivity
The durability of the layer may deteriorate and exceed 95% by mass
In some cases, an image is not formed. Also, other known methods to which the method of the present invention can be applied.
JP-A-8-276558 discloses a recording material for
Negative-type image recording materials containing the phenol derivatives described
And diazonium described in JP-A-7-306528
Negative-type recording material containing a sulfur compound, JP-A-10-20
There is an unsaturated bond in the ring described in Japanese Patent No. 3037
By using an acid-catalyzed polymer having a heterocyclic group
Examples include negative-type image-forming materials that use a crosslinking reaction.
The heat-sensitive layer described in these is a negative heat-sensitive layer according to the present invention.
It can be applied to the acid cross-linking layer. [Other components] In the present invention, it is further necessary.
Depending on the above, various compounds other than these may be added.
For example, coloring a dye with a large absorption in the visible light range
It can be used as an agent. Also phthalocyanine
Pigments, azo pigments, carbon black, titanium oxide
Any pigment can be suitably used. The heat sensitive layer
If it is a photopolymerization layer, during preparation or storage of the coating solution
In the radically polymerizable ethylenically unsaturated double bond
A small amount of heat to prevent unwanted thermal polymerization of the compound
It is desirable to add a polymerization inhibitor. In the present invention, the above negative type heat sensitive layer coating solution
In order to broaden the stability of processing against development conditions,
Japanese Patent Laid-Open Nos. 62-251740 and 3-208514
Nonionic surfactants as described in JP
Described in 59-121044 and JP-A-4-13149
Amphoteric surfactants can be added
The A lithographic plate having a negative heat-sensitive layer as described above
In order to produce a printing plate, it is usually necessary for the heat-sensitive layer coating solution.
Dissolve each component in a solvent and apply to a suitable support.
That's fine. The solvent used here is ethylene dichloromethane.
Ride, cyclohexanone, methyl ethyl ketone, meta
Nord, ethanol, propanol, ethylene glycol
Lumonomethyl ether, 1-methoxy-2-propano
, 2-methoxyethyl acetate, 1-methoxy-2
-Propyl acetate, dimethoxyethane, lactic acid methyl
, Ethyl lactate, N, N-dimethylacetamide, N,
N-dimethylformamide, tetramethylurea, N-
Methyl pyrrolidone, dimethyl sulfoxide, sulfora
Γ-butyl lactone, toluene, water, etc.
However, it is not limited to this. These melts
The medium is used alone or in combination. The above components in the solvent
The concentration of (total solid content including additives) is preferably 1-5
0% by mass. In addition, the net on the support obtained after coating and drying.
Ga type heat sensitive layer coating amount (solid content) varies depending on application
Is generally 0.5 to 5.0 g / m²Is preferred. Coating
Various methods can be used as a method for
For example, bar coater coating, spin coating, spray coating
Cloth, curtain coating, dip coating, air knife coating,
Examples thereof include blade coating and roll coating. Painting
As the amount of fabric decreases, the apparent sensitivity increases.
However, the film properties of the heat-sensitive layer that performs the image recording function are reduced.
The [Support] Lithographic plate having the above negative heat-sensitive layer
In the printing plate, as a support on which a heat-sensitive layer can be applied,
Dimensionally stable plate-like material, for example, paper, plastic
(For example, polyethylene, polypropylene, polystyrene)
Paper, metal plates (for example, aluminum)
Minium, zinc, copper, etc.), plastic film (eg
For example, cellulose diacetate, cellulose triacetate, propion
Acid cellulose, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyester
Tylene, polystyrene, polypropylene, polycarbonate
Metal, polyvinyl acetal, etc.)
Minated or evaporated paper or plastic fill
Or the like. Preferred supports are polyesters.
A tellurium film or an aluminum plate is mentioned. Used
The thickness of the aluminum plate is about 0.1 mm to 0.00 mm.
It is about 6 mm. [0166] The surface of the aluminum plate is roughened.
Surface treatment, apply negative heat sensitive layer, and planographic printing plate precursor
It can be. Before roughening the aluminum plate
An illustration for standing and removing surface rolling oil if desired
For surfactants, organic solvents or alkaline aqueous solutions
A degreasing process is performed. Next, the surface of the aluminum plate
Is roughened by mechanical roughening.
Method of surface treatment, method of electrochemically dissolving and roughening the surface
There is also a method of selectively dissolving the surface chemically. machine
Typical methods include ball polishing, brush polishing, and brass
A known method called a polishing method or buffing method is used.
Can be. In addition, as an electrochemical roughening method
Is performed by alternating current or direct current in hydrochloric acid or nitric acid electrolyte
There is a way. Also disclosed in Japanese Patent Laid-Open No. 54-63902.
Use a combination of both as shown
I can do it. The aluminum plate roughened in this way
If necessary, alkali etching treatment and neutralization treatment
After being made, the water retention and wear resistance of the surface are increased as desired.
Therefore, an anodizing process is performed. Aluminum plate anode
As the electrolyte used for oxidation treatment, porous oxide film is used.
You can use anything you want to form.
Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or
These mixed acids are used. Their electrolyte concentration is electrolysis
It is determined as appropriate according to the type of quality. The treatment conditions for anodization depend on the electrolyte used.
Since it varies, it cannot be specified unconditionally.
Concentration of quality is 1-80% solution, liquid temperature is 5-70 ° C, current density
Degree 5-60A / dm², Voltage 1-100V, electrolysis time 1
It is appropriate if it is in the range of 0 seconds to 5 minutes. Of anodized film
The amount is 1.0g / m²The above is preferred, but more preferred
Is 2.0 to 6.0 g / m²Range. Anodized film
1.0g / m²If it is less than 1, the printing durability was insufficient.
The non-image part of the planographic printing plate is easily scratched and printed.
So-called “scratch stains” where ink sometimes adheres to the scratched part
It tends to occur. In addition, such anodizing treatment
It is applied to the surface used for printing on the plate support.
0.01-3 g / m on the back side²Anode
In general, an oxide film is formed. After anodizing, aluminum
The surface is subjected to a hydrophilic treatment as necessary. With hydrophilic treatment
U.S. Pat.Nos. 2,714,066, 3,181,461,
 Disclosed in 3,280,734 and 3,902,734
Such alkali metal silicates (eg sodium silicate)
Aqueous solution) method. In this method, the support is
Soaked or electrolyzed in aqueous sodium acid solution
It is done. Also disclosed in Japanese Patent Publication No. 36-22063
Potassium zirconate fluoride and US Patent No.
3,276,868, 4,153,461 and 4,689,272
Treat with polyvinylphosphonic acid as disclosed
A method or the like is used. [Organic subbing layer] Having the above-mentioned negative heat-sensitive layer
In lithographic printing plates, aluminum plates are coated with a heat-sensitive layer
Provide an organic subbing layer or intermediate layer as required before
It is done. As organic compounds used in this organic subbing layer
For example, carboxymethylcellulose, dextri
, Gum arabic, 2-aminoethylphosphonic acid, etc.
Phosphonic acids having an amino group, may have a substituent
Phenylphosphonic acid, naphthylphosphonic acid, alkylphospho
Sulfonic acid glycerophosphonic acid, methylenediphosphonic acid
And organic phosphonic acids such as ethylenediphosphonic acid, substitution
Phenyl phosphate, naphthyl phosphate,
Organophosphoric acids, such as rualkylphosphoric acid and glycerophosphoric acid,
Optionally substituted phenylphosphinic acid, naphthyl
Phosphinic acid, alkylphosphinic acid and glycerophor
Organic phosphinic acids such as sphinic acid, glycine and β-a
Amino acids such as lanine, and triethanolamine
Hydrochlorides of amines having hydroxyl groups such as
It is selected from the above, but two or more kinds may be mixed and used. The undercoat layer coating solution contains ammonia,
Basic substances such as ethylamine and potassium hydroxide, and salts
PH is adjusted with acidic substances such as acid and phosphoric acid, pH 1
It can also be used in the range of -12. In addition, photosensitive
Add yellow dye to improve tone reproducibility of printing plate
You can also. The coating amount after drying of the organic undercoat layer is 2 to 2
00mg / m²Is suitable, preferably 5 to 100 m
g / m²It is. The above coating amount is 2 mg / m²Fewer
And the effect sufficient for the original purpose, such as dirt prevention, is not acquired.
200 mg / m²If it is larger, the printing durability is lowered. Note that the adhesion between the support and the heat-sensitive layer is improved.
An intermediate layer may be provided. For improved adhesion
In general, the intermediate layer is a diazo resin, such as aluminum.
It consists of phosphoric acid compounds adsorbed on the surface. Middle tier
Thickness is arbitrary, and uniform with upper heat-sensitive layer when exposed
The thickness must be such that a proper bond formation reaction can be performed. Through
Usually about 1 to 100 mg / m dry solid²The application ratio of
5-40 mg / m²Is particularly good. In the middle layer
The ratio of the diazo resin used is 30 to 100% by mass, preferably
Preferably, it is 60-100 mass%. [Backcoat layer]
The developer and replenisher used have a relatively high alkali strength.
In order to suppress elution of aluminum oxide from the back side
It is preferable to have a backcoat layer. Such a bar
As the back coat layer, for example, JP-A-5-45885
Gazette, Japanese Patent Application No. 4-57902 and Japanese Patent Application No. 4-189
You can use what is described in detail in 448
Yes. [0174] The present invention will be described in detail with reference to the following examples.
The The percentages in the examples below are specified elsewhere.
Unless otherwise indicated, all are mass%. Example 1 <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 [0177] Embedded image <Synthesis of Copolymer 1> Stirrer, cooling pipe and
In a 500 ml three-necked flask equipped with a dropping funnel
31.0 g (0.36 mol) of formic acid, ethyl chloroformate 3
9.1 g (0.36 mol) and 200 ml of acetonitrile
The mixture was stirred while cooling with an ice-water bath. this
To the mixture, 36.4 g (0.36 mol) of triethylamine
Was dropped by a dropping funnel over about 1 hour. End of dripping
Then remove the ice-water bath and stir the mixture at room temperature for 30 minutes
did. P-aminobenzenesulfone amine was added to this reaction mixture.
51.7 g (0.30 mol) was added and 70 ° C. in an oil bath.
The mixture was stirred for 1 hour while warming up. After the reaction is complete
Add this mixture to 1 liter of water while stirring this water.
And the resulting mixture was stirred for 30 minutes. This mixture
The precipitate is removed by filtration, and this is slurried with 500 ml of water.
The slurry was filtered and the resulting solid was dried.
Drying, N- (p-aminosulfonylphenyl)
A white solid of tacrylamide 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. The following heat-sensitive layer coating solution was applied on the obtained support,
Dry coating amount is 1.8 g / m²Apply so that
A dilithographic lithographic printing plate precursor was obtained. <Coating solution for heat-sensitive layer>   Copolymer 1 [Component (B)] 0.4 g   m, p-cresol novolak (P-1) [component (B)] (m / p ratio = 6/4) , Weight average molecular weight 8000, containing 0.5% of unreacted cresol) 0.6 g   Cyanine dye A [component (A + C)] 0.1 g   Phthalic anhydride [component (D)] 0.05 g   p-Toluenesulfonic acid 0.002 g   Ethyl violet 0.02 g   (Counterion: 6-hydroxy-β-naphthalenesulfonic acid)   Naphthoquinone 1,2-diazide-5-sulfonylcroid and pyrogallol 0.01 g esterified product with seton resin   Fluorosurfactant 0.05 g   (Product name: Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)   Methyl ethyl ketone 8 g   1-methoxy-2-propanol 4 g Next, apply the following developer A1 and replenisher B1.
Prepared.Developer A1 ・ SiO₂・ K₂O 4.0 mass% (SiO₂/ K₂O = 1.18 (molar ratio)) ・ Citric acid 0.5% by mass ・ Polyethylene glycol (weight average molecular weight = 1000) 0.5 mass% ・ P-1 0.08 mass% ・ Water 94.92 mass% [0182]Developer replenisher B1 ・ SiO₂・ K₂O 5.0% by mass (SiO₂/ K₂O = 1.0 (molar ratio)) ・ Citric acid 0.6% by mass ・ Polyethylene glycol (weight average molecular weight = 1000) 0.6 mass% ・ Water 93.8% by mass In the development processing tank of an automatic processor having an immersion type developing tank,
20 liters of developer A1 (about pH 13) with composition
And kept at 30 ° C. In the second bath, tap water for 8 liters.
Toru and the third bath, FP-2w (1: 1) (Fuji Photo
8 liters of Film Co., Ltd. was charged. Planographic printing plate precursor (1030 m × 800 m
m × 0.24mm thickness) Creo Plate Setter T
Using the rendsetter 3244F, (Output:
9.0W, rotation speed: 150rpm, resolution: 2400d
pi, image area: approx. 20%) and prepared as above
The lithographic printing plate was obtained by developing with an automatic machine. that time,
80 cc of developer replenisher B1 having the above composition per plate
While replenishing 100 cc of developer replenisher B1 every hour
Processed. 160 plates per day for 3 months
did. Reference fine lines on the planographic printing plate obtained by this development process
When measuring the line width of (8μm), at the start of development processing
No change was observed until 3 months after treatment. Also
There was no adhesion of residue on the plate. Development after 3 months
A slight sludge was observed in the developing tank from which the liquid was removed. Ma
The obtained lithographic printing plate
25 printed by Komori Printing Machine Manufacturing Co., Ltd.
B) Good ink fillability, 15 stains after printing
Beautiful prints, and 70,000 satisfied content
A printed material was obtained. Example 2 Hereinafter, the present invention will be described in detail by way of examples. The bottom
The percentages in the examples are unless otherwise specified.
All are mass%. [Preparation of support] An aluminum plate having a thickness of 0.03 mm
Nylon brush and 400 mesh pumiston water suspension
The surface was grained using a liquid, and then washed with water. 10%
Etch by soaking in sodium hydroxide at 60 ° C for 40 seconds
, Washed with running water, neutralized with 20% nitric acid, washed with water
did. This is an alternating sine wave under the condition of VA = 12.7V.
160 coulomb / in 1% nitric acid solution using waveform current
dm²Electrolytic surface roughening treatment was performed with the anode electric quantity. The table
When the surface roughness was measured, it was 0.6 μm (Ra indication).
It was. Subsequent immersion in 30% nitric acid aqueous solution 55
After desmutting for 1 minute at ℃, in 20% nitric acid aqueous solution,
Current density 2A / dm²The thickness is 2.7 g / m²Nina
The substrate (I) was prepared by anodizing as described above. [Formation of hydrophilic layer] The group thus treated
A hydrophilic layer coating solution having the following composition is applied to the surface of the plate (I), and 8
Dry at 0 ° C. for 30 seconds. The amount of film after drying is 20mg /
m²Met. [0186] -Hydrophilic layer coating solution composition-   ・ Β-alanine 0.10 g   ・ Methanol 100 g [Formation of heat-sensitive layer] -Synthesis of cross-linking agent [KZ-9]- 1- [α-methyl-α- (4-hydroxyphenyl) ester
Til] -4- [α, α-bis (4-hydroxypheny
L) ethyl] benzene in aqueous potassium hydroxide solution,
Reacted with formalin. The reaction solution is acidified with sulfuric acid and crystallized.
And recrystallizing from methanol,
A cross-linking agent [KZ-9] having the following structure was obtained. For reverse phase HPLC
When the purity was measured, it was 92%. [0188] Embedded image -Obtaining the binder polymer [BP-1]
− Poly (p-hydroxystyrene) manufactured by Maruzen Petrochemical Co., Ltd.
), Marca Linker MS-4P (trade name)
[BP-1]. Next, the following heat-sensitive layer coating solution [P] was prepared,
This solution is supported on aluminum with the above hydrophilic layer formed
Apply on body substrate (I) and dry at 100 ° C for 1 minute
Thus, a heat sensitive layer was formed to obtain a negative type lithographic printing plate precursor. Dry
The coating amount after drying is 1.5 g / m ²Met. Coating liquid [P]
Acid generator [SH-1] and infrared absorber [I
The structure of K-1] is shown below. [0191] Thermal layer coating solution [P]   ・ Acid generator [SH-1] 0.3 g   ・ Crosslinking agent [KZ-9] 0.5 g   -Binder polymer [BP-1] (P-2) 1.5 g   Infrared absorber [IK-1] 0.07 g   ・ AIZEN SPILON BLUE C-RH 0.035 g (Hodogaya Chemical Co., Ltd.)   ・ Fluorine-based surfactant 0.01 g    (Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)   ・ Phthalic anhydride 0.05 g   ・ Methyl ethyl ketone 12 g   ・ Methyl alcohol 10 g   1-methoxy-2-propanol 4 g   ・ 4-methoxy-1-propanol 4 g [0192] Embedded image Next, apply the following developer A2 and replenisher B2.
Prepared.Developer A2 ・ Potassium silicate (SiO₂/ M₂O = 2.0 mol of 50% aqueous solution)                                                          4.49% by mass ・ Potassium hydroxide 1.05% by mass ・ P-2 0.06% by mass ・ Water 94.40 mass% [0194]Developer replenisher B2 ・ Potassium silicate (SiO₂/ M₂O = 2.0 mol of 50% aqueous solution)                                                          6.88% by mass ・ Potassium hydroxide 3.13% by mass ・ Water 89.99 mass% The photosensitive lithographic printing plate 2 was subjected to a wavelength of 820 to 850.
Scanning exposure with a semiconductor laser emitting infrared rays of about nm
(Scanning exposure conditions: 100 μJ / cm²With an exposure amount of 40
With a condition of 175 lines / inch at 00 dpi,
1-99% halftone image (in 1% increments)
Use a plate that has been heated at 110 ° for 30 seconds with a heater.
And an automatic developing machine charged with the developer A2 and development auxiliary
Using the replenisher B2, in the same manner as in Example 1, development processing, washing with water,
It was then dried. However, the replenishment amount is 12cc per plate
It was set to 100 cc every hour. 160 per day
Each plate was developed for 3 months. Obtained in this development process
The line width of the reference thin line (8 μm) on the lithographic printing plate was measured
However, there is no change from the start of the development process until after 3 months of processing.
There was no change. After 3 months, the developer is removed
Some sludge was seen in the statue. Also, the obtained flat
Plate printing plate is offset printing machine Sprint 25 (Komori Printing
Ink fillability when printing was performed by Koki Kogyo Co., Ltd.
Good, beautiful print with no smudges after printing 15
Followed by 70,000 satisfactory prints.
It was. In addition, sensitivity fluctuations are steptable during laser exposure.
Investigated by the change in the number of steps of the robot, but there was no change at 8.5 steps
It was. Comparative Example In Examples 1 and 2, the alk
Does not contain re-soluble resin or alkali-soluble resin
Except for the point containing 0.2% by mass of the above developer, replenishment
Using the same liquid as the liquid, the same evaluation as in Examples 1 and 2 was performed.
However, any plate material has a residue in the image area and the non-image area.
Adhesion was observed, and poor printing and soiling occurred during printing.
In addition, the developer tank from which the developer has been removed after 3 months has a large amount of
Dro was seen. [0197] By using the processing method of the present invention,
Heat-sensitive lithographic printing plate even after long-term running
There is no adhesion of debris derived from layer components,
No soiling occurs. In addition,
There is little occurrence of b.

Claims (1)

What is claimed is: 1. A processing method in which a lithographic printing plate having a heat-sensitive layer on a support is image-exposed and then developed using an alkali developer and a development replenisher. A processing method for a lithographic printing plate, wherein the developer contains an alkali metal silicate and contains 0.02 to 0.1% by mass of an alkali-soluble resin.