JP2003295417A - Method for making planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for making a planographic printing plate causing no stain to the background of a print and capable of satisfactorily achieving improvement of printing resistance by burning treatment and to particularly provide a method for making a planographic printing plate from a positive- working IR sensitive planographic printing plate. <P>SOLUTION: In the method for making the planographic printing plate, a positive-working IR sensitive planographic printing plate obtained by disposing an image forming layer containing an IR absorbing dye on a support having pits formed by electrolytic surface roughening with hydrochloric acid, wherein ≥60% by number of all the pits have 5-30 μm pit diameter, is exposed with IR, developed, washed and subjected to burning treatment without applying a surface conditioning liquid for burning. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lithographic printing plate making.
For more details on the method, please refer to positive infrared photosensitive lithographic printing
The present invention relates to a plate making method of a lithographic printing plate using a plate. [0002] 2. Description of the Related Art In lithographic printing, water and oil are essentially mixed.
It is a printing method that skillfully utilizes the properties that are not, and the printing plate is
The area that accepts water and repels oil-based ink and the oil that repels water
The former is a non-image area.
The latter is the image area. For example, positive photosensitive lithographic printing
In the plate, o-quinonediazide compound alone or
Rack type phenol resin, cresol resin, etc.
Suitable for metal or plastic mixed with potash soluble resin
Coated on a transparent support and through a transparent positive
When exposed to actinic light, the exposed portion of o-quinone
Diazide compounds decompose and change to alkali-soluble
Easily removed with alkaline aqueous solution to give positive images
Yeah. Therefore, it is necessary to use a support having a hydrophilic surface.
The hydrophilic surface of the support is exposed at the part removed with the aqueous potassium solution.
So this part accepts water and repels ink
The On the other hand, the remaining part of the image is lipophilic and
Accept key. A large number of printed materials were obtained from a single printing plate.
If not, after exposing and developing the photosensitive lithographic printing plate,
By heating at high temperature (so-called burning treatment)
A method for enhancing the image portion is effective. Among various photosensitive materials
Infrared with an image forming layer containing an infrared absorbing dye
When making a plate from a photosensitive lithographic printing plate, develop the non-image area.
If the alkali concentration of the developer is increased to improve the
There is a tendency that the image area tends to be thinned.
After development, there is a problem that the screen is relatively narrow
Burning is especially useful for enhancing the image area
It is. However, printing that was hydrophilic before processing
The non-image area of the plate (that is, the hydrophilic support surface is
In the exposed part)
The component that pops out from the image part becomes dirty and becomes hydrophilic
Printed because it is lost and will accept printing ink
Dirt (so-called ground dirt) occurs in the background of
Therefore, this non-image area contamination caused by the burning process.
To prevent this, the plate should be washed with a surface-adjusting solution before burning.
It has been proposed to process. This surface conditioning liquid is usually water soluble
Containing a functional polymer and an inorganic salt. On the other hand
A hydrophilic compound is immersed in the image area by treatment with a surface-adjusting solution.
Cross-linking of novolac binder by see-through and burning treatment
It is also known that the printing durability of the plate decreases slightly.
The maximum printing durability is improved by the burning process.
Is a problem. Therefore, so-called soil pollution
While preventing this, improve the printing durability of the plate as much as possible
It is hoped that. [0004] The object of the present invention is to print
Without causing dirt in the background of the object,
The printing durability can be fully demonstrated by the printing process.
Lithographic printing plate making method, especially positive type infrared photosensitive flat plate
It is to provide a plate making method from a plate printing plate. [0005] [Means for Solving the Problem]
As a result of diligent studies to achieve
Positive red with a support with pits formed by reason
By using an external photosensitive lithographic printing plate, after exposure and development,
Even if no surface-conditioning solution is applied before the burning process, scumming will occur.
It is possible to fully demonstrate the effect of improving printing durability without rubbing
The headline and the present invention have been completed. Therefore, the present invention
Pits are formed by hydrochloric acid electrolytic roughening treatment, and
60% or more of the total number of pits has a pit diameter of 5 to 30 μm
A podium having an image forming layer containing an infrared-absorbing dye on a support.
Di-type infrared photosensitive lithographic printing plate exposed to infrared and developed
After that, it is washed with water, and the burning treatment is performed without applying the burning surface preparation liquid.
A method for making a lithographic printing plate,
The The above specific support has a pit diameter of 5 to 30 μm.
Because of its good water retention, vernier can be used without using a surface preparation liquid.
It is a support suitable for removing deposits during polishing. [0006] The present invention will be described in detail below.
First, the positive infrared photosensitive lithographic printing plate used in the present invention
explain about. Positive infrared photosensitive lithographic printing plates
It has an image forming layer on the carrier and, if necessary, other layers
The image forming layer comprises (A) an infrared absorbing dye.
In addition, (B1) alkali having a carboxyl group
Soluble polymer compound, (B2) alkali-soluble resin,
(C) Alkali-soluble polymer of (B1) and (B2)
The alkali-soluble polymer compound and
Reducing the solubility of the resin in an aqueous alkaline solution
And a compound whose solubility-reducing action is reduced by heating,
(D) It comprises a cyclic acid anhydride. Less than
The components of the positive infrared lithographic printing plate are described below.
I will explain. [Support] Positive infrared sensation used in the present invention
The photolithographic printing plate is made of hydrochloric acid electrolytic roughening treatment.
Pits are formed, and more than 60% of the total number of pits
Aluminum support with pit diameter of 5-30μm
It is a body. Support for lithographic printing plate precursor
Therefore, an aluminum plate is usually used. Suitable al
The minium plate is mainly pure aluminum plate and aluminum.
It is an alloy plate containing a small amount of foreign elements as a component.
Plastic laminated or vapor-deposited with minium
It may be a film. Foreign elements in aluminum alloys
Includes silicon, iron, manganese, copper, magnesium, black
, Zinc, bismuth, nickel, titanium, etc. Together
The content of foreign elements in gold is at most 10% by mass. Special
The preferred aluminum for this is pure aluminum, but
Pure aluminum is difficult to manufacture due to scouring technology
Therefore, it may contain slightly different elements. like this
However, the composition of aluminum plate is not specified.
In addition, a well-known and publicly-used aluminum plate is appropriately used.
Can be used. Usually specified in JIS A,
1050, 1100, 1200, 3003, 3103,
An aluminum plate such as 3005 is used. Armini
Umm plate thickness is preferably about 0.1mm to 0.6mm
Or 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. Hydrochloric acid electrolytic roughening treatment is mainly composed of hydrochloric acid.
Meaning electrochemical surface roughening in an aqueous solution
In hydrochloric acid aqueous solution, alternating current, high frequency alternating current, triangular wave alternating current or
There is a method of performing electrolysis by direct current. In general, hydrochloric acid
An electrode facing the aluminum plate in an aqueous solution containing
The surface is electrochemically roughened by applying an alternating current. hydrochloric acid
Compound concentration from 1.0 g / liter to saturation limit
Can be employed, preferably 2.5 to 100 g / liter
The range of tuttle. More preferably 5-50 g / liter
Torr range. The preferred compound is aluminum chloride
Hydrochloric acid, sodium chloride, ammonium chloride or chloride
It contains hydrochloric acid ions made of magnesium.
These are used alone or in combination. Also other
It may be combined with hydrochloric acid ions. In addition to hydrochloric acid electrolyte
Aluminum salt mixed in an amount of 20-150 g / liter
It is preferable to do. If necessary, sulfuric acid, phosphoric acid,
It is safe to add boric acid or ammonium salt.
Yes. The temperature of the electrolyte mainly composed of hydrochloric acid is usually 10 to 60.
° C, preferably in the range of 30-55 ° C. 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 5 to 200A / dm²Is preferably in the range of 10-50
A / dm²More preferably, the amount of electricity is 1-1000.
C / dm²The range of 100 to 800 C / dm is preferable.²Range of
An enclosure is more preferred. The frequency is preferably 50 Hz or more,
A range of 60 to 500 Hz is more preferable. Hydrochloric acid concentration, electricity
5-30μ depending on the combination of flow density, quantity of electricity, frequency
A pit diameter of m can be formed. Hydrochloric acid above
De-roughening treatment, other roughening treatment, for example, mechanically roughening
You may combine the method to make. As a mechanical method
The ball polishing method, brush polishing method, blast polishing method,
A known method such as a polishing method can be used. As described above, hydrochloric acid electrolytic surface roughening is performed.
More than 60% of the total number of pits has a pit diameter of 5 to 30 μm
To obtain a support having More preferably 6 of the total number of pits
0% or more of a support having a pit diameter of 10 to 20 μm
obtain. Such pit diameters can be enlarged by taking SEM photos.
The pit diameter can be measured and confirmed with a photograph. average
If the pit diameter is smaller than 5 microns, it will adhere to the photosensitive layer.
On the other hand, if it is larger than 30 microns, the dirt is bad.
Become. As described above, the roughened support is a surface.
The average roughness (Ra) is generally 0.6 microns or less,
Preferably it is 0.5 micron or less. Electrochemically in an aqueous solution mainly composed of hydrochloric acid
The roughened aluminum plate is the surface of the aluminum plate.
In order to remove the smut component formed in the
Desmutting and / or mild etching in aqueous solution of Lucari
Ching processing may be performed. Specific examples of acid or alkali
Such as hydrofluoric acid, zirconate fluoride, phosphoric acid, sulfuric acid, hydrochloric acid, glass
Acids such as acids, sodium hydroxide, potassium hydroxide, third
Sodium phosphate, sodium aluminate, sodium silicate
And alkali such as sodium carbonate. These acids
Or alkaline aqueous solution is 1 type or 2 types or more respectively.
Can be used as a mixture. Etching is 0.0
1-3g / m²Etch aluminum equivalent to
It is preferable. Etching of such an etching amount
The concentration of acid or alkali is 0.05-40.
%, The liquid temperature is 40 to 100 ° C., and the treatment time is 5 to 300 seconds.
This is performed by appropriately selecting from the range. Such a mild etching process is neutral.
In a salt solution, an aluminum plate is used as a cathode and DC voltage is applied.
It is also possible to perform electrochemical treatment. aluminum
If the surface is lightly etched,
Insoluble matter or smut is formed. This smut is
Phosphoric acid, sulfuric acid, nitric acid, chromic acid, etc., or mixtures thereof
It can be removed by washing with. Furthermore, the aluminum treated in this way
The plate can improve surface water retention and wear resistance if desired.
Therefore, an anodizing treatment can be performed. aluminum
The electrolyte used for anodizing the plate is porous
Various electrolytes that form oxide films can be used.
Inorganic such as sulfuric acid, phosphoric acid, chromic acid, nitric acid, boric acid
Acids or organic acids such as succinic acid, sulfamic acid, it
Mixed acids, their aqueous solutions or non-aqueous solutions alone
Or a combination of two or more, and their electrolytes
The concentration of is appropriately determined depending on the type of electrolyte. The anodic oxidation conditions 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. The lithographic printing plate precursor was prepared as described above.
Provided by laminating at least an image forming layer on a support
However, if necessary, an undercoat layer may be provided on the support.
You can. The components used in the undercoat layer include various
For example, carboxymethyl cellulose
, Dextrin, gum arabic, 2-aminoethyl phosphate
Phosphonic acids having an amino group such as sulfonic acid; substituents
Phenylphosphonic acid, naphthylphos
Phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, meso
Presence of tylene diphosphonic acid and ethylene diphosphonic acid
Phosphonic acid; phenyl phosphorus which may have a substituent
Acid, naphthyl phosphate, alkyl phosphate and glyceroline
Organic phosphoric acid such as acid; phenyl which may have a substituent
Ruphosphinic acid, naphthylphosphinic acid, alkylphosphine
Organic phosphines such as finic acid and glycerophosphinic acid
Acid; amino acids such as glycine and β-alanine;
Has hydroxyl groups such as ethanolamine hydrochloride
And the amine hydrochloride. The organic compound
May be used alone or in combination of two or more
May be. Also, undercoat the diazonium salt described above
This is also a preferred embodiment. The undercoat layer has the following general formula:
Of the organic polymer compound having the structural unit represented by (I)
An organic undercoat layer containing at least one kind is also preferred. [0018] [Chemical 1] Where R⁵¹Is a hydrogen atom, a halogen atom or
Represents an alkyl group, R⁵²And R⁵³Each independently water
Elementary atom, hydroxyl group, halogen atom, alkyl group, substituted al
Kill group, aryl group, substituted aryl group, -OR⁵⁴, -C
OOR⁵⁵, -CONHR⁵⁶, -COR⁵⁷Or -CN
And R⁵²And R⁵³Bond together to form a ring structure
May be. Where R⁵⁴~ R⁵⁷Are each independently
Represents an aryl group or an aryl group. X is a hydrogen atom, a metal atom,
-NR⁵⁸R⁵⁹R⁶⁰R⁶¹Represents. Good faith R here⁵⁸~ R⁶¹Is
Each independently a hydrogen atom, alkyl group, substituted alkyl
Represents a group, aryl group or substituted aryl group, R⁵⁸And R
⁵⁹May be bonded to each other to form a ring structure. m is 1 to
An integer of 3 is represented. The dry coating amount of the undercoat layer is 2 to 2
00mg / m²Is preferably 5 to 100 mg / m²Is more
preferable. The dry coating amount is 2 mg / m²To be less than
Sufficient film properties may not be obtained. Meanwhile 200mg /
m²Even if it is applied beyond
Can not. The undercoat layer can be provided by the following method.
Yes. That is, water or methanol, ethanol, methyl ether
For organic solvents such as tilketone or mixed solvents
A solution for the undercoat layer in which the organic compound is dissolved is aluminized.
A method of coating and drying on a support such as a um plate,
Water or methanol, ethanol, methyl ethyl ketone
In any organic solvent or a mixed solvent thereof,
An undercoat layer solution in which an object is dissolved, an aluminum plate, etc.
So that the organic compound is adsorbed, and then
It is a method of cleaning and drying with water or the like. In the former method, 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.
0.05 to 10% by mass is more preferable, and 0.1 to 5%.
More preferred is mass%. The immersion temperature is 20
-90 degreeC is preferable and 25-50 degreeC is more preferable. Immersion
The pickling time is preferably 0.1 second to 20 minutes, and 2 seconds to 1 minute.
Is more preferable. The solution for the undercoat layer is ammonia, trie
Basic substances such as tilamine and potassium hydroxide, hydrochloric acid,
Adjust to pH 1-12 using acidic substances such as phosphoric acid.
It can also be adjusted. For the purpose of improving tone reproducibility
You can also add a yellow dye. Next, positive infrared photosensitivity used in the present invention.
The components of the image forming layer of the lithographic printing plate will be described. -(A) Infrared absorbing dye- The infrared absorbing dye used in the image forming layer absorbs infrared light.
There is no particular limitation as long as it is a dye that generates heat and generates heat.
Various dyes known as absorbing dyes can be used
The Infrared absorbing dyes include commercially available dyes or literature (eg
For example, “Dye Handbook”, edited by the Society of Synthetic Organic Chemistry, Showa 45
For example, azo dyeing
Materials, metal complex azo dyes, pyrazolone azo dyes, naphtho
Non dye, anthraquinone dye, phthalocyanine dye,
Carbonium dye, quinoneimine dye, methine dye,
Anine dyes, squarylium pigments, pyrylium salts, metals
And dyes such as thiolate complexes. Of these dyes
Among them, those that absorb infrared light or near infrared light are infrared.
Suitable for use with lasers that emit light or near infrared light
Is particularly preferable. Absorbs such infrared light or near infrared light.
Examples of dyes to be collected include, for example, JP-A-58-125246.
JP, 59-84356, JP 59-2028
No. 29, cyanine described in JP-A-60-78787, etc.
Dye, JP-A-58-173696, JP-A-58-18
1690, Japanese Patent Laid-Open No. 58-194595, etc.
Chin dyes, JP-A-58-112793, JP-A-58-
224793, JP-A-59-48187, JP-A-5
9-73996, JP-A-60-52940, JP-A
Naphthoquinone dyes described in JP-A-60-63744, etc.
Squarylium color described in Sho58-112792 etc.
Cyanine described in British Patent 434,875
Dyes described in US Pat. No. 5,380,635
Preferred examples include hydroperimidine squarylium dyes.
It is. Also, as a dye, US Pat. No. 5,156,
Also preferred is a near-infrared absorption sensitizer described in No. 938,
The substitution described in US Pat. No. 3,881,924
Aryl benzo (thio) pyrylium salts,
-142645 (US Pat. No. 4,327,169)
Trimethine thiapyrylium salt described in Japanese Patent Publication No.
-181051, 58-220143, 59-
41363, 59-84248, 59-842
49, 59-146063, 59-14606
The pyrylium compound described in No. 1, JP 59-216 A
146, a cyanine dye described in US Pat. No. 4,28.
Pentamethine thiopylium described in 3,475 specification
To salt etc., Japanese Patent Publication Nos. 5-13514 and 5-19702
The described pyrylium compounds, commercially available products include Epolight I
II-178, Epolight III-130, Epolight III-12
5. Epolight IV-62A (Eporin) is also preferred.
Yes. Further, the formula described in U.S. Pat.
Suitable near infrared absorbing dyes represented by (I) and (II)
Can be mentioned. Of the above, cyanine color
Element, squarylium dye, pyrylium salt, nickelthio
A rate complex is more preferred. More specifically, it is represented by the following general formula (Z).
Can be mentioned. [0027] In the general formula (Z), R^{twenty one}~ R^{twenty four}It
Each independently a hydrogen atom or an optionally substituted carbon
Prime number 1-12 alkyl group, alkenyl group, alkoxy
Group, cycloalkyl group, aryl group, R^{twenty one}When
R^{twenty two}, R^{twenty three}And R^{twenty four}Are bonded together to form a ring structure
May be. R^{twenty one}~ R^{twenty four}As, for example, a hydrogen atom,
Methyl group, ethyl group, phenyl group, dodecyl group, naphthy
Group, vinyl group, allyl group, cyclohexyl group, etc.
These groups may further have a substituent.
Yes. Here, as the substituent, for example, a halogen atom,
Carbonyl group, nitro group, nitrile group, sulfonyl group,
Carboxyl group, carboxylic acid ester, sulfonic acid ester
And the like. Where R^{twenty five}~ R³⁰Are each independently replaced
Represents an alkyl group having 1 to 12 carbon atoms which may have a group.
And R^{twenty five}~ R³⁰For example, methyl group, ethyl
Group, phenyl group, dodecyl group, naphthyl group, vinyl
Groups, allyl groups, cyclohexyl groups, etc., and these
This group may further have a substituent. Where
Examples of the substituent include a halogen atom, a carbonyl group,
Nitro group, nitrile group, sulfonyl group, carboxyl
Groups, carboxylic acid esters, sulfonic acid esters, etc.
It is done. Where R³¹~ R³³Are each independently hydrogen
Atoms, halogen atoms, or carbon atoms that may have a substituent
Represents an alkyl group of 1 to 8;³²R³¹Or
R³³To form a ring structure, and m> 2
If more than one R³²Are linked together to form a ring structure
May be. R³¹~ R³³For example, chlorine source
Child, cyclohexyl group, R³²Cyclo formed by bonding each other
Pentyl ring, cyclohexyl ring, etc., and these
The group may further have a substituent. Where replace
Examples of the group include a halogen atom, a carbonyl group, and a nitrogen group.
Toro group, nitrile group, sulfonyl group, carboxyl group,
Examples include carboxylic acid esters and sulfonic acid esters.
The M represents an integer of 1 to 8, with 1 to 3 being preferred.
Good. Where R³⁴~ R³⁵Are each independently hydrogen
Atoms, halogen atoms, or carbon atoms that may have a substituent
Represents an alkyl group of 1 to 8;³⁴Is R³⁵Combined with
May form a ring structure, and if m> 2,
R³⁴They may be bonded to each other to form a ring structure. Previous
R³⁴~ R³⁵For example, chlorine atom, cyclohex
Sil group, R³⁴Cyclopentyl ring formed by bonding together,
Chlorohexyl ring, etc., and these groups are further substituted.
It may have a substituent. Here, examples of the substituent include
For example, halogen atom, carbonyl group, nitro group, nitrile
Group, sulfonyl group, carboxyl group, carboxylic acid ester
And sulfonic acid esters. M
Represents an integer of 1 to 8, among which 1 to 3 is preferable. Where X^-Represents an anion, for example
Perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triiso
Propylnaphthalenesulfonic acid, 5-nitro-O-toluene
Ensulfonic acid, 5-sulfosalicylic acid, 2,5-dimethyl
Tylbenzenesulfonic acid, 2,4,6-trimethylben
Zensulfonic acid, 2-nitrobenzenesulfonic acid, 3-
Chlorobenzenesulfonic acid, 3-bromobenzenesulfone
Acid, 2-fluorocaprylnaphthalenesulfonic acid,
Decylbenzenesulfonic acid, 1-naphthol-5-sulfur
Phosphonic acid, 2-methoxy-4-hydroxy-5-benzoy
Ru-benzenesulfonic acid, paratoluenesulfonic acid, etc.
Is mentioned. Among them, hexafluorophosphoric acid, triisopro
Pyrnaphthalene sulfonic acid, 2,5-dimethylbenzene
Alkyl aromatic sulfonic acids such as sulfonic acids are preferred. Among the compounds represented by the general formula (Z),
However, specifically, the following compounds are preferably used.
However, the present invention is not limited to these.
Yes. [Chemical 2]The content of the infrared absorbing dye as described above
Is 0.01 to 5 based on the total solid mass of the image forming layer.
0% by mass is preferable, and 0.1-10% by mass is more preferable.
Furthermore, 0.5-10 mass% is the most preferable. Including
If the content is less than 0.01% by mass, the sensitivity may be lowered.
If it exceeds 50% by mass, the uniformity of the image forming layer
May decrease and its durability may deteriorate. -(B1) Alkaline having a carboxyl group
Re-soluble polymer compound (hereinafter referred to as “component (B1)”
There is also. ) (B1) Component polymer compound includes a carboxyl group
Any alkali-soluble polymer compound having
Although it is good, the high molecular compound (b1-1) defined below,
(B1-2) is preferred. (B1-1) A polymerizable monomer represented by the following general formula (1)
-Alkali-soluble polymer compound having a unit (hereinafter referred to as high
(Also referred to as molecular compound (b1-1))(Wherein Xm is a single bond or a divalent linking group, Y is hydrogen or
Is a carboxyl group, Z is hydrogen, alkyl group or carbo
Represents a xyl group. ) Constructs a polymerizable monomer unit represented by the general formula (1)
As monomers, carboxyl groups and polymerizable unsaturated
There are polymerizable monomers having at least one group in the molecule.
The Specific examples of such polymerizable monomers include acrylics.
Phosphoric acid, methacrylic acid, maleic acid, maleic anhydride,
Α, β-unsaturated carboxylic acids such as taconic acid and itaconic anhydride
Acids can be mentioned. Polymerizable monomer having a carboxyl group
As a monomer to be copolymerized with-, for example, the following (1) ~
(11), but is not limited to these.
Yes. (1) 2-hydroxyethyl acrylate or 2-hydroxy
Acyl having an aliphatic hydroxyl group such as
Rylic acid esters and methacrylic acid esters. (2) Methyl acrylate, ethyl acrylate, acrylic acid
Propyl, butyl acrylate, amyl acrylate, acrylic
Hexyl rillate, octyl acrylate, benzoic acid benzoate
Jill, 2-chloroethyl acrylate, glycidyl acrylate
Relate, N-dimethylaminoethyl acrylate, etc.
Alkyl acrylate. (3) Methyl methacrylate, ethyl methacrylate, methacrylate
Propyl propyl, butyl methacrylate, methacrylate
Mill, hexyl methacrylate, cyclohexyl methacrylate
Sil, benzyl methacrylate, methacrylic acid-2-chloro
Roethyl, glycidyl methacrylate, N-dimethyla
Alkyl methacrylates such as minoethyl methacrylate
G. (4) Acrylamide, methacrylamide,
N-methylolacrylamide, N-ethylacrylic
Mido, N-hexyl methacrylamide, N-cyclohex
Silacryl amide, N-hydroxyethyl acrylic
Mido, N-phenylacrylamide, N-nitropheny
Luacrylamide, N-ethyl-N-phenylacrylic
Acrylamide such as amide or methacrylamide. (5) Ethyl vinyl ether, 2-chloroethyl vinyl ether
Ether, hydroxyethyl vinyl ether, propyl vinyl
Nyl ether, butyl vinyl ether, octyl vinyl
Vinyl ethers such as ether and phenyl vinyl ether
Kind. (6) Vinyl acetate, vinyl chloroacetate, vinyl
Vinyl esters such as rubutylate and vinyl benzoate. (7) Styrene, α-methylstyrene, methylstyrene,
Styrenes such as chloromethylstyrene. (8) Methyl vinyl ketone, ethyl vinyl ketone
T, propyl vinyl ketone, phenyl vinyl ketone, etc.
Vinyl ketones. (9) Ethylene, propylene, isobutylene, butadiene
And olefins such as isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole,
4-vinylpyridine, acrylonitrile, methacryloni
Trill etc. (11) Maleimide, N-acryloylacrylamide, N
-Acetylmethacrylamide, N-propionylmetac
Rilamide, N- (p-chlorobenzoyl) methacryl
Unsaturated imides such as amides. Also preferred are monomers of general formula (2)
Used. Wherein X is O, S, or N—R¹²Represents. R^Ten~ R
¹²Each independently represents a hydrogen atom or an alkyl group.
m, n and o each independently represents an integer of 2 to 5;
_mH_2m, C_nH_2n, C_oH_2oAre each a straight chain or branched structure
But you can. p, q, and r are each independently 0 to 3,000.
P + q + r ≧ 2. R^Ten~ R¹²As the alkyl group in
Those having 1 to 12 carbon atoms are preferred.
Til, ethyl, n-propyl, isopropyl, etc.
And so on. p, q, r are preferably from 0 to 500
An integer of 0 to 100, more preferably an integer of 0 to 100
The Corresponds to the repeating unit represented by the general formula (2)
Although the example of a monomer is given below, it is not this limitation. [0041] [Chemical 3][0042] [Formula 4]The repeating unit represented by the general formula (2)
Is a commercially available hydroxypoly (oxyalkylene) material,
For example, the product name Pluronic (Asahi Denka Kogyo)
ADEKA polyether (Asahi Denka Kogyo Co., Ltd.)
Manufactured by Carbowax (Glico Product)
), Triton (Rohm and Haas)
(Rohm and Haas) and P.E.G (Daiichi Kogyo Seiyaku)
A product sold as
Kuryl acid, methacrylic acid, acrylic chloride, methacrylate
By reacting with luchloride or acrylic anhydride, etc.
Can be manufactured. Separately, poly (o
Xylalkylene) diacrylate can also be used
The Commercially available monomers include Nippon Oil & Fats Co., Ltd.
Company-made hydroxyl-terminated polyalkylene glycol mono (medium
B) Blemmer PE-90, Blemmer P as acrylate
E-200, Blemmer PE-350, Blemmer AE-90, Blemma
ー AE-200 、 Blemmer AE-400 、 Blemmer PP-1000 、
Lemmer PP-500, Bremmer PP-800, Bremmer AP-15
0, Blemmer AP-400, Blemmer AP-550, Blemmer A
P-800, Blemmer 50PEP-300, Blemmer 70PEP-350B,
BLEMMER AEP series, BLEMMER 55PET-400, blur
Nimmer 30PET-800, Blemmer 55PET-800, Blemmer AE
T series, Bremmer 30PPT-800, Bremmer 50PPT-80
0, Bremmer 70PPT-800, Bremmer APT series,
Renmer 10PPB-500B, Bremer 10APB-500B, etc.
It is done. Similarly, alkyl-terminated poly made by NOF Corporation
As alkylene glycol mono (meth) acrylate
Blemmer PME-100, Blemmer PME-200, Blemmer PM
E-400, Blemmer PME-1000, Blemmer PME-4000,
Lemmer AME-400, Bremmer 50POEP-800B, Bremmer
50AOEP-800B, Blemmer PLE-200, Blemmer ALE-20
0, Blemmer ALE-800, Blemmer PSE-400, Blemma
-PSE-1300, Blemmer ASEP series, Blemmer PKEP
Series, Blemmer AKEP series, Blemmer ANE-30
0, Bremmer ANE-1300, Bremmer PNEP series,
Lemmer PNPE series, Bremmer 43ANEP-500, Blen
MER 70ANEP-550 etc., and Kyoeisha Chemical Co., Ltd. Light
Ester MC, light ester 130MA, light ester 041
MA, light acrylate BO-A, light acrylate EC-
A, light acrylate MTG-A, light acrylate 130
A, Light acrylate DPM-A, Light acrylate P-20
0A, light acrylate NP-4EA, light acrylate NP
-8EA. Carbo in polymer compound (b1-1)
Xyl group and polymerizable unsaturated group in the molecule
Minimum structural unit having one or more polymerizable monomer components
Does not have to be one kind in particular, and has the same acidic group
2 or more minimum structural units having different acidic groups
Use a copolymer of two or more minimum structural units
You can also. Conventionally known copolymerization methods
Graft copolymer, block copolymer, random copolymer
The method etc. can be used. (B1-2) The following having a carboxyl group
Diol represented by general formula (3), (4) or (5)
Compound and diisocyanate represented by the following general formula (8)
Carboxyl group with reaction product with compound as basic skeleton
Alkali-soluble polymer compound (hereinafter referred to as “polymerization”)
Also referred to as compound (b1-2). ) [0047]In the above formula, R¹³Is a hydrogen atom, a substituent (eg alkyl,
Aryl, alkoxy, ester, urethane, amide,
Ureido and halogeno groups are preferred. )
May be alkyl, alkenyl, aralkyl, aryl,
An alkoxy or aryloxy group, preferably a hydrogen atom
Child, alkyl group having 1 to 8 carbon atoms or carbon atom
An alkenyl group having 2 to 8 carbon atoms and an ant having 6 to 15 carbon atoms
Represents an alkyl group. R¹⁴, R¹⁵, R¹⁶Are the same but
May be different, single bond, substituent (eg alkyl,
Alkenyl, aralkyl, aryl, alkoxy and ha
Each group of Logeno is preferred. ) Which may have
Indicates an aliphatic or aromatic hydrocarbon. Preferably a carbon atom
An alkylene group having 1 to 20 carbon atoms, an ant having 6 to 15 carbon atoms
-Lene group, more preferably an alkyl having 1 to 8 carbon atoms.
Rene group is shown. If necessary, R¹⁴, R¹⁵, R¹⁶During ~
Other functional groups that do not react with isocyanate groups, e.g.
Steal, urethane, amide, ureido, carbon-
It may have a carbon unsaturated bond. R¹³,
R¹⁴, R¹⁵, R¹⁶Even if two or three of them constitute a ring
Good. Ar is a trivalent aromatic carbon which may have a substituent.
A hydrogen fluoride, preferably an aromatic having 6 to 15 carbon atoms
Indicates a group. OCN-R¹⁸-NCO (8) Where R¹⁸Is a substituent (eg alkyl, alkenyl,
Aralkyl, aryl, alkoxy, and halogeno groups are preferred
Good. ) May be divalent aliphatic or aromatic
Indicates hydrocarbon. R if necessary¹⁸Isocyanate in
Other functional groups that do not react with groups, eg esters, ureta
, Amide, ureido group, carbon-carbon unsaturated bond
It may be. It is represented by the general formula (3), (4) or (5)
Specific examples of diol compounds having a carboxyl group
Includes the following: That is, 3,5-dihydride
Loxybenzoic acid, 2,2-bis (hydroxymethyl) propyl
Lopionic acid, 2,2-bis (2-hydroxyethyl) propyl
Lopionic acid, 2,2-bis (3-hydroxypropyl)
Propionic acid, bis (hydroxymethyl) acetic acid, bis
(4-Hydroxyphenyl) acetic acid, 4,4-bis (4-
Hydroxyphenyl) pentanoic acid, tartaric acid, N, N-bi
(2-hydroxyethyl) -3-carboxy-propi
And onamide. (B1-2) having a carboxyl group
The alkali-soluble polymer compound is represented by the following general formula (6) or
(7) is a reaction product that combines the diol represented by
It is preferable. Where R¹⁷Are each a hydrogen atom or 1-8 carbon atoms
Represents an alkyl group, and n represents an integer of 2 or more. R¹⁷In
Examples of the alkyl group having 1 to 8 carbon atoms include
Til, ethyl, i-propyl, n-butyl, i-butyl
And the like. In the following, the general formula (6) or
Specific examples of the diol represented by (7) are shown below.
It is not limited to these. Specific example of formula (6) HO-(-CH₂CH₂O-)_Three-H HO-(-CH₂CH₂O-)_Four-H HO-(-CH₂CH₂O-)_Five-H HO-(-CH₂CH₂O-)₆-H HO-(-CH₂CH₂O-)₇-H HO-(-CH₂CH₂O-)₈-H HO-(-CH₂CH₂O-)_Ten-H HO-(-CH₂CH₂O-)₁₂-H Polyethylene glycol (average molecular weight 1000) Polyethylene glycol (average molecular weight 2000) Polyethylene glycol (average molecular weight 4000) HO-(-CH₂CH (CH_Three) O-)_Three-H HO-(-CH₂CH (CH_Three) O-)_Four-H HO-(-CH₂CH (CH_Three) O-)₆-H Polypropylene glycol (average molecular weight 1000) Polypropylene glycol (average molecular weight 2000) Polypropylene glycol (average molecular weight 4000) Specific example of formula (7) HO-(-CH₂CH₂CH₂O-)_Three-H HO-(-CH₂CH₂CH₂O-)_Four-H HO-(-CH₂CH₂CH₂O-)₈-H HO-(-CH₂CH₂CH (CH_Three) O-)₁₂-H Diisocyanation represented by the general formula (8)
Specific examples of the compound include those shown below. You
That is, 2,4-tolylene diisocyanate, 2,4-
Dimer of tolylene diisocyanate, 2,6-tolylene
Diisocyanate, p-xylylene diisocyanate,
m-xylylene diisocyanate, 4,4'-dipheni
Lumethane diisocyanate, 1,5-naphthalene diiso
Cyanate, 3,3'-dimethylbiphenyl-4,4 '
-Aromatic diisocyanates such as diisocyanates
Compound; hexamethylene diisocyanate, trimethyl
Hexamethylene diisocyanate, lysine diisocyanate
Aliphatic diesters such as
Isocyanate compounds, isophorone diisocyanate,
4,4'-methylenebis (cyclohexylisocyanate
G), methylcyclohexane-2,4 (or 2,6)-
Diisocyanate, 1,3- (isocyanate methyl)
Aliphatic diisocyanate compounds such as cyclohexane
Product; 1 mol of 1,3-butylene glycol and tolylene di
Diols and dimers such as adducts with 2 moles of cyanate
Diisocyanate compound that is a reaction product with isocyanate
Such as things. Used for the synthesis of polymer compound (b1-2)
The molar ratio of diisocyanate and diol compound is preferred.
Or 0.8: 1 to 1.2 to 1 at the end of the polymer.
If isocyanate groups remain, alcohols or alcohol
Isocyanate is finally treated by treatment with mines.
Is synthesized in such a way that no radical remains. As the component (B1), the above polymer compound
Using one kind alone from (b1-1) and (b1-2)
Alternatively, two or more kinds may be used in combination. (B1) completion
Repeating unit having a carboxyl group contained in a minute
The content of is based on the total amount of each monomer of the component (B1)
2 mol% or more, preferably 2 to 70 mol%
More preferably, it is the range of 5-60 mol%. (B
1) The preferred weight average molecular weight of the component is 3000-30.
0.00 is preferred, 6,000 to 100,000 are
More preferred. Furthermore, a preferable addition amount of the component (B1)
Is 0.005 to 8 based on the total solid mass of the image forming layer
The range is 0% by mass, preferably 0.01 to 50% by mass.
%, More preferably in the range of 1-20% by weight
It is. (B1) Component addition amount is not 0.0005 mass%
If it is full, the effect is insufficient, and more than 80% by mass.
If this happens, the coating film will not dry sufficiently or
The material performance (eg sensitivity) is adversely affected. -(B2) Alkali-soluble resin- Usable alkali-soluble resin (hereinafter referred to as “(B2)
Sometimes it is "minute". ) As the following (1) ~
(3) Acid group in main chain and / or side chain structure
Alkaline water-soluble polymer compounds can be used
The (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 has a substituent.
Represents a divalent aryl linking group which may be
The hydrocarbon group which may have a substituent is represented. The following
Specific examples are shown below, but the present invention is not limited to these.
Is not something (1) Alkali-soluble with a phenol group
Examples of the functional polymer compound include phenol and form.
Condensation polymer with aldehyde, m-cresol and formal
Condensation polymer with aldehyde, p-cresol and formaldehyde
A polycondensation polymer with m- / p-mixed cresol and formua
Condensation polymer with aldehyde, phenol and cresol (m
Any of-, p- or m- / p-mixing may be used. ) And ho
Novolac resin such as condensation polymer with rumaldehyde or
Mention may be made of condensation polymers of rogalol and acetone.
The In addition, monomers with phenol groups in the side chain
There may also be mentioned combined polymer compounds. Polymer having a phenolic hydroxyl group in the side chain
Compounds include unsaturated polymers that can polymerize with phenolic hydroxyl groups.
Consists of low-molecular compounds each having one or more sum bonds
Homopolymerization of a polymerizable monomer, or the polymerizable monomer
Polymerization obtained by copolymerizing with other polymerizable monomers
Compound may be mentioned. Monomers having a phenol group in the side chain
As for acrylamido having a phenol group in the side chain.
, Methacrylamide, acrylic ester, methacrylate
Examples of the acid ester include hydroxyester and hydroxystyrene. Specifically, N- (2-hydroxypheny
E) Acrylamide, N- (3-hydroxyphenyl)
Acrylamide, N- (4-hydroxyphenyl) aqua
Rilamide, N- (2-hydroxyphenyl) methacryl
Luamide, N- (3-hydroxyphenyl) methacryl
Amide, N- (4-hydroxyphenyl) methacrylamide
Imide, o-hydroxyphenyl acrylate, m-hydride
Roxyphenyl acrylate, p-hydroxyphenyl
Acrylate, o-hydroxyphenyl methacrylate
, M-hydroxyphenyl methacrylate, p-hydride
Roxyphenyl methacrylate, o-hydroxystyrene
, M-hydroxystyrene, p-hydroxystyrene
2- (2-hydroxyphenyl) ethyl acrylate
2- (3-hydroxyphenyl) ethyl acrylate
2- (4-hydroxyphenyl) ethyl acrylate
2- (2-hydroxyphenyl) ethyl methacrylate
2- (3-hydroxyphenyl) ethyl methacrylate
Rate, 2- (4-hydroxyphenyl) ethyl methacrylate
Preferable examples include relation. Alkali soluble having the phenol group
The weight average molecular weight of the polymer compound is 5.0 × 10
²~ 2.0 × 10^FiveAs for the number average molecular weight,
2.0 × 10²~ 1.0 × 10^FiveThat is image-forming
This is preferable. Alkaline with phenol group
Soluble polymer compounds are not only used alone but also two types
The above may be used in combination. When combining
Is described in U.S. Pat. No. 4,123,279.
Such as t-butylphenol and formaldehyde
Condensation polymers of octylphenol and formaldehyde
An alkyl group having 3 to 8 carbon atoms, such as a condensation polymer with
Condensation of phenol and formaldehyde as a substituent
A polymer may be used in combination. These condensation polymers are also
Average molecular weight is 5.0 × 10²~ 2.0 × 10^FiveThings, few
Average molecular weight 2.0 × 10²~ 1.0 × 10^FiveLike things
That's right. (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. [0063] Where X¹, X²Each independently
Child or NR⁷Represents. R¹, R^FourAre each independently hydrogen
Atom or CH_ThreeRepresents. R², R^Five, R⁹, R¹², R¹⁶Is
1 to 1 carbon atoms that may each independently have a substituent
2 alkylene group, cycloalkylene group, arylene group
Or represents an aralkylene group. R^Three, R⁷, R¹³Is that
Independently, a hydrogen atom and optionally having 1 substituent
~ 12 alkyl groups, cycloalkyl groups, aryl groups or
Represents an aralkyl group. R⁶, R¹⁷Respectively
C 1-12 al which may have a substituent independently
Kill group, cycloalkyl group, aryl group, aralkyl group
Represents. R⁸, R^Ten, R¹⁴Are independently hydrogen atoms
Or CH_ThreeRepresents. R¹¹, R¹⁵Are each independent
Or an alkyl having 1 to 12 carbon atoms which may have a substituent
A xylene group, a cycloalkylene group, an arylene group or ara
Represents a ruxylene group. Y¹, Y²Are each independently a single bond or
Represents CO. Among them, m-aminosulfonylphenyl meta
Acrylate, N- (p-aminosulfonylphenyl)
Tacrylamide, N- (p-aminosulfonylpheny
E) Acrylamide and the like can be preferably used. (3) Alkali-soluble with an active imide group
Examples of the functional polymer compound include an active imide group
A polymer whose main monomer constituent unit is
Can be. Mainly compounds with active imide groups
As a polymer as a monomer constituent unit, in one molecule,
An active imide group represented by the following formula and a polymerizable unsaturated bond
Mono-comprising low molecular weight compounds each having one or more
Homopolymerization of the monomer, or other polymerizable monomers
List polymer compounds obtained by copolymerization of mer
Can do. [0067] 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 resin has the acidic group (1).
Monomer constituting unit having any one selected from (3)
And other structural units of polymerizable monomers
In the case of a copolymer, the acidic group in the copolymer
Monomer having any one selected from (1) to (3)
It is preferable to contain 10 mol% or more of structural units,
More preferably, it is contained in excess of 1%. Monomer constituent unit
If the content of the position is less than 10 mol%, sufficient
The development latitude is reduced without re-solubility.
There is. As a method for synthesizing the copolymer, conventionally,
Known graft copolymerization method, block copolymerization method, random
A copolymerization method or the like can be used. Selected from the acidic groups (1) to (3)
Polymerizable monomer comprising monomer having a difference
Examples of other polymerizable monomers copolymerized with
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 and methacrylamid
, N-methylolacrylamide, N-ethylacryl
Luamide, N-hexyl methacrylamide, N-cyclo
Hexyl acrylate amide, N-hydroxyethyl acrylate
Luamide, N-phenylacrylamide, N-nitrof
Phenyl acrylamide, N-ethyl-N-phenyl acrylate
Acrylamide such as rilamide, or methacrylamid
De. (E) Ethyl vinyl ether, 2-chloroethyl vinyl
Ether, hydroxyethyl vinyl ether, propyl
Vinyl ether, butyl vinyl ether, octyl vinyl
Vinyl ethers such as ruether and phenyl vinyl ether
Le. (F) Vinyl acetate, vinyl chloroacetate, vinyl
Vinyl esters such as nilbutyrate and vinyl benzoate
Kind. (G) Styrene, α-methylstyrene, methylstyrene
And styrenes such as chloromethylstyrene. (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 alkali-soluble resin, single weight is used.
Regardless of the polymer or copolymer, the weight average
A molecular weight of 2000 or more and a number average molecular weight of 500 or more
Is preferred, and the weight average molecular weight is 5,000 to 30,000.
0, number average molecular weight is 800-250,000, dispersed
The degree (weight average molecular weight / number average molecular weight) is 1. .1-10
Are more preferred. The alkali-soluble resin
Is phenol-formaldehyde resin, cresol-
In the case of an aldehyde resin or the like, the weight average molecular weight is 5
It is 00-20000, and the number average molecular weight is 200-1
Those of 0000 are preferred. As the content of the alkali-soluble resin,
Is 30 to 99 mass relative to the total solid mass of the image forming layer
% Is preferable, 40 to 95 mass% is more preferable, 50
-90% by weight is most preferred. The content is 30 mass
If it is less than%, the durability of the image forming layer may decrease.
Yes, if it exceeds 99% by mass, the sensitivity and durability will decrease.
Sometimes. The alkali-soluble resin is one kind.
Can be used alone or in combination of two or more
Yes. -(C) a containing the carboxyl group
Lucari-soluble polymer and alkali-soluble resin
The aqueous solution of the polymer compound and the resin
Reduces solubility in liquid and dissolves by heating
Compound with reduced activity--this component (C) is a molecule
By the action of the hydrogen bonding functional group present in the
Good compatibility with the components (B1) and (B2)
A single coating solution for an image forming layer can be formed, and the (B
1) and (B2) due to the interaction with component (B1)
And (B2) the function of inhibiting alkali solubility of the component (soluble
It refers to a compound having a degrading inhibitory action. Further, (B1) and (B2) can be formed by heating.
The above-mentioned solubility-inhibiting effect on the minute disappears, but infrared absorption
When the collector itself is a compound that decomposes by heating,
Enough energy for decomposition, laser output, irradiation time, etc.
(B1) and (B2)
Can sufficiently reduce the solubility-inhibiting action of ingredients
Therefore, the sensitivity may be reduced. For this reason, (C)
The thermal decomposition temperature of the minute is preferably 150 ° C. or higher. As the component (C), the above (B1) and
Considering the interaction with the component (B2), for example, sulfo
Compounds, ammonium salts, phosphonium salts, amidation
Interaction with the alkali-soluble polymer compound such as a compound
Can be suitably selected from the possible compounds.
Arrangement of component (C) with component (B1) and component (B2)
The ratio (C / (B1 + B2) mass ratio) is generally 1
/ 99 to 25/75 is preferable. The above (A) red
The compound represented by the general formula (Z) described for the external absorption dye
Has the action of the component (C), for example, the general formula (Z)
By using a cyanine dye as shown in (A)
Can exert both effects of component and component (C)
The -(D) Cyclic acid anhydride- Further, a cyclic acid anhydride may be used in the image forming layer.
Yes. The cyclic acid anhydride has a carboxylic acid anhydride in its structure.
Having a bond conjugated to the carbonyl group of
By controlling the degradation rate by increasing the stability of the group,
The acid decomposes at an appropriate rate. for that reason,
Suppresses developability during storage and stabilizes developability for a long time
Can be maintained. As the cyclic acid anhydride, the following general formula
The compound represented by (9) or (10) is mentioned. [0081] In the general formula (9), 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, R⁴²For 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 (10), 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, hex
Sahydrophthalic anhydride, 3,6-endooxy-Δ^Four−
Tetrahydrophthalic anhydride, tetrachlorophthalic anhydride
Acid, 3-hydroxyphthalic anhydride, 3-methylphthalic anhydride
Phosphoric acid, 3-phenylphthalic anhydride, trimellitic anhydride
Acid, pyromellitic anhydride, maleic anhydride, no phenyl
Maleic anhydride, dimethylmaleic anhydride, dichloroanhydride
Maleic acid, chloromaleic anhydride, succinic anhydride,
Are preferred. As content of cyclic acid anhydride
Is 0.5 to 20 quality with respect to the total solid content of the image forming layer.
% By weight is preferred, 1-15% by weight is more preferred,
10% by mass is most preferred. The content is 0.5% by mass
If the amount is less than 1, the developability maintenance effect may be insufficient.
If it exceeds 20% by mass, images may not be formed.
The -Other components- If necessary, the image forming layer of the lithographic printing plate precursor
Various additives can be added. For example, sensitivity
Phenols, organic acids, sulfo
Known additives such as nil compounds can be used in combination.
The Phenols include bisphenol A, p-ni
Trophenol, p-ethoxyphenol, 2,4,
4'-trihydroxybenzophenone, 2,3,4-to
Lihydroxybenzophenone, 4-hydroxybenzofu
Enon, 4,4 ', 4 "-trihydroxytriphenyl
Methane, 4,4 ', 3 ", 4" -tetrahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane
Etc. 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
Addition of phenols, organic acids or sulfonyl compounds
The amount of addition is 0. 0 to the total solid mass of the image forming layer.
05-20% by mass is preferable, 0.1-15% by mass is good
More preferably, 0.1-10 mass% is the most preferable. Further, the stability of the processability with respect to the development conditions is improved.
For the purpose of expanding, JP-A-62-251740, JP-A-6-251740
Nonionic surface activity described in Japanese Patent Laid-Open No. 3-208514
Agent, JP-A-59-121044, JP-A-4-1314
Amphoteric surfactant described in No. 9 publication, etc., EP950517
Siloxane compounds such as those described in
As described in Kaihei 11-288093
Fluorine-containing monomer copolymer can be added
The Examples of nonionic surfactants include sorbitant
Restearate, sorbitan monopalmitate, sorbi
Tantrioleate, stearic acid monoglyceride, poly
Such as oxyethylene nonylphenyl ether
The Examples of amphoteric surfactants include alkyldi (amido).
Noethyl) glycine, alkylpolyaminoethylglyci
Hydrochloride, 2-alkyl-N-carboxyethyl-N-
Hydroxyethylimidazolinium betaine, N-teto
Radecyl-N, N-betaine type (for example, trade name: AMOR
Gen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. Shiroki
Sun compounds include dimethylsiloxane and polyal
Preference is given to block copolymers of xylene oxide, specific examples
As a product of Chisso Corporation, DBE-224, DBE-6
21, DBE-712, DBP-732, DBP-53
4. Polyalkylene such as Tego Glide 100 made by Tego, Germany
Mention may be made of oxide-modified silicones. Above
Use amount of nonionic surfactant or amphoteric surfactant
Is 0.05 to 15 based on the total solid mass of the image forming layer.
% By mass is preferable, and 0.1 to 5% by mass 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.
0.01 to 10% by mass is preferable based on the mass of the part,
0.1-3 mass% is more preferable. If necessary, the coating film can be flexible.
For the purpose of imparting, a plasticizer can be added. OK
Examples of plasticizers include butylphthalyl and polyethylene group.
Recall, tributyl citrate, diethyl phthalate,
Dibutyl tartrate, dihexyl phthalate, dioctyl phthalate
Chill, tricresyl phosphate, tributyl phosphate, phosphoric acid
Trioctyl, tetrahydrofurfuryl oleate, a
Such as oligomers and polymers of crylic acid or methacrylic acid
And so on. If necessary, the following various additives can be added.
Can be added. For example, onium salt, o-kino
Diazide compounds, aromatic sulfone compounds, aromatic sulfones
In pyrolytic and undecomposed state, such as phosphonate compounds
Substantially reduces the solubility of alkaline water-soluble polymer compounds
A compound to be reduced can be used in combination. Addition of the compound
Is to improve the ability to prevent dissolution of the image area in the developer.
preferable. Examples of the onium salt include diazonium.
Salt, ammonium salt, phosphonium salt, iodonium
Salt, sulfonium salt, selenonium salt, arsonium salt
Etc. Among them, for example, S.I.Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al,
Polymer, 21, 423 (1980), JP-A-5-158230
The diazonium salts described in the publication, US Pat. No. 4,069,
No. 055, No. 4,069,056, JP-A-3-140
Ammonium salt described in No. 140, D. C. Necker et a
l, Macromolecules, 17, 2468 (1984), C. S. Wen et a
l, The Proc. Conf. Rad. Curing ASIA, p478 Tokyo, O
ct (1988), U.S. Pat. No. 4,069,055, 4,
Phosphonium salts described in No. 069,056, J. V. Criv
elloet et al. Macromolecules, 10 (6), 1307 (1977),
Chem. & Eng. News, Nov. 28, p.31 (1988), European patent
No. 104,143, US Pat. No. 339,049,
No. 410,201, JP-A-2-150848, JP-A-2-150848
An iodonium salt described in JP-A-2-296514, J. V. Crivello et al, Polymer J. 17, 7
3 (1985), J. V. Crivello et al, J. Org. Chem., 43,
3055 (1978), W.R, Watt et al, J. Polymer Sci., Po
lymerChem. Ed., 22, 1789 (1984), J. V. Crivello et
 al, Polymer bull., 14, 279 (1985), J. V. Crivello
 et al, Macromolecules, 14 (5), 1141 (1981), J.V.Cr
ivello et al, J. Polymer Sci., Polymer Chem. Ed.,
17. 2877 (1979), European Patent No. 370,693, 2
33,567, 297,443, 297,44
2, U.S. Pat. Nos. 4,933,377 and 3,90
2,114, 410,201, 399,049
No. 4,760,013, No. 4,734,444
No. 2,833,827, German Patent No. 2,904
626, 3,604,580, 3,604,5
The sulfonium salt according to No. 81, J. V. Crivello et al, Macromolecules,
10 (6), 1307 (1977), J.V.Crivelloet al, J. Polymer
 Sci., Polymer Chem. Ed., 17, 1047 (1979)
Selenonium salt, C. S. Wen et al, The Proc. Conf. R
ad. Curing ASIA, p.478, Tokyo, Oct (1988)
Examples include arsonium salts. Of the above, diazo
Nilium salts are preferred, and above all, JP-A-5-158230.
More preferred are those described in Japanese Patent Publication. The counter ion of the onium salt is tetrafluoride.
Boric acid, hexafluorophosphoric acid, triisopropylnaphthalene
Sulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfo
Acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfuric acid
Phosphonic acid, 3-bromobenzenesulfonic acid, 2-fluoro
Capryl naphthalene sulfonic acid, dodecyl benzene sul
Phosphonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy
Ci-4-hydroxy-5-benzoyl-benzenesulfo
Acid, paratoluenesulfonic acid, etc.
it can. Among them, hexafluorophosphate, triisopropyl na
Phthalenesulfonic acid, 2,5-dimethylbenzenesulfone
Alkyl aromatic sulfonic acids such as acids are preferred. As the o-quinonediazide compound,
Compound having at least one o-quinonediazide group
And those that increase alkali solubility by thermal decomposition.
In addition, compounds having various structures can be used. O
-Quinonediazide has the ability to inhibit the dissolution of the binder by thermal decomposition.
And o-quinonediazide itself is alkali-soluble
Lithographic printing plate precursor due to both effects
Help solve. O-quinonediazide compounds as described above and
For example, J. et al. By Korser "Light-Sensity
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 with respect to the total solid content 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
The total solid content of the image forming layer is 0.1-10.
% By mass is preferable, and more preferably 0.5 to 5% by mass.
is there. In addition, for the purpose of imparting resistance to scratches,
It is also possible to add compounds that reduce the static friction coefficient of the surface.
Yes. Specifically, US Pat. No. 6,117,913
Of long-chain alkyl carboxylic acids as disclosed in
Tell. Preferred as its addition amount
The reason is that 0.1 to 1 relative to the total solid mass of the image forming layer.
0% by mass, more preferably 0.5-5% by mass
The In addition, for the purpose of adjusting the solubility of the image forming layer,
A dissolution inhibitor may be included. As a dissolution inhibitor, JP
Disulfur as described in JP-A-11-119418
Hong compounds or sulfone compounds are preferably used.
Using 4,4'-bishydroxyphenyl sulfone as an example
It is preferable. The preferred addition amount is
0.05 to 20% by mass relative to the total solid mass of the image forming layer
Yes, more preferably 0.5 to 10% by mass. A planographic printing plate to which the plate making method of the present invention can be applied
As a specific example of the original version, in Japanese Patent Application No. 2000-378507
A positive-type heat-sensitive layer having a two-layer structure as an image forming layer as disclosed
Also included are lithographic printing plate precursors. That is, this positive feeling
The thermal layer has a laminated structure and is set at a position close to the surface (exposed surface).
On the side close to the support.
Alkali-soluble resin, alkali-soluble polymer compound
It has the lower layer to contain, It is characterized by the above-mentioned. The thermosensitive layer and
(A) Infrared rays that have been described above for both or one of the lower layers
Absorbing dye, (B1) Alkali having carboxyl group
Soluble polymer compound, (B2) alkali-soluble resin,
(C) Alkali-soluble polymer of (B1) and (B2)
The alkali-soluble polymer compound is dissolved in a compound.
It reduces the solubility in aqueous solution of Lucari and at the same time for heating
Compounds that reduce the solubility-lowering effect, other components
Etc. can be contained. Al used in the lower layer
As potash-soluble resin, acrylic resin has a buffering action.
Alkali development based on organic compounds and bases
Because it can maintain good solubility of the lower layer in the liquid, development
This is preferable from the viewpoint of image formation. Furthermore this acrylic
A resin having a sulfoamide group is particularly preferred.
Yes. In addition, alkali-soluble resin used in the heat-sensitive layer
As a result, strong hydrogen bonding occurs in the unexposed areas and
In some cases, some hydrogen bonds are easily released.
In particular, a resin having a phenolic hydroxyl group is desirable. Even better
Preferably it is a novolac resin. Infrared absorbing dye
It can be added not only to the thermal layer but also to the lower layer. Underlayer
By adding an infrared absorbing dye to the lower layer as a heat sensitive layer
Can function. Infrared absorbing dye added to the lower layer
If you want to do the same thing as in the upper thermal layer
May be used, or different ones may be used. Other
The additive may be included only in the lower layer, or only the heat-sensitive layer
May be included in both layers.
Yes. The image forming layer of the planographic printing plate precursor (the above two-layer structure)
In addition, the above components are dissolved in a solvent to give appropriate support.
It can be applied on the carrier. Examples of solvents include
Tylene dichloride, cyclohexanone, methyl ethyl
Ketone, methanol, ethanol, propanol, ethyl
Lenglycol monomethyl ether, 1-methoxy-2
-Propanol, 2-methoxyethyl acetate, 1-
Methoxy-2-propyl acetate, dimethoxyethane
, Methyl lactate, ethyl lactate, N, N-dimethylacetate
Amides, N, N-dimethylformamide, tetramethyl
Urea, N-methylpyrrolidone, dimethylsulfoxy
, Sulfolane, α-butyrolactone, toluene, etc.
Although it is mentioned, it is not limited to these. Above
A solvent may be individual or may mix 2 or more types. When the image forming layer has a two-layer structure, the heat-sensitive layer
Alkali-soluble resin used for coating and alkali used for lower layer
It is preferable to select ones with different solubility for soluble resins
That's right. In other words, after applying the lower layer, adjacent to the upper layer
When applying a heat-sensitive layer
Use a solvent that can dissolve the alkali-soluble resin of the layer
In the extreme case, mixing at the layer interface cannot be ignored.
There is a case where it becomes a uniform single layer without becoming a multilayer.
For this reason, the solvent used to apply the upper thermosensitive layer is
It is a poor solvent for the alkali-soluble resin contained in the lower layer.
It is preferable. 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 50% 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 forming layer is generally 0.
5 to 5.0 g / m²Is preferred. For a two-layer structure
The heat sensitive layer is 0.05 to 1.0 g / m²And the lower layer is
0.3-3.0 g / m²It is preferable that Application amount
As the value decreases, the apparent sensitivity increases.
The film properties of the image forming layer are reduced. One to apply on support
As a method, it can select suitably from well-known various methods.
For example, bar coater coating, spin coating, spray coating
Cloth, curtain coating, dip coating, air knife coating,
Grade coating, roll coating and the like can be mentioned.
In the coating solution for the image forming layer, a boundary is formed for the purpose of improving the coating property.
Surfactant, for example, described in JP-A-62-170950
The above-mentioned fluorine-based surfactants can be added.
The amount added is based on the total solid mass of the image forming layer.
0.01 to 1 mass% is preferable, 0.05 to 0.5 quality
The amount% is more preferable. A lithographic printing plate source prepared as described above
The plate can be recorded with infrared laser, UV
Lamp recording or thermal recording with a thermal head
Is also possible. The infrared laser has a wavelength of 700
Laser that emits infrared light of ~ 1200nm is preferred
A solid-state laser that emits infrared light in the same wavelength range
A conductor laser is more preferable. The exposed lithographic printing plate precursor is developed and processed.
The The developer used in the present invention is an alkaline aqueous solution.
Thus, it can be appropriately selected from conventionally known alkaline aqueous solutions.
You can. As alkaline aqueous solution, alkali silicate
Or a developer comprising a non-reducing sugar and a base.
Particularly preferred are those having a pH of 12.5 to 14.0. Ke
Alkali acid is alkaline when dissolved in water
For example, sodium silicate, silicate potassium
Alkali metal silicates such as lithium and lithium silicate,
Examples include ammonium silicate. Alkali silicate
May be used alone or in combination of two or more
Yes. The alkaline aqueous solution is a silicate component.
Some silicon oxide SiO₂And alkali oxide M₂O (M is a
Represents a Lucari metal or ammonium group. Mixing ratio with
The developability can be easily adjusted by adjusting the rate and density.
You can. Among the alkaline aqueous solutions, the oxidation catalyst
Ion SiO₂And alkali oxide M₂Mixing ratio with O (Si
O₂/ M₂O: molar ratio) of 0.5 to 3.0 is preferred
More preferably 0.75 to 1.5. Si
O₂/ M₂When O is less than 0.5, the alkali strength is strong.
Therefore, a general-purpose assembly is used as a support for lithographic printing plate precursors.
Detrimental effects such as etching of luminium plates
If it exceeds 3.0, developability deteriorates.
Sometimes. Further, the concentration of alkali silicate in the developer and
1 to 10% by mass with respect to the mass of the aqueous alkali solution
Is preferable, 3 to 8% by mass is more preferable, and 4 to 7% by mass.
% Is most preferred. If this concentration is less than 1% by weight,
Image quality and processing capacity may be reduced. Over 10% by mass
It tends to form precipitates and crystals,
Gelling easily during neutralization, hindering waste liquid treatment
There are times. In a developer comprising a non-reducing sugar and a base
Non-reducing sugars have free aldehyde groups and ketone groups.
Means a non-reducing saccharide because
Trehalose-type oligosaccharides bound by a person, saccharide reducing groups and non-
Glycosides linked to sugars, sugars reduced by hydrogenation of sugars
Classified as alcohol. In the present invention, both of these
It can be used suitably. Trehalose type oligosaccharide
Examples include sucrose and trehalose,
Examples of the glycoside include alkyl glycosides and phenols.
For example, le glycosides and mustard oil glycosides. Sugar Arco
For example, D, L-arabit, rebit,
Xylit, D, L-Sorbit, D, L-Mannic
D, L-exit, D, L-talit, slippery
And allozul sit. Furthermore, disaccharide
Of maltitol and oligosaccharides obtained by hydrogenation
Preferred examples include reduced form (reduced water candy) obtained by addition.
Can be. Among the above, as non-reducing sugar, sugar alcohol
And saccharose are preferred, and in particular, D-sol
Bit, saccharose, and reduced water candy in moderate pH range
It is more preferable in that it has a buffering action. These non-reducing sugars
It can be used alone or in combination of two or more.
The proportion occupied is preferably 0.1 to 30% by mass.
-20 mass% is more preferable. To the alkali silicate or non-reducing sugar
As appropriate, an alkali agent as a base is appropriately selected from conventionally known substances.
You can select and combine them. As the alkaline agent
For example, sodium hydroxide, potassium hydroxide, hydroxide
Lithium iodide, trisodium phosphate, tripotassium phosphate,
Triammonium phosphate, disodium phosphate, diphosphate
Potassium, diammonium phosphate, sodium carbonate, charcoal
Potassium acid, ammonium carbonate, sodium bicarbonate,
Potassium bicarbonate, ammonium bicarbonate, sodium borate
No such as lithium, potassium borate, ammonium borate
Alkaline agent, potassium citrate, tripotassium citrate
And sodium citrate. Further, monomethylamine and dimethylamino
, Trimethylamine, monoethylamine, diethylamine
Min, triethylamine, monoisopropylamine, di
Isopropylamine, triisopropylamine, n-butyl
Tylamine, monoethanolamine, diethanolamine
, Triethanolamine, monoisopropanolamine
, Diisopropanolamine, ethyleneimine, ethyl
Organic alkali agents such as range amine and pyridine are also suitable.
Can be mentioned. These alkaline agents are used alone
Alternatively, two or more kinds may be used in combination. Above all water
Sodium oxide and potassium hydroxide are preferred. The reason
Adjusts the amount of non-reducing sugar added
This is because the pH can be adjusted in a high pH range.
In addition, trisodium phosphate, tripotassium phosphate, sodium carbonate
Thorium, potassium carbonate, etc. have their own buffering effect.
Therefore, it is preferable. As a developer, as described above, an aluminum silicate
Use developer containing potash or non-reducing sugar and base
However, as its cation component, Li⁺, Na⁺, K
⁺, NH_Four ⁺In particular, a small ion radius
In systems containing a large amount of thione, the permeability to the image forming layer is low.
Highly developable, but dissolves to the image area and causes image defects
Is produced. Therefore, to increase the alkali concentration,
There is a limit of the degree, without causing defects in the image area, and
Complete so that the image forming layer (residual film) does not remain in the non-image area
Therefore, it is necessary to set delicate liquid conditions.
It was. However, as the cation component, its ionic radius
Into the image-forming layer by using large cations
Can suppress the permeability of the developer,
Degree, i.e., dissolution of the image area without reducing developability.
The deterrent effect can also be improved. The cation formation
The above-mentioned alkali metal cation and ammonium
In addition to muon, other cations can be used. In the developer used in the present invention, an interface is further added.
An activator can be added. Non-surfactant
Ionic surfactant, anionic surfactant, cation
System surfactants and amphoteric surfactants. Non-ion
As surface activity, polyoxyethylene alkyl ether
, Polyoxyethylene alkyl phenyl ether
Polyoxyethylene polystyryl phenyl ether
Polyoxyethylene polyoxypropylene alkyl
Ethers, glycerin fatty acid partial esters, sorbi
Tan fatty acid partial esters, pentaerythritol fat
Acid partial esters, propylene glycol monofatty acid ester
Stealth, sucrose fatty acid partial esters, polyoxye
Tylene sorbitan fatty acid partial ester, polyoxye
Tylene sorbitol fatty acid partial esters, polyethylene
Glycol fatty acid esters, polyglycerol fatty acid
Partial esters, polyoxyethylenated castor oil, polyester
Lioxyethylene glycerin fatty acid partial esters, fat
Fatty acid diethanolamides, N, N-bis-2-hydro
Xylalkylamines, polyoxyethylene alkylamines
Min, triethanolamine fatty acid ester, trial
Killamine oxide, sugar alcohol ethylene oxide
Preferred examples include adducts. As an anionic surfactant, for example, fat
Acid salts, abietic acid salts, hydroxyalkanesulfo
Phosphates, alkane sulfonates, dialkyl sulfos
Succinate esters, α-olefin sulfonates, direct
Chain alkylbenzene sulfonates, branched chain alkylbenzenes
Sulfonates, alkyl naphthalene sulfonic acids
Salts, alkylphenoxypolyoxyethylenepropyl
Sulfonates, polyoxyethylene alkylsulfof
Phenyl ether salts, N-methyl-N-oleyl tauri
Sodium salt, N-alkylsulfosuccinic acid monoamide
Disodium salt, petroleum sulfonates, sulfated beef oil,
Sulfuric acid ester salts of fatty acid alkyl esters, alkyl
Sulfate esters, polyoxyethylene alkyl ether
Sulfate esters, fatty acid monoglyceride sulfate ester
Salts, polyoxyethylene alkylphenyl ether
Sulfate esters, polyoxyethylene styryl pheny
Ruether sulfates, alkyl phosphates
Salts, polyoxyethylene alkyl ether phosphates
Tell salt, polyoxyethylene alkylphenyl ether
Luric acid ester salts, styrene / maleic anhydride copolymer
Partially saponified compounds, olefin / maleic anhydride copolymer
Partially saponified compounds, naphthalene sulfonate formal
Condensates are preferred. Examples of cationic surfactants include a
Rukylamine salts, tetrabutylammonium bromide
Quaternary ammonium salts such as polyoxyethylene alcohol
Killamine salts, polyethylene polyamine derivatives, etc.
Can be mentioned. Examples of amphoteric surfactants include carboxy
Sibetaines, alkylaminocarboxylic acids, sulfobe
Tines, amino sulfates, imidazolines, etc.
Is mentioned. Among the above surfactants, “polyoxy
The term “ethylene” refers to polyoxymethylene,
Polyoxya such as xylene, polyoxybutylene
It can also be read as Rukiren,
Included in surfactants. Surfactant concentration in developer
The degree is preferably 0.001 to 10.0% by mass,
0.01-5.0 mass% is more preferable, 0.1-1.
0% by mass is most preferred. The developer has the purpose of further improving the development performance.
The following additives can be added. For example
NaCl, KC described in JP-A-58-75152
Neutral salts such as l and KBr, Japanese Patent Laid-Open No. 58-190952
Chelating agents such as EDTA and NTA described in the publication, JP
As described in JP-A-59-121336, [Co (N
H_Three)₆] Cl_ThreeCoCl₂・ 6H₂Complexes such as O, JP
Alkylnaphthalene described in JP-A-50-51324
Sodium sulfonate, n-tetradecyl-N, N-dihydride
Anionic or amphoteric surface activity such as loxyethyl betaine
Agent described in US Pat. No. 4,374,920.
Nonionic surface activity such as tramethyldecindiol
Agent, p-dimethyl described in JP-A-55-95946
Methyl chloride quaternization of ruaminomethyl polystyrene
Cationic polymers such as compounds, JP-A-56-142
Vinylbenzyltrimethylammo described in Japanese Patent No. 528
Copolymer of sodium chloride and sodium acrylate
Amphoteric polymer electrolytes, JP-A-57-192951
Reducing inorganic salts such as sodium sulfite described in JP-A-58
-59444 Inorganic lithium such as lithium chloride
A thium compound described in JP-A-59-75255
Organometallic surfactants containing organic Si, Ti, etc.
An organic boron compound described in Japanese Patent No. 59-84241, E
Tetraalkyl ammo described in P101010 specification
And quaternary ammonium salts such as nium oxide
It is. In the developer, development property is promoted or suppressed, and development residue is reduced.
For the purpose of improving the dispersion and the ink affinity of the printing plate image part,
If necessary, an organic solvent may be included, for example benzyl
Alcohol and the like are preferable. Polyethylene glycol
Or its derivatives, or polypropylene glycol
It is also preferable to add benzene or a derivative thereof. More essential
Hydroquinone, resorcin, sulfurous acid or
Such as sodium or potassium bisulfite
Inorganic salt reducing agent, organic carboxylic acid, antifoaming agent, water softener
Can also be added. In recent years, particularly in the plate making and printing industries,
For rationalization and standardization of plate making work,
Dynamic developing machines are widely used. This automatic processor
Generally consists of a development section and a post-processing section, and transports printing plates.
It consists of a device, each processing solution tank and a spray device, and has been exposed.
Each plate pumped up while being transported horizontally
The processing liquid is sprayed from the spray nozzle and developed.
It is. Also, recently, in the processing liquid tank filled with processing liquid
The printing plate material is immersed and conveyed by a guide roll in the liquid.
There is also a known method of processing. Such automatic processing
In processing, depending on the processing volume and operating time for each processing solution
And processing while replenishing the replenisher. In this case, the alkali strength is higher than that of the developer.
By adding an aqueous solution as a replenisher to the developer.
Without changing the developer in the developer tank for a long time.
An amount of imaging material can be processed. In the plate making method of the present invention,
However, it is preferable to adopt this replenishment method.
is there. As the replenisher, the above-described developer can be used.
Used as an aqueous solution with higher alkali strength than image developer.
Can be used. In addition, substantially unused development processing
Adopting a so-called disposable treatment method that uses liquid.
Both are possible. A lithographic printing plate developed as described above is
After washing with water, if necessary, after drying, burning
Processing is performed. The burning process is performed by a burning process.
Sir (for example, sold by Fuji Photo Film Co., Ltd.)
Heating to a high temperature with a burning processor 1300)
Is done. The heating temperature and time in this case will not form an image.
Depending on the type of ingredients, it is in the range of 180-300 ° C
The range of 1 to 20 minutes is preferable. Burned
A lithographic printing plate can proceed directly to the printing process.
The Or if necessary, washing with water, gum arabic or
Conventionally, such as gumming with a desensitizing solution containing starch derivatives
Further processing can be performed. [0120] According to the plate making method of the present invention, burning is performed.
Even without applying a surface-adjusting solution before processing, it is resistant to soiling.
A lithographic plate that maximizes the effect of improving printability
A printing plate can be produced. Also conventionally required
The application of surface preparation liquid before burning can be omitted.
This leads to simplification of the plate making process. [0121] The present invention will now be described in detail with reference to examples.
However, the present invention is not limited to these. In addition,
“%” In the examples represents “mass%”. [Example 1] <Preparation of lithographic printing plate precursor> 0.3 mm thick
Aluminum plate (material 1050) with trichlorethylene
After degreasing and cleaning with nylon, nylon brush and 400 mesh
Pumice-water suspension, and this surface is grained,
Washed well with water. After cleaning, this aluminum plate is
Soak for 9 seconds in 25% aqueous sodium hydroxide at
12g / liter after etching and washing with water
In a hydrochloric acid bath having a concentration of 80 A / dm²Current density
And after 10 seconds of electrolytic surface roughening,
3 seconds at 50 ° C in a liter concentration sodium hydroxide bath
The mat was desmutted and washed with water. Next, this aluminum
The current density is 15 A / dm using 7% sulfuric acid as the electrolyte.
²3 g / m for direct current²After providing an anodic oxide coating of water
Washed and dried. This is the substrate (I). The substrate (I) was treated with sodium silicate at 30 ° C.
Treat with 5% aqueous solution for 10 seconds and apply the following undercoat layer coating solution.
And dried at 80 ° C. for 15 seconds. Undercoat layer after drying
The dry coating amount of 15 mg / m²Met. <Coating liquid for undercoat layer> The following copolymer P (molecular weight 28000) 0.3 g Methanol 100g 1g of water [0124][Copolymer P] Synthesis Example 1 (B1 component: having carboxyl group
Of alkali-soluble polymer compounds (copolymers) 20ml three-necked fan equipped with stirrer, condenser and dropping funnel
To Lasco, 6.39 g of n-propyl methacrylate (0.
045 mol), 1.29 g (0.015 mol) of methacrylic acid
And 20 g of 1-methoxy-2-propanol
Stirring the mixture while heating to 65 ° C in a hot water bath
It was. To this mixture, “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.)
Add 0.15g and keep at 70 ° C for 2 hours under nitrogen flow
The mixture was stirred. The reaction mixture is further methacrylic.
6.39 g (0.045 mol) of n-propyl acid,
1.29 g (0.015 mol) of lauric acid, 1-methoxy-
2-Propanol 20g and "V-601" 0.15g
The mixture was added dropwise by a dropping funnel over 2 hours. drop
After completion, the mixture obtained was further stirred at 90 ° C for 2 hours
did. After completion of the reaction, 40 g of methanol is added to the mixture,
Cool and stir the resulting mixture into 2 liters of water
Then, the mixture was stirred for 30 minutes, and the precipitate was removed.
15g white by removing by filtration and drying
A solid was obtained. Gel permeation chromatography
The weight average molecular weight of this copolymer (polystyrene standard)
Quasi) was 53,000. Synthesis Example 2 (B1 component: having carboxyl group
Of alkali-soluble polymer compounds (copolymers) By the same operation as in Synthesis Example 1 above,
/ Isobutyl methacrylate / methacrylic acid (mol%: 3
5/35/30) was used to synthesize the copolymer. Its weight
When the average molecular weight (polystyrene standard) was measured, 50,
000. Synthesis Example 3 (B1 component: having carboxyl group
Of polyurethane resin) 500ml three-neck with condenser and condenser
In a round bottom flask, add 2,2-bis (hydroxymethyl)
14.6 g (0.109 mol) of lopionic acid, tetraethyl
13.3 g (0.0686 mol) of lenglycol and
1,5-butanediol 2.05 g (0.0228 mol)
And add 118 g of N, N-dimethylacetamide.
Dissolved. To this, 4,4'-diphenylmethanediiso
30.8 g (0.123 mol) of cyanate, hexamethyl
Range isocyanate 13.8 g (0.0819 mol)
And di-n-butyltin dilaurate 0.1 as a catalyst
g was added, and the mixture was heated with stirring at 90 ° C. for 7 hours. This
In the reaction solution, 100 ml of N, N-dimethylacetamide, methano
And 50 ml of acetic acid and 50 ml of acetic acid.
Is added to 4 liters of water with stirring to give a white polymer.
-Precipitated. The polymer is filtered off and washed with water
Then, 60 g of polymer was obtained by drying under reduced pressure.
It was. Gel permeation chromatography (GP
When the molecular weight was measured in (C), the weight average (polystyrene)
Ren standard) was 70,000. Also, by titration
The carboxyl group content was measured to be 1.43 meq / g
Met. Synthesis Example 4 (B1 component: having carboxyl group
Of polyurethane resin) The following diisocyanate compounds (mol%) And the following diol compounds (mol%) Was used in the same manner as in Synthesis Example 3 to synthesize a copolymer.
The acid content of the obtained copolymer by titration is 1.72 meq /
g, and the weight average molecular weight (polystyrene standard) is 8
It was 0.00. Synthesis Example 5 (Synthesis of B2 component) 500ml three-neck equipped with stirrer, condenser and dropping funnel
In a flask, 31.0 g (0.36 mol) of methacrylic acid,
39.1 g (0.36 mol) ethyl chloroformate and aceto
Add 200ml of trinitrile and mix while cooling in an ice-water bath
The thing was stirred. To this mixture was added triethylamine 36.4.
g (0.36 mol) by dropping funnel over about 1 hour
It was dripped. After the dripping is complete, remove the ice-water bath and remove at room temperature 3
The mixture was stirred for 0 minutes. The reaction mixture is mixed with p-aminobenzene.
Nesesulfonamide 51.7g (0.30mol) was added.
Agitate the mixture for 1 hour while warming to 70 ° C in an oil bath.
It was. After completion of the reaction, the mixture is poured into 1 liter of water.
Stir with stirring and stir the resulting mixture for 30 minutes
It was. The mixture is filtered to remove the precipitate, which is
After slurrying with 500 ml, the slurry is filtered,
The obtained solid is dried to give N- (p-aminosulfur
A white solid of (phenylphenyl) methacrylamide was obtained.
(Yield 46.9 g) Next, a stirrer, a cooling pipe and a dropping funnel are provided.
N- (p-aminosulfonylphenol) was added to a 20 ml three-necked flask.
Nyl) methacrylamide 4.61 g, (0.0192 mole)
), 2.94 g (0.0258 mol) of ethyl methacrylate.
), 0.80 g (0.015 mol) of acrylonitrile
And 20 g of N, N-dimethylacetamide in a hot water bath
The mixture was stirred while heating to 65 ° C. This mixture
Add 0.15 g of “V-65” (Wako Pure Chemical Industries, Ltd.) to the product
And stirring the mixture for 2 hours under a nitrogen stream while maintaining at 65 ° C
did. This reaction mixture is further mixed with N- (p-aminosulfonyl).
Phenyl) methacrylamide 4.61 g, methacrylic acid
2.94 g of ethyl, 0.80 g of acrylonitrile, N, N-
Dimethylacetamide and 0.15 g of “V-65”
The compound was added dropwise through a dropping funnel over 2 hours. End of dripping
After completion, the mixture obtained was further stirred at 65 ° C. for 2 hours.
It was. After completion of the reaction, 40 g of methanol is added to the mixture and cooled.
And the resulting mixture is stirred into 2 liters of water.
And stirred the mixture for 30 minutes,
15g white by removing by filtration and drying
A solid was obtained. Gel permeation chromatography
The weight average molecular weight of this particular copolymer (polis
Tylene standard) was 53,000.
It was. On the obtained support, the following image forming layer coating solution
And dry at 150 ° C. for 30 seconds.
1.8 g / m²A positive type lithographic printing plate precursor was obtained. <Coating liquid for image forming layer>   Copolymer of Synthesis Example 2 [(B1) component] 0.050 g   Copolymer of Synthesis Example 4 [(B1) component] 0.050 g   Copolymer of Synthesis Example 5 [component (B2)] 0.4 g   m, p-cresol novolak [component (B2)] 0.6 g   (M / p ratio = 6/4, weight average molecular weight 8000,     0.5% unreacted cresol)   Cyanine dye A [(A + C) component] 0.1 g   Phthalic anhydride [component (D)] 0.05 g   0.002 g of p-toluenesulfonic acid   Ethyl violet 0.02g   (Counterion: 6-hydroxy-β-naphthalenesulfonic acid)   Naphthoquinone 1,2-diazide-5-sulfonyl chloride and     0.01 g esterified product with pyrogallol-acetone resin   Fluorosurfactant 0.05g   (Product name: Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)   Methyl ethyl ketone 8g   1-methoxy-2-propanol 4g (SiO 2₂Preparation of alkaline developer solution
(Made by) silicon oxide SiO₂And potassium oxide K₂Mixing ratio of O
SiO₂/ K₂4.0% potassium silicate with an O of 1.1,
Ionine C-158-G (made by Takemoto Yushi) 0.025%,
Pionein D-1105 (made by Takemoto Yushi) 0.005%,
Orphine AK-02 (manufactured by Nissin Chemical) 0.015%
A contained alkali developing solution was prepared. Output to the lithographic printing plate precursor obtained as described above
500 mW, wavelength 830 nm, beam diameter 17 μm (1 / e
²) At a main scanning speed of 5 m / sec.
Exposed and held at 25 ° C. This lithographic printing plate precursor
Automatic processor PS900N filled with alkaline developer
Developer temperature 25 by P (Fuji Photo Film Co., Ltd.)
Development was carried out at 12 ° C., 28 ° C., 30 ° C. Development
After the treatment, a water washing step was performed. Then burn process
270 by Sir 1300 (Fuji Photo Film Co., Ltd.)
After burning at ℃ for 7 minutes, washed with water, gum GU-7
(1: 1) (Fuji Photo Film Co., Ltd.)
As a result, a lithographic printing plate having been subjected to plate making was obtained. Using the lithographic printing plate thus obtained,
Commercially available ink with Heidelberg KOR press
Print on high quality paper and use non-image stains and burning.
The printing durability was evaluated as follows. [Dirty non-image area] -Standard- ○: Nothing remains on the non-image area of the lithographic printing plate and stains on the printed matter
There was no such thing. Δ: There is some residue in the non-image area of the lithographic printing plate, but printing
There was no dirt on the object. ×: There is a residue in the non-image area of the planographic printing plate, and on the printed matter
Dirt has occurred. [Printing effect by burning process]
No sticking and normal printed matter cannot be obtained.
This is represented by the number of printed normal printed materials. Inferior printing durability
Is a small number. [0135] [Comparative Example 1] Surface preparation before burning with 2.5% aqueous solution of boric acid
Except that it was used as a liquid, it was made in the same manner as in Example 1 and evaluated.
I was worth it. Example 2 Electrolysis in a hydrochloric acid bath having a concentration of 10 g / liter
Made in the same manner as in Example 1 except that the roughening treatment was performed.
Printed and evaluated. Example 3 Electrolytic roughening in a hydrochloric acid bath having a concentration of 15 g / liter
Plate making as in Example 1 except that the surface treatment was performed
And evaluated. Example 4 Electrolytic roughening in a hydrochloric acid bath having a concentration of 20 g / liter
Plate making as in Example 1 except that the surface treatment was performed
And evaluated. Example 5 In a hydrochloric acid bath with a concentration of 12 g / l, 20
Example 1 except that the electrolytic surface roughening treatment was performed at 0 ° C.
In the same manner, the plate was made and evaluated. [0136] Example 6 In a hydrochloric acid bath with a concentration of 12 g / l, 30
Example 1 except that the electrolytic surface roughening treatment was performed at 0 ° C.
In the same manner, the plate was made and evaluated. Example 7 In a hydrochloric acid bath with a concentration of 12 g / l, 35
Example 1 except that the electrolytic surface roughening treatment was performed at 0 ° C.
In the same manner, the plate was made and evaluated. Example 8 In a hydrochloric acid bath with a concentration of 12 g / l, 25
50A / dm at ℃²Electrolytic roughening treatment was performed at a current density of
Except for this, the plate was made and evaluated in the same manner as in Example 1. EXAMPLE 9 25 in a hydrochloric acid bath with a concentration of 12 g / l
100 A / dm at ℃²Electrolytic surface roughening at a current density of
In the same manner as in Example 1, the plate was made and evaluated. Example 10 In a hydrochloric acid bath having a concentration of 12 g / liter, 2
150 A / dm at 5 ° C²Electrolytic roughening treatment at a current density of
Except that, the plate was made and evaluated in the same manner as in Example 1.
It was. [0137] Comparative Example 2 In a hydrochloric acid bath having a concentration of 150 g / liter, 2
250 A / dm at 5 ° C²Electrolytic rough surface for 10 seconds at a current density of
Plate making in the same manner as in Example 1 except that the lithographic treatment was performed
And evaluated. Comparative Example 3 In a nitric acid bath having a concentration of 12 g / liter, 25
50A / dm at ℃²Electrolytic surface roughening treatment at a current density of 5 seconds
Plate making and evaluation in the same manner as in Example 1
did. Comparative Example 4 In a nitric acid bath having a concentration of 20 g / liter, 35
150 ° C / dm at ℃²Electrolytic roughening at a current density of 10 seconds
Except having performed processing, it made a plate like Example 1,
evaluated. [0138] Example 11 Non-reduction prepared as follows for development processing
Example 1 using a sugar-containing alkali developing solution
And lithographic printing plate was obtained and evaluated. (Non-reduction
Preparation of sugar-containing alkaline developing solution) Non-reducing sugar and base
D-sorbite / potassium oxide K₂O
Rinari potassium salt 5.0%, Pionine C-158-G
(Made by Takemoto Yushi) 0.025%, Pionein D-1105
(Made by Takemoto Yushi) 0.005% and Olfine AK-0
2 (manufactured by Nissin Chemical) Alkaline development containing 0.015%
A liquid was prepared. [0139] EXAMPLE 12 Electricity in a hydrochloric acid bath having a concentration of 10 g / liter.
Same as Example 11 except that the de-roughening treatment was performed
The plate was made and evaluated. Example 13 Electrolysis in a hydrochloric acid bath having a concentration of 15 g / liter
Similar to Example 11 except that the roughening treatment was performed.
Plate making and evaluation were performed. Example 14 Electrolysis in a hydrochloric acid bath having a concentration of 20 g / liter
Similar to Example 11 except that the roughening treatment was performed.
Plate making and evaluation were performed. Example 15 In a hydrochloric acid bath having a concentration of 12 g / liter, 2
Example 1 except that the electrolytic surface roughening treatment was performed at 0 ° C.
Plate making and evaluation were conducted in the same manner as in 1. [0140] Example 16 In a hydrochloric acid bath having a concentration of 12 g / liter, 3
Example 1 except that the electrolytic surface roughening treatment was performed at 0 ° C.
Plate making and evaluation were conducted in the same manner as in 1. EXAMPLE 17 In a hydrochloric acid bath having a concentration of 12 g / liter, 3
Example 1 except that an electrolytic surface roughening treatment was performed at 5 ° C.
Plate making and evaluation were conducted in the same manner as in 1. Example 18 In a hydrochloric acid bath having a concentration of 12 g / liter, 2
50A / dm at 5 ℃²Electrolytic surface roughening at a current density of
Except that, the plate was made and evaluated in the same manner as in Example 11.
It was. Example 19 In a hydrochloric acid bath having a concentration of 12 g / liter, 2
100 A / dm at 5 ° C²Electrolytic roughening treatment at a current density of
Except that, the plate was made and evaluated in the same manner as in Example 11.
It was. Example 20 In a hydrochloric acid bath having a concentration of 12 g / liter, 2
150 A / dm at 5 ° C²Electrolytic roughening treatment at a current density of
Except that, the plate was made and evaluated in the same manner as in Example 11.
It was. [0141] [Comparative Example 5] Surface preparation before burning with 2.5% aqueous solution of boric acid
Except that it was used as a liquid, it was made in the same manner as in Example 11,
evaluated. Comparative Example 6 In a hydrochloric acid bath having a concentration of 150 g / liter, 2
250 A / dm at 5 ° C²Electrolytic rough surface for 10 seconds at a current density of
Plate making in the same manner as in Example 11 except that the pretreatment was performed
And evaluated. Comparative Example 7 25 in a nitric acid bath having a concentration of 12 g / liter.
50A / dm at ℃²Electrolytic surface roughening treatment at a current density of 5 seconds
A plate was made in the same manner as in Example 11 except that
I was worth it. [Comparative Example 8] In a nitric acid bath having a concentration of 20 g / liter, 35
150 ° C / dm at ℃²Electrolytic roughening at a current density of 10 seconds
Plate making as in Example 11 except that processing was performed
And evaluated. Table 1 below shows Examples 1 to 20 and Comparative Examples.
Conditions for electrolytic surface roughening treatment used in 1 to 8 and support
To summarize. Furthermore, Table 2 and Table 3 show stains on the non-image area and
The evaluation result of the printing durability effect by the burning process is described. [0143] [Table 1] ^*  Pits with a pit diameter of 5-30 μm account for the total number of pits
Percentage [0144] [Table 2] [0145] [Table 3]

Claims (1)

What is claimed is: 1. An image forming layer comprising an infrared absorbing dye on a support on which pits are formed by hydrochloric acid electrolytic surface-roughening treatment and 60% or more of the total number of pits have a pit diameter of 5 to 30 μm A method for making a lithographic printing plate, comprising: exposing a positive infrared-sensitive lithographic printing plate provided with an infrared ray, developing, washing with water, and performing a burning treatment without applying a burning surface-adjusting solution.