JP2003246161A - Method for lithography - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing method for a lithographic printing plate wherein the hydrophilicity of a hydrophilic layer of a substrate is high and the power of bonding to the substrate is not impaired and wherein the scumming property on the occasion of printing a large number of copies is improved, in particular, and no deterioration of printability is brought about even in long-time continuous printing. <P>SOLUTION: An original plate for the lithographic printing plate which has the hydrophilic layer constituted of a polymer compound bonding chemically directly to the surface of the substrate and having a hydrophilic functional group, and an image forming layer, sequentially on the substrate is subjected to image exposure, developed and made into the plate. Using the lithographic printing plate thus made, printing is executed with dampening water containing a specific solvent used. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
On a support having a hydrophilic surface in which a rimmer chain is present,
A lithographic stamp obtained from a lithographic printing plate precursor provided with an image forming layer
Related to lithographic printing method using fountain solution using printing plate
The More specifically, lithographic plates with good long-term printability
It relates to printing methods. [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
Area that accepts water and repels oil-based ink, and repels water and oil
Consisting of areas that accept sexual inks, the former being non-image areas
Yes, the latter is the image area. In lithographic printing, usually dampening
Wet the non-image area with water to make the image area and non-image
Enlarge the interfacial chemical difference from the region to increase the
Increase the rebound and ink acceptance of the image area
Is made. Conventionally known fountain solution
Alkaline metal salt or ammonium dichromate
Salt, phosphoric acid or salt thereof, such as ammonium salt, arabi
A gum, carboxymethylcellulose (CMC), etc.
There is an aqueous solution to which Lloyd's substance is added. However,
A fountain solution containing only these compounds will be applied to the non-image area of the plate.
There is a fault that is hard to get wet, so the printed matter sometimes gets dirty
In addition, considerable skill is required to adjust the supply amount of dampening water.
It was a problem. To remedy this drawback, isopropyl alcohol
Aqueous solution containing about 20-25% lecol is used as dampening water
The Dahlglen system to be used has been proposed. To this method
According to this, wetting on non-image areas is improved and the amount of dampening water is small.
No need to adjust the balance of printing ink and water supply
It is easy to adjust and the emulsification amount of dampening water in printing ink is small.
In addition, the transfer of printing ink to the blanket
Workability and accuracy of the printed matter obtained, such as improvement
There are a number of advantages. However, this isop
Since propyl alcohol is easy to evaporate,
A special device to keep the ropyl alcohol concentration constant
Necessary and expensive in terms of price. Ma
In addition, isopropyl alcohol has a characteristic unpleasant odor
At the same time, there are problems in terms of toxicity.
Absent. Also, this isopropyl alcohol added moisture
Applying water to offset printing using ordinary water rods
Isopropyl alcohol on the roller and the plate surface
Because it evaporates, the effect cannot be demonstrated.
It was a problem. On the other hand, from the viewpoint of the configuration of a lithographic printing plate,
After the printing plate precursor is exposed and developed, the surface of the support
The ability of exposed parts (non-image areas) to retain water is
The hydrophilicity of the support surface is greatly affected by the printing stain
Technology that enhances this has been developed. For example, lithographic printing plate
Various hydrophilic substrates or hydrophilic layers have been proposed.
The An example of this is the glow on the PET film surface.
Treatment (irradiation with oxygen plasma in vacuum) and PET
Inducing active species such as radicals on the film surface,
Add monomer with hydrophilic group to start reaction
Of polymer compound obtained by surface graft polymerization
Layer, i.e. polymer chain ends chemically bonded to support substrate
A lithographic printing plate precursor using a modified hydrophilic layer was proposed.
(Japanese Patent Laid-Open No. 2001-166491). This plan
According to the printing plate precursor, the hydrophilic layer is highly hydrophilic and
Excellent binding force between the hydrophilic layer and the support,
It is possible to make a lithographic printing plate with improved
The However, the conventional lithographic printing plate described above
Using a dampening solution containing isopropyl alcohol
When printing is performed, the print stain performance is not fully exhibited and the print stain
In addition, the printing durability deteriorates. This is support
The hydrophilic layer structure of the body contains a relatively large amount in the fountain solution.
By using a rare solvent such as isopropyl alcohol.
This is thought to be due to destruction. Therefore, the support
Planes made from lithographic printing plate precursors with improved surface hydrophilicity
Use a printing plate and maintain good hydrophilicity while maintaining good hydrophilicity.
There is a need for a printing method that can exhibit printability. [0006] The object of the present invention is to provide a planographic plate.
Maintains high hydrophilicity of the hydrophilic layer on the support surface of the printing plate
Can be made without damaging the bonding force between the hydrophilic layer and the support.
In addition, the stain resistance when printing many copies is improved, and it is continuous for a long time.
Providing a lithographic printing method that does not degrade printability even after printing
It is to be. [0007] The present inventors have achieved the above object.
As a result of earnest research to achieve, hydrophilic graft
On a support having a hydrophilic surface in which polymer chains are present,
The lithographic printing plate precursor provided with the image forming layer is image-exposed to
Using a lithographic printing plate that has been
By printing using a dampening solution containing a relatively small amount,
Printing stains do not occur even during long-term printing, and printing durability is also
It was found that it was good and led to the completion of the present invention.
It was. Therefore, the present invention has a hydrophilic graft polymer chain.
An image forming layer on a support having a hydrophilic surface
A lithographic printing plate obtained by plate-making a lithographic printing plate precursor
Is a lithographic printing method that uses fountain solution to print.
The fountain solution is a compound represented by the following general formula (1),
The compound represented by the general formula (2) and 6 or more carbon atoms
At least one selected from the group consisting of
A lithographic printing method characterized by containing seeds. (Wherein R¹Represents an alkyl group having 1 to 8 carbon atoms,
R²Represents a hydrogen atom or a methyl group, and n is an integer of 1 to 15.
Number, R^ThreeRepresents a methyl group or an ethyl group, R^FourIs water
Represents an elementary atom or a methyl group. ) [0008] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, it is used in the lithographic printing method of the present invention.
The fountain solution to be described will be described. In addition, dampening water is usually commercial
When used as a base, it is generally concentrated and commercialized.
When using, concentrate such a concentrated solution as appropriate.
Will be. Including the various components mentioned below in this specification.
Amounts and amounts added are dampening water during use unless otherwise stated.
Based on the total mass of The fountain solution used in the present invention has the above general formula.
The compound represented by (1), represented by the above general formula (2)
Selected from compounds and diol compounds with 6 or more carbon atoms
At least one compound. In the general formula (1), R¹Is from 1 to 8 carbon atoms
Represents a linear, branched or cyclic alkyl group of
Represents an alkyl group having 1 to 4 carbon atoms, and n is 1 to 1
The integer of 5 is represented, Preferably 1-3 is represented. General formula
Specific examples of the compound represented by (1) include ethylene glycol
Monomethyl ether, ethylene glycol monoethyl ether
Ether, ethylene glycol mono-n-propyl ether
-Tel, ethylene glycol monoisopropyl ether
Ethylene glycol mono-n-butyl ether
Tylene glycol monoisobutyl ether, ethylene glycol
Recall mono-t-butyl ether, ethylene glycol
Rumono-n-pentyl ether, ethylene glycol
Non-n-hexyl ether, ethylene glycol mono-
Cyclohexyl ether, ethylene glycol mono-n
-Heptyl ether, ethylene glycol mono-n-o
Cutyl ether, diethylene glycol monomethyl ether
Tellurium, diethylene glycol monoethyl ether, die
Tylene glycol mono-n-propyl ether, diethyl
Lenglycol monoisopropyl ether, diethylene
Glycol mono-n-butyl ether, diethylene glycol
Cole monoisobutyl ether, diethylene glycol
Mono-t-butyl ether, triethylene glycol
Nomethyl ether, triethylene glycol monoethyl
Ether, triethylene glycol mono-n-propyl
Ether, triethylene glycol monoisopropyl ether
-Tel, triethylene glycol mono-n-butyl ether
Tere, triethylene glycol monoisobutyl ether
Triethylene glycol mono-t-butyl ether
Le, Propylene glycol monomethyl ether
Propylene glycol monoethyl ether, propylene
Lenglycol mono-n-propyl ether, propylene
Glycol monoisopropyl ether, propylene glycol
Recall-n-butyl ether, propylene glycol
Monoisobutyl ether, propylene glycol mono-
t-butyl ether, propylene glycol mono-n-
Pentyl ether, propylene glycol mono-n-he
Xyl ether, propylene glycol mono-cyclohe
Xyl ether, propylene glycol mono-n-hept
Chill ether, propylene glycol mono-n-octy
Luether, dipropylene glycol monomethyl ether
Dipropylene glycol monoethyl ether, dip
Lopylene glycol mono-n-propyl ether, dip
Lopylene glycol monoisopropyl ether, dipro
Pyrene glycol-n-butyl ether, dipropylene
Glycol monoisobutyl ether, propylene glycol
Mono-t-butyl ether, tripropylene glycol
Monomethyl ether, tripropylene glycol
No ethyl ether, tripropylene glycol mono-n
-Propyl ether, tripropylene glycol monoy
Sopropyl ether, tripropylene glycol-n-
Butyl ether, tripropylene glycol monoisobut
Tyl ether, tripropylene glycol mono-t-butyl
There is chill ether. Among them, propylene glycol
Rumono-n-butyl ether, ethylene glycol mono
-T-butyl ether can be preferably used. Specific examples of the compound represented by the general formula (2)
Are 3-methoxybutanol, 3-methoxy-3-methyl
Rubutanol, 3-ethoxybutanol, 3-ethoxy
There is -3-methylbutanol. Among them, 3-methoxy-
3-methylbutanol can be preferably used. Geo having 6 or more carbon atoms for use in the present invention
Is an aliphatic compound having 6 or more carbon atoms.
Or an alicyclic compound in which two hydroxyl groups are
The carbon atom chain may be a straight chain or a
It may be a branched chain, saturated or unsaturated. Or carbon
There may be oxygen atoms between the atoms. The number of carbon atoms is
6 to 20 is suitable, more preferably 6 to 14
The Specifically, glycols, unsaturated glycols (eg
Acetylene glycols), polyalkyleneglycol
For example. Diol compound having 6 or more carbon atoms
Specific examples of 1,6-hexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
9-nonanediol, 1,10-decanediol, 2-
Ethyl-1,3-hexanediol, 2,5-dimethyl
-Hexane-2,5-diol, cyclohexane-1,
2-diol, cyclohexane-1,4-diol,
2,5-dimethyl-3-hexyne-2,5-diol,
3,6-dimethyl-4-octyne-3,6-diol,
2,4,7,9-tetramethyl-5-decyne-4,7-
Diol, 2,4,7,9-tetramethyl-5-decyne
-4,7-diol ethylene oxide adduct (ethylene oxide)
2,4,7,9-)
Oxidation of tetramethyl-5-decyne-4,7-diol
Tylene / propylene oxide adduct (total number of moles added: 30 moles)
2,5,8,11-tetramethyl-6-
Dodecine-5,8-diol triethylene glycol,
Tetraethylene glycol, pentapropylene glycol
, Dipropylene glycol, tripropylene glycol
, Tetrapropylene glycol, pentapropylene glycol
Examples include recalls. Among them, 2-ethyl-1,3
-Hexanediol, 3,6-dimethyl-4-octyne
-3,6-diol, 2,4,7,9-tetramethyl-
5-decyne-4,7-diol, 2,4,7,9-teto
Ethylene oxide of lamethyl-5-decyne-4,7-diol
4 mol adduct can be preferably used. The above compounds may be used alone.
Two or more kinds may be used in combination. Dampening used in the present invention
A compound represented by the above general formula (1) in water;
The compound represented by the general formula (2) and having 6 or more carbon atoms
Of at least one compound selected from diol compounds
A content of 0.01 to 10% by mass is appropriate and preferred.
Or 0.05-3 mass%, more preferably 0.1-1.
5% by mass. If less than the above range, printing performance
This is likely to cause uneven supply of dampening water and
Wow. On the other hand, if the above range is exceeded, the graft hydrophilic layer is broken.
It is easy to break, and is easy to get dirt at the time of rubbing printing
Become. The fountain solution used in the present invention includes the above components.
Can include the following: (a) Aid for improving wettability (b) Water-soluble polymer compound (c) pH adjuster (d) chelating agent (e) Odor masking agent (f) Others (preservatives, colorants, rust preventives, antifoaming agents)
Such) (A) Surfactant as an aid for improving wettability
And solvents can be used. Examples of surfactants
For example, anionic surfactants include fatty acid salts, abi
Ethinates, hydroxyalkane sulfonates, a
Lucan sulfonates, dialkylsulfosuccinates,
Linear alkyl benzene sulfonates, branched alkyl
Benzene sulfonates, alkyl naphthalene sulfones
Acid salts, alkylphenoxy polyoxyethylene propylene
Sulfonic acid salts, polyoxyethylene alkylsulfur
Phenyl ether salts, N-methyl-N-oleyl tauri
Sodium salt, N-alkylsulfosuccinic acid monoami
Dosodium salts, petroleum sulfonates, sulfated castor
Sulfur oil, sulfated beef oil, fatty acid alkyl ester sulfate
Steal salt, alkyl sulfate ester salt, polyoxye
Tylene alkyl ether sulfate ester, fatty acid mono
Glyceryl sulfate salts, polyoxyethylene alcohol
Quilphenyl ether sulfates, polyoxye
Tyrene tyrylphenyl ether sulfates,
Rualkyl phosphates, polyoxyethylene alkyl
Ether phosphate esters, polyoxyethylene alkyl
Ruphenyl ether phosphate, styrene-anhydrous
Partially saponified products of maleic acid copolymer, olefin-none
Partially saponified products of water maleic acid copolymer, naphthalene
Examples thereof include sulfonic acid formalin condensates. these
Among them, dialkyl sulfosuccinates, alkyl sulfate esters
Stealth salts and alkylnaphthalene sulfonates are special features
Is preferably used. Nonionic surfactants include polyoxy
Siethylene alkyl ethers, polyoxyethylene
Rukylphenyl ethers, polyoxyethylene polices
Tyryl phenyl ethers, polyoxyethylene polio
Xylpropylene alkyl ethers, glycerin fatty acids
Partial esters, sorbitan fatty acid partial esters,
Intererythritol fatty acid partial ester, propylene
Glycol mono fatty acid esters, sucrose fatty acid partial es
Tells, polyoxyethylene sorbitan fatty acid partial ester
Tells, polyoxyethylene sorbitol fatty acid partial ester
Stealth, polyethylene glycol fatty acid esters,
Polyglycerin fatty acid partial esters, polyoxyethylene
Renated castor oil, polyoxyethylene glycerin fat
Acid partial esters, fatty acid diethanolamides, N,
N-bis-2-hydroxyalkylamines, polyoxy
Siethylene alkylamines, triethanolamine fat
Fatty acid esters, trialkylamine oxides, etc.
Can be mentioned. Other fluorine-based surfactants, silicon-based materials
Surfactants can also be used. Among them, polyoki
Siethylene alkyl phenyl ethers, polyoxye
Tylene-polyoxypropylene block polymers
Preferably used. In addition, silicon derivatives or fluorine
Surfactants such as derivatives are also included. Use surfactant
If the content of the fountain is
1.0 mass% or less, preferably 0.001 to 0.5
A mass% is suitable. Also, two or more types can be used together
Yes. As other auxiliaries or wetting solvents,
Tylene glycol, diethylene glycol, glycerin
, Diglycerin, polyglycerin, trimethylol group
Lopan, propylene glycol, etc. can be used
The These solvents may be used alone, but two or more
May be used in combination. In general, these solvents are
It is appropriate and preferably used in the range of 0.1 to 3% by mass.
Or 0.3 to 2% by mass. (B) Water-soluble polymer compound used in dampening water
Examples of the product include gum arabic and starch derivatives (for example,
Dextrin, enzymatic degradation dextrin, hydroxy
Propylated enzymolysis dextrin, carboxymethylation
Starch, phosphate starch, octenyl succinated starch), Argi
Phosphates, fibrin derivatives (eg carboxymethyl cell
Loin, carboxyethyl cellulose, methyl cellulose
And other natural products and modified products thereof, polyethylene glycol
And its copolymers, polyvinyl alcohol and its derivatives
Conductors, polyvinylpyrrolidone, polyacrylamide and
Its copolymer, polyacrylic acid and its copolymer, vinyl
Rumethyl ether / maleic anhydride copolymer, vinyl acetate
/ Maleic anhydride copolymer, polystyrene sulfonic acid
And a composite of such a copolymer. Water-soluble polymer
Compound content is 0.0001-0.1 quality in dampening water
% Is suitable, more preferably 0.0005-
0.05% by mass. (C) used as a pH adjusting agent in dampening water
Water-soluble organic acids and / or inorganic acids or their salts
These compounds can be used to adjust the pH of the fountain solution.
Is pH buffered, moderate etching of lithographic printing plate support or
Effective for corrosion prevention. Preferred organic acids include, for example,
Citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid,
Acetic acid, gluconic acid, acetic acid, hydroxyacetic acid, succinic acid, malo
Acid, levulinic acid, sulfanilic acid, p-toluenesulfuric acid
Examples include phosphonic acid, phytic acid, and organic phosphonic acid.
Examples of inorganic acids include phosphoric acid, nitric acid, sulfuric acid, polyphosphoric acid
Is mentioned. Further, these organic acids and / or inorganic acids
Lucari metal salt, alkaline earth metal salt or ammonia
And organic amine salts are also preferably used.
Acids, inorganic acids and / or their salts can be used alone,
Or you may use it as a mixture of 2 or more types. this
The amount of pH adjuster added in the fountain solution is 0.001 to 0.001.
A range of 0.3% by mass is preferable, and the pH value of the fountain solution is 3 to 3.
Preferably in the acidic range of 7
Li metal hydroxide, phosphoric acid, alkali metal salt, carbonate carbonate
PH 7-11 Al containing lithium metal salt, silicate, etc.
It can also be used in the potash region. In the fountain solution, (d) a chelating agent is further added.
Can be added. The fountain solution is usually concentrated when used.
Prepared by diluting the water composition with tap water or well water
In this case, it is included in the tap water and well water to be diluted.
Calcium ions etc. adversely affect printing
It may cause the dirt to become dirty easily. Such a place
The above disadvantages by adding a chelating agent.
Can be eliminated. As a preferred chelating agent
For example, ethylenediaminetetraacetic acid, its potassium
Salt, its sodium salt; diethylenetriaminepentavinegar
Acid, its potassium salt, sodium salt; triethylenetet
Lamin hexaacetic acid, its potassium salt, its sodium
Salt, hydroxyethylethylenediaminetriacetic acid, its
Potassium salt, sodium salt thereof; nitrilotriacetic acid, salt
Sodium salt of 1-hydroxyethane-1,1-difo
Sphonic acid, its potassium salt, its sodium salt; amino
Tri (methylenephosphonic acid), its potassium salt, its
Organic phosphonic acids such as thorium salts or phosphines
Examples include phonoalkanetricarboxylic acids.
Sodium salt or potassium salt of the above chelating agent
Instead of these, organic amine salts are also effective. These keys
The rate agent is stably present in the fountain solution during use and is printable.
Those that do not interfere with are selected. Chelating compounds in dampening water
Appropriate content of the product is 0.001 to 0.5% by mass.
Preferably, it is 0.002 to 0.25% by mass
The (E) Conventional fragrances as odor masking agents
Including esters known for use as: For example, below
There are those represented by the general formula (I). R₁-COOR₂                (I) In the compounds of general formula (I)₁Is 1 carbon atom
~ 15 alkyl groups, alkenyl groups or aralkyl groups,
Or it is a phenyl group. Alkyl group or alkenyl
In the case of a group, the number of carbon atoms is preferably 4-8.
R₁Represents an alkyl group, an alkenyl group or an aralkyl group.
They may be linear or branched. Alkenyl
A group having one double bond is particularly suitable. Ara
Examples of alkyl groups include benzyl and phenylethyl groups.
I can get lost. R₁An alkyl group represented by
One or more of a ru group or an aralkyl group or a phenyl group
Even if the hydrogen atom is substituted with a hydroxyl group or an acetyl group
Good. R₂Is an alkyl group having 3 to 10 carbon atoms, arral
A kill group or a phenyl group, which are linear or branched
It may be a chain. In the case of an alkyl group, the number of carbon atoms is preferred.
Or 3 to 9. As an aralkyl group,
Benzyl group and phenylethyl group. Can be used as an (e) odor masking agent
Physically, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid,
2-ethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid
Acid, hexanoic acid (caproic acid), 4-methylpentanoic acid
(Isohexanoic acid), 2-hexenoic acid, 4-pentene
Acid, heptanoic acid, 2-methylheptanoic acid, octanoic acid
(Caprylic acid), nonanoic acid, decanoic acid (capric acid),
2-esters of decenoic acid, lauric acid or myristic acid
Is mentioned. Others, benzyl phenylacetate, aceto
Acetovine such as ethyl acetate or 2-hexyl acetoacetate
There are acid esters. Of these, acetic acid is preferred.
n-pentyl, isopentyl acetate, n-butyl butyrate, dairy
N-pentyl acid and isopentyl butyrate, in particular
N-butyl butyrate, n-pentyl butyrate and isopentybutyrate
Is preferred. In the fountain solution of these acid esters
The appropriate content is 0.0001 to 10% by mass.
More preferably, it is 0.001-1 mass%. Use these
To improve the work environment.
The Also. Even with vanillin, ethyl vanillin, etc.
Good. (F) As a preservative used in dampening water
Is phenol or its derivative, formalin, imidazo
Derivatives, sodium dehydroacetate, 4-isothiazo
Phosphorin-3-one derivatives, benztriazole derivatives, a
Midine or guanidine derivatives, quaternary ammonium salts
, Derivatives of pyridine, quinoline or guanidine, dyes
Derivatives of azine or triazole, oxazole or
Derivatives of xazine, bromonitroalcohol bromo
Nitropropanol, 2,2-dibromo-2-nitroe
Tanol, 3-bromo-3-nitropentane, 2,4-
Diol etc. are mentioned. The preferred addition amount is bacteria,
It is an amount that exerts a stable effect on bi, yeast, etc.
Depending on the type of bacteria, mold and yeast,
In water, a range of 0.001 to 1.0% by weight is preferred,
Two species that are effective against various molds, bacteria, and yeast
It is preferable to use the above preservatives in combination. (F) Colorant used in dampening water
Is preferably a food coloring or the like. For example, yellow
CI No. 19140, 15985, red color
CI No. 16185, 45430, 1625 as prime
5, 45380, 45100, CIN as purple pigment
o. 42640, CI No. 4209 as the blue pigment
0, 73015, CI No. 4209 as the green pigment
5, etc. are mentioned. (F) Rust preventive agent usable in the present invention
For example, benzotriazole, 5-methylben
Zotriazole, thiosalicylic acid, benzimidazole
And derivatives thereof. Can be used in the present invention
(f) The antifoaming agent is preferably a silicon antifoaming agent,
Both emulsified dispersion type and solubilized type can be used
it can. The balance of the fountain solution is water. Wet
Water is usually concentrated and commercialized when used on a commercial basis.
It is common to do. Thus water, preferably desalted
The above-mentioned various components were dissolved using water, that is, pure water.
A concentrated fountain solution composition can be obtained as an aqueous solution. This
When using concentrated liquids such as
Dilute 10 to 200 times with water, well water, etc.
Use fountain solution. Use of dampening water for the lithographic printing method of the present invention
The usage may be according to a conventional method. The following is a support for a lithographic printing plate used in the present invention.
The body and the lithographic printing plate precursor using it
Light up. [Hydrophilicity with hydrophilic graft polymer chain
Support having surface] The hydrophilic surface in the support is:
Refers to the surface where the hydrophilic graft polymer chain exists
The This is because the hydrophilic graft polymer chain is directly on the support surface
It may be bonded to the
An intermediate layer to which the polymer is easily bonded is provided on the layer.
It may be grafted with a hydrophilic polymer. Ma
The hydrophilic graft polymer chain bonded to the trunk polymer compound
Polymer or hydrophilic graft polymer chain
Functional groups that can bind to and crosslink molecular compounds are introduced.
The support by coating or coating cross-linking using a polymer
It may be arranged on the surface. Or
Hydrophilic polymer having a crosslinkable group at the end of the remer and a crosslinking agent
And placed on the support surface by coating or coating crosslinking.
It may be. The hydrophilic polymer is characterized by the end of the polymer.
Is bonded to the support surface or support surface layer
Is characterized by having a substantially uncrosslinked structure
The This limits the mobility of the hydrophilic polymer part.
It has a characteristic that can maintain high mobility and is highly hydrophilic
Is considered to be expressed. Hydrophilic graft polymer
-The molecular weight range of the chain is in the range of Mw 5 to 5 million
The preferred molecular weight is in the range of Mw 1000 to 1 million.
Yes, more preferably in the range of Mw 2000 to 500,000
is there. Here, the hydrophilic graft polymer chain is straight.
On the contact support surface or on the intermediate layer provided on the support surface
What is bonded to the surface is called "surface graft" and is hydrophilic
Graft polymer chains are introduced into the polymer cross-linked membrane structure
When using the existing one, select "Hydrophilic graft chain introduction rack".
This is referred to as a “bridge hydrophilic layer”. Also here, the support or
A material provided with an intermediate layer on a support is referred to as a substrate. (Method for producing surface graft)
Create a surface with hydrophilic groups made of ftpolymer
As a method, the substrate and the graft polymer are chemically bonded.
And a double layer that can be polymerized from the base material
A compound having a bond is polymerized to form a graft polymer.
There are two ways. Chemical bonding of substrate and graft polymer
Explaining the method of adhering together, the polymer ends are also
Or a polymer having a functional group that reacts with the substrate in the side chain.
Used and chemically reacts with the functional group on the substrate surface
Can be grafted. The government that reacts with the substrate
In particular, functional groups react with functional groups on the substrate surface.
If there is no particular limitation, for example, alkoxysilane
Silane coupling group, isocyanate group, amino
Group, hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid
Group, epoxy group, allyl group, methacryloyl group, acrylic group
Examples include a Royl group. The end of the polymer
Or as a polymer having a reactive functional group in the side chain
Useful compounds include trialkoxysilyl groups in the polymer powder
Hydrophilic polymer at the end, amino group at the polymer end
Hydrophilic polymer having a carboxyl group at the end of the polymer
Hydrophilic polymer having an epoxy group at the end of the polymer
Hydrophilic polymer having isocyanate group with polymer powder
It is a hydrophilic polymer at the end. Also used at this time
The hydrophilic polymer is not particularly limited as long as it is hydrophilic.
Specifically, polyacrylic acid, polymethacrylic
Acid, polystyrenesulfonic acid, poly-2-acrylamido
Do-2-methylpropanesulfonic acid and salts thereof,
Polyacrylamide, polyvinylacetamide, etc.
I can make it. In addition, the following surface graft polymerization
Polymer of hydrophilic monomer used, or hydrophilic module
Copolymers containing nomers can be used advantageously. Has a double bond polymerizable from the base material.
To polymerize the compound to form a graft polymer
The method is commonly referred to as surface graft polymerization. Surface gra
Polymerization method means plasma irradiation, light irradiation, heating, etc.
To give active species on the substrate surface and
By polymerization of a compound having a polymerizable double bond.
This is a method of bonding with the base material. The surface graft polymerization method is described in the literature.
Any known method can be used. for example
For example, New Polymer Experiments 10, edited by Polymer Society, 1994,
Issued by Kyoritsu Publishing Co., Ltd.
As photo graft polymerization method, plasma irradiation graft polymerization method
Is described. Adsorption Technology Handbook, NTS
Co., Ltd., supervised by Takeuchi, published in 1999.2, p203, p6
95, radiation-induced graft polymerization of γ rays, electron beams, etc.
The law is described. Specific methods of photograft polymerization and
JP-A-63-92658 and JP-A-10-2
No. 96895 and JP-A-11-119413
The methods described in the report can be used. Plasma irradiation
In graft polymerization and radiation-induced graft polymerization
Documents described above, and Y.M. Ikada et al,
  Macromolecules vo 1.19, p
age 1804 (1986), etc.
Can be made. Specifically, polymer table such as PET
Treat the surface with plasma or electron beam,
Generate cal, then its active surface and hydrophilic functional groups
By reacting with a monomer having
It is possible to obtain a remer surface layer, that is, a surface layer having a hydrophilic group.
You can. In addition to the above-mentioned documents, photografting polymerization
JP 53-17407 (Kansai Paint),
Kai 2000-212313 (Dainippon Ink)
Apply the photopolymerizable composition to the surface of the film substrate
After that, contact with the aqueous radical polymerization compound and light
It can also be created by irradiation. (Polymerization useful for surface graft polymerization)
Description of the compound having a functional double bond) hydrophilic graft
Compounds useful for forming remer chains are polymerizable doubles
It has a bond and has hydrophilic properties.
Is necessary. These compounds are double in the molecule
Hydrophilic polymer or hydrophilic oligomer having a bond
-Either a hydrophilic monomer or a compound may be used. Especially
Useful compounds are hydrophilic monomers. Parents useful in the present invention
Aqueous monomers include ammonium, phosphonium, etc.
A positively charged monomer or sulfonic acid group,
Negative charges such as boxyl, phosphate, and phosphonate groups
Monomers with acidic groups that can have or dissociate into negative charges
In addition, for example, hydroxyl group, amide
Group, sulfonamido group, alkoxy group, cyano group, etc.
Using a hydrophilic monomer having a nonionic group of
You can also. Particularly useful hydrophilic monomers in the present invention
As specific examples, the following monomers can be mentioned.
The For example, (meth) acrylic acid or its alkali gold
Metal salt and amine salt, itaconic acid or its alkali
Metal salts and amine salts, allylamine or its
Hydrogenoates, 3-vinylpropionic acid or so
Alkali metal salts and amine salts, vinyl sulfonic acid
Or its alkali metal salts and amine salts, vinyl
Rensulfonic acid or its alkali metal salts and amino acids
Salt, 2-sulfoethylene (meth) acrylate, 3-
Sulfopropylene (meth) acrylate or its
Lucari metal salt and amine salt, 2-acrylamide-2
-Methylpropanesulfonic acid or its alkali metal
Salts and amine salts, acid phosphooxypolyoxye
Tylene glycol mono (meth) acrylate, allyla
Carboxy, such as min or its hydrohalide
Group, sulfonic acid group, phosphoric acid, amino group or the like
Salt of 2-trimethylaminoethyl (meth) acrylate
Or carboxyl such as its hydrohalides
Group, sulfonic acid group, phosphoric acid, amino group or their
Salt, etc. can be used. 2-hydroxy
Ethyl (meth) acrylate, (meth) acrylami
N-monomethylol (meth) acrylamide, N-
Dimethylol (meth) acrylamide, N-vinyl pyro
Lidon, N-vinylacetamide, allylamine or
Is its hydrohalide, polyoxyethyleneglycol
Also useful are mono (meth) acrylates. (Creation of hydrophilic graft chain-introduced crosslinked hydrophilic layer)
Method) The cross-linked hydrophilic layer into which the hydrophilic graft chain is introduced is
Generally known methods are used for synthesizing graft polymers.
By creating a graft polymer and crosslinking it.
Can be made. Specifically, synthesis of graft polymer
"Graft polymerization and its application" by Fumio Ide, 1977
Publication, Polymer Publication Society, and “New Polymer Experiments 2, Takaita
"Synthesis and reaction of children" edited by Polymer Society, Kyoritsu Publishing Co., Ltd. 199
5. The synthesis of the graft polymer is basically as follows. Trunk height
1. polymerize branch monomers from molecules; Branch high on trunk polymer
Bind molecules; 3. Branched polymer is copolymerized with trunk polymer
(Macromer method). this
Of these three methods, the hydrophilicity of the present invention is used.
Can be made, but in particular, the production suitability and the film structure
"3. Macromer method" is superior from the viewpoint of manufacturing control
ing. Synthesis of graft polymers using macromers
Is the above-mentioned "New Polymer Experimental Science 2, Polymer Synthesis and Reaction"
Described in Molecular Science Society, Kyoritsu Publishing Co., Ltd. 1995
The Also, Yu Yamashita et al. “Chemical Monomer Chemistry and Industry”
Also described in detail in IPC, 1989. Concrete
In particular, acrylic acid, acrylamide, 2-acrylamid
Do-2-methylpropanesulfonic acid, N-vinylacetate
Specifically described as an organic cross-linked hydrophilic layer such as amide
In accordance with the method described in the literature
Sex macromers can be synthesized. Particularly useful among the hydrophilic macromers
Contains carboxyl groups such as acrylic acid and methacrylic acid.
Macromer derived from a monomer with 2-acrylic
Amido-2-methylpropanesulfonic acid, vinyl styrene
Derived from monomers of sulfonic acid and its salts
Sulfonic acid based macromer, acrylamide, methacryl
Amide-based macromers such as amide, N-vinylacetoa
N-vinylcarbo such as amide, N-vinylformamide
Amide-based macromers derived from acid amide monomers
-Hydroxyethyl methacrylate, hydroxyethyl
Acrylate, glycerol monomethacrylate, etc.
, A macromer derived from a hydroxyl group-containing monomer
Xylethyl acrylate, methoxy polyethylene glycol
Acrylate, polyethylene glycol acrylate
Containing alkoxy groups such as
Macromers derived from monomers. Polie also
Tylene glycol chain or polypropylene glycol
A monomer having a chain is also useful as a macromer of the present invention.
Can be used. Among these macromers, the useful molecular weight is
The range of 400 to 100,000, preferably 1000 to 5
A particularly preferred range is from 1500 to 20,000.
If the molecular weight is 400 or less, the effect cannot be exhibited, and 100,000
As described above, the polymerizability with the comonomer forming the main chain is poor.
Become. After synthesizing these hydrophilic macromers,
A cross-linked hydrophilic layer with a grafted graft chain introduced
The method has a reactive functional group with the hydrophilic macromer described above
Graft copolymer with other monomers
And then the synthesized graft copolymer and
A crosslinker that reacts with the reactive functional group of the polymer on the support
It can be applied to and cross-linked by reaction with heat
it can. Or hydrophilic macromers and photocrosslinkable groups,
Alternatively, a graft polymer having a polymerizable group is synthesized and
Is coated on a support and allowed to react by light irradiation to crosslink.
Can be created. In this way, a hydrophilic graft is formed on the substrate.
Can provide a hydrophilic surface with polymer chains present
The The thickness of the layer that forms the hydrophilic surface can be selected according to the purpose.
Generally, the range of 0.001 μm to 10 μm
Preferably, a range of 0.01 μm to 5 μm is more preferable.
The range of 0.1 μm to 2 μm is most preferable. Film thickness
If it is too thin, scratch resistance tends to decrease.
In some cases, ink repellency tends to deteriorate. Of substrate surface
If the hydrophilicity is high, the graft polymer will complete the substrate surface.
It is not necessary to cover it completely. In this case, graft poly
Mer is preferred to be 0.01% or more based on the total surface area of the substrate.
Or 0.1% or more, more preferably 1% or more. [Support] Presence of hydrophilic graft polymer
The support used to form the hydrophilic surface that
There is no restriction in particular, it is a dimensionally stable plate-like material and is necessary
Any one that meets flexibility, strength, durability, etc.
For example, paper, plastic (eg, polyester
Tylene terephthalate, polyethylene naphthalate, polyethylene
Lethylene, polypropylene, polystyrene, etc.)
Paper, metal plates (eg, aluminum,
Lead, copper, etc.), plastic film (eg, diacetic acid
Roulose, cellulose triacetate, cellulose propionate
, Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate
, Polyethylene terephthalate, polyethylene naphth
Talate, polyethylene, polystyrene, polypropylene
, Polycarbonate, polyvinyl acetal, etc.), top
Paper youth with laminated or vapor-deposited metal
For example, a plastic film may be used. Of the present invention
As the support, polyester film or aluminum
A plate is preferred. Aluminum is also laminated
Also preferred are vapor deposited plastic films. Suitable
Aluminum plate is pure aluminum plate and aluminum
Is an alloy plate containing a small amount of foreign elements
The foreign elements contained in the minium alloy include silicon, iron and man
Gun, copper, magnesium, chromium, zinc, bismuth, nickel
There are nickel and titanium. The content of foreign elements in the alloy is
It is at most 10% by mass. Particularly preferred in the present invention
Aluminum is pure aluminum but completely pure
Aluminum is difficult to manufacture due to refining technology.
It may contain a different element. The aluminum plate applied in this way is
Its composition is not specified, it is a publicly known material
An aluminum plate can be used as appropriate. Used
The thickness of the aluminum plate is about 0.1 mm to 0.6
mm, preferably 0.15 mm to 0.4 mm, especially
Preferably it is 0.2 mm-0.3 mm. (Surface properties of the support) Graft polymer
The support used to form the hydrophilic surface consisting of
Improving the hydrophilicity of the hydrophilic surface, or provided on it
From the viewpoint of adhesion to the image forming layer, a hydrophilic surface is formed.
It is preferable to use a roughened surface.
In the following, preferable surface properties of the support surface (solid surface)
An example will be described. A preferred roughened state of the support and
The center line average roughness (R
a) 0.1-1 μm, maximum height (Ry) 1-10 μm
m, 10-point average roughness (Rz) of 1 to 10 μm, average of unevenness
Spacing (Sm) is 5 to 80 μm, average sum of local peaks
(S) is 5 to 80 μm, maximum height (Rt) is 1 to 10 μm
m, centerline mountain height (Rp) is 1-10 μm, centerline valley depth
(Rv) ranges from 1 to 10 μm, and these
One that satisfies one or more conditions is preferable, and all are satisfied
It is more preferable. The two-dimensional roughness parameter is defined as follows:
Is based. Centerline average roughness (Ra): From the roughness curve to the centerline direction
Pull out the part of the measurement length L,
The value obtained by arithmetically averaging the absolute value of the deviation from the roughness curve. Maximum height (Ry): Based on the average curve direction from the roughness curve
Extract only a quasi-length, and the peak line and valley bottom of this extracted part
A value obtained by measuring the interval between lines in the direction of the vertical magnification of the roughness curve. Ten-point average roughness (Rz): direction of the average value from the roughness curve
In this case, only the reference length is extracted and the average line
Measured in the direction of the vertical magnification from the highest peak to the fifth.
Average of the absolute value of the altitude (YP) of the summit at the lowest
The absolute value of the elevation (Yv) of the valley bottom from the valley bottom to the fifth
Value expressed as the sum of the average value in micrometers (μm). Average interval of unevenness (Sm): From the roughness curve, the average line
In the direction of the reference length.
Average line corresponding to one mountain and one adjacent valley
Is calculated, and the arithmetic average value of the intervals between the many irregularities is expressed.
Value. Average distance between local peaks (S): From the roughness curve,
Extract only the reference length in the direction.
Find the length of the average line corresponding to the local peak next to each other,
A value that represents the arithmetic mean of the intervals between the many local peaks. Maximum height (Rt): A reference length is extracted from the roughness curve.
The extracted part is sandwiched between two straight lines parallel to the center line
The value of the interval between two straight lines. Centerline height (Rp): Measured from the roughness curve in the direction of the centerline
A fixed length L is extracted and parallel to the center line of the extracted part.
The distance from the straight line through the highest peak in Centerline valley depth (Rv): From the roughness curve to the centerline direction
The part of the measurement length L is extracted and the center of this extracted part
The distance from a straight line parallel to the line and passing through the deepest valley bottom. [Method of creating uneven surface] (Type of preparation method) To provide a rough surface on the solid surface,
Various means can be employed. For example, a solid surface
Mechanically rubbed by sandblasting or brushing
The surface can be shaved to form a recess, and a rough surface can be provided.
Yes. Also, provide unevenness even with mechanical embossing.
Can do. Furthermore, the convex part is formed on the surface by gravure printing etc.
And a rough surface may be provided. Solid fine particles (matting agent)
The contained layer can be solidified by means such as coating or printing.
A rough surface may be provided by forming on the surface. Solid fine particles
Contained in polymer film at the stage of making a child film
(Internal addition), forming irregularities on the surface of the polymer film
You can also. In addition, solvent treatment, corona discharge treatment, plastic
Coarse using Zuma processing, electron beam irradiation processing, X-ray irradiation processing, etc.
A surface can also be formed. Combining the above means
You may implement. Sand blasting or resin marking
Add means to form rough surface by printing or solid fine particles
Thus, means for forming irregularities can be particularly preferably implemented. (Solid fine particle method)
Metal fine particles, metal oxide fine particles, organic or inorganic
Utilizes various types of substances such as polymer or low-molecular particles
Can be used. Specific examples of fine particles include copper powder, tin powder, iron
Powder, zinc oxide powder, silicon oxide powder, titanium oxide powder, aluminum oxide
Minium powder, molybdenum disulfide powder, calcium carbonate powder,
Clay, mica, corn starch, boron nitride, silico
Resin particles, polystyrene resin particles, fluororesin particles
Child, acrylic resin particles, polyester resin particles, acrylic
Ronitrile copolymer resin particles, zinc stearate and
Mention may be made of calcium behenate. Particle flat
The average particle size is preferably 0.05 μm or more,
More preferably, it is 0.1 μm or more. Fine particles
Adhere to the sheet surface or seal the particle-containing layer.
The average particle size of the fine particles is rough on the rough surface.
Almost corresponds to the size of. Add fine particles into the sheet
The roughness of the rough surface is the average particle size of the fine particles and the
It is determined by the thickness of the Therefore, the latter is optimal
A combination of sheets and fine particles to obtain the size of the irregularities
Therefore, it is necessary to determine the optimum particle diameter experimentally. The solid fine particles are fixed on the surface of the support to form irregularities.
As a specific example of the forming method, the film is fixed before film formation.
Method of forming a film by adding fine particles, solid fine particles
A method of applying and drying a liquid in which a binder is dispersed in a binder,
After film formation, the fine particles are pushed into the film with mechanical pressure.
Method of soldering, electrodeposition of solid fine particles after film formation
Law. Add solid particles before film formation
As a specific method of forming a film,
Examples can be given. Face as solid particulate
After melt-extrusion of PET masterbatch with blending agent, cool
A film is formed on the rejection drum and then stretched in the longitudinal and lateral directions.
Finally, by performing a heat treatment,
Film is obtained. The pigments include titanium oxide, alumina,
Use one or more of Rica
Can. Film centerline average surface roughness is blended
It can be adjusted by the particle size and blending amount of the pigment. For example, the pigment
About 0.5 to 5% by mass with a particle size of about 1 to 10 μm
It can be adjusted by blending, the larger the particle size of the pigment,
The centerline average surface roughness increases as the blending amount increases. Objective
In order to obtain an uneven surface, determine the pigment particle size and blend amount
Need to be adjusted. (Sandblasting method) What is sandblasting?
High-speed projection of fine-grained abrasive on the surface of polymer film
This is a method of making the film surface uneven.
Sand blasting may be performed by a known method, such as carbon.
N random (silicon carbide powder), metal particles, etc. together with compressed air
Powerfully spray the film surface, then wash and dry
To achieve the goal. For sandblasting
According to the film centerline average surface roughness control, spraying
Depending on the particle size and processing amount (processing frequency per area)
The larger the particle size, the higher the throughput
The higher the film surface, the larger the centerline average surface roughness of the film surface.
Become. More specifically, the sandblasting process
By spraying abrasive material onto the film surface with compressed air.
Is formed by the surface treatment
The unevenness is adjusted according to the sandblasting conditions.
The processing conditions are from the sandblast blowing nozzle.
The material is blown out and sprayed onto the film.
Cutting amount of blasting material (blasting amount), sandblasting
Angle and distance between discharge nozzle and film (blast angle)
Degree, blast distance) must be adjusted. And d
Inside the hopper by compressed air sent out from the chamber
The abrasive material is blown out from the sandblast blowing nozzle
And optimized by spraying on the film surface
Sandblasting is performed under the processing conditions. these
Specifically, this method is disclosed in, for example, Japanese Patent Laid-Open No. 8-34866.
JP, 11-90827, A JP 11-2
It is described as a known method in Japanese Patent No. 54590
The Here, in the sandblasting process,
The processing conditions are as follows.
It does not remain on the surface, and the strength of the film does not decrease
Conditions, but such processing conditions are empirically appropriate.
It can be set appropriately. Specifically, as an abrasive
Silica sand and other abrasives are used, but in particular the particle size
0.05-10mm and even 0.1-1mm silica sand
It is preferable to use it. Also, the blast distance is 100 ~
300 mm is preferable, and the blast angle is 45 to 45 mm.
The angle is preferably 90 degrees, more preferably 45 to 60 degrees. Ma
The blast amount is preferably 1 to 10 kg / min.
Good. Polyimide fill by sandblasting
So that the abrasive material and workpieces do not remain on the surface,
This is for controlling the grinding depth. The grinding depth is 0.
It is preferable to limit the thickness to 01 to 0.1 μm.
To prevent the film strength from decreasing.
The (Film thickness of hydrophilic layer and image forming layer)
Sex layer: 0.001 g / m²To 10 g / m²Until, preferred
0.01g / m²To 5g / m²Until too little
Hydrophilic effect does not appear, and if too much,
Adhesion deteriorates and printing durability decreases. Image forming layer: 0.
1g / m²To 10 g / m²Up to, preferably 0.5 g /
m²To 5g / m²If the amount is too small, the printing durability decreases,
If the amount is too large, the fine line reproducibility of the printed matter will deteriorate. [Description of Image Forming Layer] (Photosensitive layer or heat-sensitive layer) having the above hydrophilic surface
The image forming layer provided on the support is particularly limited.
Means a photosensitive layer or a heat-sensitive layer.
Di-sensitive composition or negative-sensitive composition
It is a layer. (Positive action sensitive composition) Positive action sensitive
The composition has the following known positive action sensitivity.
It is preferable to use the composition [(a) to (d)]
Among them, (a) and (b) are the most suitable positive action sensitive groups.
It is an adult. (A) containing quinonediazide and novolac resin
Conventionally used positive working photosensitive compositions. (B) a water-insoluble and alkali-soluble polymer compound and
Light-to-heat conversion agent, alkali by the action of light or heat
-Sensitive positive with increased solubility in aqueous solutions
Composition. (C) Thermally decomposable sulfonic acid ester polymer or acid
Decomposable carboxylic acid ester polymer and infrared absorber
A laser-sensitive positive composition comprising: (D) an alkali-soluble compound protected with an acid-decomposable group;
Chemically amplified positive containing a combination with an acid generator
Working photosensitive composition. Used in the positive action sensitive composition shown in the above (a) to (d)
The compounds that can be used are described below. <Quinonediazide> Suitable quinonediazide
Examples of compounds include o-quinonediazide compounds.
be able to. O-Quinonediazide used in the present invention
The compound has at least one o-quinonediazide group.
Compound that increases alkali solubility by thermal decomposition
It is possible to use compounds having various structures. One
Mario, o-quinonediazide is soluble in alkali by thermal decomposition
Losing the ability to inhibit the dissolution of functional compounds and o-quinonediazi
Both of itself changing to an alkali-soluble substance
The effect helps the solubility of the sensitive material system. Used in the present invention
Examples of o-quinonediazide compounds that can be used include J.
“Wright-Sensitive Systems” by Korser (J
oh Wiley & Sons. Inc. ) Third
The compounds described on pages 39 to 352 can be used.
Aromatic polyhydroxy compounds or aromatic amino
O-Quinonediazide sulfonates reacted with compounds
Stealth or sulfonic acid amides are preferred. Also special
Ben as described in Japanese Patent Publication No. 43-28403
Zoquinone- (1,2) -diazide sulfonic acid chloride
Or naphthoquinone- (1,2) -diazide-5-sulfo
Of acid chloride and pyrogallol-acetone resin
Tell, US Pat. Nos. 3,046,120 and 3,1
Benzoquinone described in No. 88,210 etc.
(1,2) -diazide sulfonic acid chloride or naphtho
Quinone- (1,2) -diazide-5-sulfonic acid chlora
Esters of id with phenol-formaldehyde resins
Are also preferably used. Further, naphthoquinone- (1,2) -diazi
Do-4-sulfonic acid chloride and phenol-former
Rudehydr resin or cresol-formaldehyde tree
Esters with fat, naphthoquinone- (1,2) -diazide
-4-sulfonic acid chloride and pyrogallol-acetone
Ester with resin is also preferably used. Other
Useful o-quinonediazide compounds include a number of special features.
There are reports in the pertinent literature. For example, JP
Sho 47-5303, JP 48-63802, JP
Sho 48-63803, JP-A 48-96575, Special
No. 49-38701, JP-A-48-13354,
JP-B 41-11222, JP-B 45-9610,
Japanese Examined Patent Publication No. 49-17481, US Pat. No. 2,797,2
13, No. 3,454,400, No. 3,544
No. 323, No. 3,573,917, No. 3,67
No. 4,495, No. 3,785,825, British Patent No.
Nos. 1,227,602, Nos.1,251,345,
No. 1,267,005, No. 1,329,888,
No. 1,330,932, German Patent No. 854,89
What is described in No. 0 etc. can be mentioned. The content of the o-quinonediazide compound is
1 to 50% by mass in the total solid content of the light-sensitive layer or heat-sensitive layer
About 5 to 30% by mass, preferably 10 to 30% by mass
% Is more preferable. These compounds are used alone
It can be used as a mixture of several kinds.
The content of the o-quinonediazide compound is less than 1% by mass
As a result, the image recordability deteriorates, whereas it exceeds 50% by mass.
As a result, the durability of the image area deteriorates and the sensitivity decreases. <Novolac resin or insoluble in water
And alkali-soluble polymer compound>
It is the main component that forms the photosensitive layer of the printing plate precursor
Polymer insoluble in water and soluble in alkaline aqueous solution
The compound refers to the main chain or side chain of the polymer compound as follows:
It has such an acid group structure. Phenolic hydroxyl group
(—Ar—OH), carboxylic acid group (—CO₂H), Sul
Phonoic acid group (-SO_ThreeH), phosphate group (-OPO_ThreeH), Su
Ruhonamide group (-SO₂NH-R), substituted sulfone
Mido acid group (active imide group) (-SO₂NHCOR,-
SO₂NHSO₂R, -CONHSO₂R). Where A
r represents a divalent aryl group which may have a substituent.
And R has a hydrocarbon group which may have a substituent.
The Among these, as a preferable acid group, (a-1) pheno
A hydroxyl group, (a-2) a sulfonamide group, (a-
3) Active imide groups are mentioned, especially (a-1) pheno
An alkali-soluble polymer compound having a rutile hydroxyl group
Hereinafter, it is referred to as “resin having a phenolic hydroxyl group”. )But
Most preferably, it can be used. (A-1) A having a phenolic hydroxyl group
Examples of Lucari-soluble polymer compounds include phenol
Polymer of formaldehyde and formaldehyde (hereinafter “Phenol”)
"Formaldehyde resin". ), M-cresol
Polymer of formaldehyde and formaldehyde (hereinafter referred to as “m-creso”)
"Formaldehyde resin". ), P-Crezo
Condensation polymer of aldehyde and formaldehyde, m- / p-mixed polymer
Resol and formaldehyde condensation polymer, phenol
And cresol (m-, p-, or m- / p-mixture)
) And formaldehyde condensation polymers, etc.
Volac resin and the condensation of pyrogallol and acetone
A polymer can be mentioned. Or phenol group
Using a copolymer obtained by copolymerizing a monomer having a side chain
You can also. Monomers with phenol groups used
As examples, acrylamide having a phenol group,
Kurylamide, acrylic acid ester, methacrylic acid ester
Tellurium or hydroxystyrene. Concrete
Specifically, N- (2-hydroxyphenyl) acrylamido
N- (3-hydroxyphenyl) acrylamide,
N- (4-hydroxyphenyl) acrylamide, N-
(2-hydroxyphenyl) methacrylamide, N-
(3-hydroxyphenyl) methacrylamide, N-
(4-hydroxyphenyl) methacrylamide, o-hy
Droxyphenyl acrylate, m-hydroxypheny
Acrylate, p-hydroxyphenyl acrylate
, O-hydroxyphenyl methacrylate, m-hydride
Roxyphenyl methacrylate, p-hydroxypheny
Methacrylate, o-hydroxystyrene, m-hydride
Loxystyrene, 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, 2
-(4-hydroxyphenyl) ethyl methacrylate,
2- (N '-(4-hydroxyphenyl) ureido)
Tyl acrylate, 2- (N ′-(4-hydroxyphen
Nyl) ureido) ethyl methacrylate and the like are preferably used
can do. The weight average molecular weight of the polymer is 5.0 × 10²
~ 2.0 × 10^FiveAnd the number average molecular weight is 2.0 × 10²~
1.0 × 10^FiveAre preferable from the viewpoint of image formability.
In addition to using these resins alone, there are two types
A combination of the above may also be used. When combining
Is described in U.S. Pat. No. 4,123,279.
T-Butylphenol and formaldehyde
Condensation polymers with octylphenol and formaldehyde
An alkyl group having 3 to 8 carbon atoms, such as a condensation polymer with
Of phenol and formaldehyde as substituents
A condensation polymer may be used in combination. Further, US Pat. No. 4,123,279
T-Butylphenolform as described in
Aldehyde resin, octylphenol formaldehyde
As a substituent, an alkyl group having 3 to 8 carbon atoms such as resin
Condensation product of phenol and formaldehyde
May be used. Resin having such a phenolic hydroxyl group
Can be used alone or in combination of two or more
Good. (A-2) Al having a sulfonamide group
In the case of potash-soluble polymer compounds,
(A-2) sulfonamide which is the main monomer
As a monomer having a group, in one molecule, on a nitrogen atom
Sulfonamide having at least one hydrogen atom bonded thereto
Group and at least one polymerizable unsaturated bond
Examples thereof include monomers composed of low molecular compounds. inside that
Or an acryloyl group, an allyl group, or a vinyloxy group
A substituted or monosubstituted aminosulfonyl group or
Low molecular weight compounds having a substituted sulfonylimino group are preferred.
Yes. Specifically, m-aminosulfonylphenyl methacrylate
Relate, N- (p-aminosulfonylphenyl) meta
Kurylamide, N- (p-aminosulfonylphenyl)
Acrylamide or the like can be preferably used. (A
-3) Alkali-soluble polymer compound having an active imide group
In the case of a product, it has an active imide group in the molecule,
It is a main monomer constituting this polymer compound. This
Specific examples of such a compound include N- (p-tolu
Enesulfonyl) methacrylamide, N- (p-tolue)
Nsulfonyl) acrylamide etc. are preferably used.
Can do. In the present invention, these alkali-soluble substances
The content of the polymer compound is the same as that of the photosensitive layer
It is about 10-90 mass% in the total solid content, and is 20-85.
% By mass is preferable, and 30 to 80% by mass is more preferable.
Yes. Content of alkali-soluble polymer compound is 10% by mass
If it is less than the durability of the photosensitive layer or heat-sensitive layer, the durability deteriorates.
In addition, if it exceeds 90% by mass, both sensitivity and durability are achieved.
It is not preferable. In addition, these alkali-soluble polymers
The compound may be used alone or in combination
You may use combining more than a kind. <Photothermal conversion agent> Planographic printing plate used in the present invention
When recording an image of the original plate with an IR laser or the like,
Photothermal conversion to convert light energy into heat energy
Containing an agent somewhere in the lithographic printing plate precursor
Is preferred. As a part to contain the photothermal conversion agent
Is, for example, any of hydrophilic layer, support surface layer, and support
Or it may be added between the support surface layer and the support.
Yes. The lithographic printing plate precursor used in the present invention
As the photothermal conversion agent that may be contained, ultraviolet rays, acceptable
Absorbs visible light, infrared light, white light, etc., and converts it into heat
Any material that can be obtained can be used, for example carbon black.
, Carbon graphite, pigment, phthalocyanine face
Material, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, oxidation
Examples thereof include chromium, iron sulfide, chromium sulfide and the like. Especially good
The best one is infrared light with a wavelength of 760nm to 1200nm.
Is a dye, pigment or metal that effectively absorbs. As the dye, commercially available dyes and literature (for example,
For example, "Dye Handbook" edited by the Society of Synthetic Organic Chemistry, 1970
The publicly known thing described in the publication) can be used. concrete
Azo dyes, metal complex azo dyes, pyrazolone azo dyes
Material, anthraquinone dye, phthalocyanine dye, carbo
Nium dye, quinoneimine dye, methine dye, cyanine
And dyes such as dyes and metal thiolate complexes. Like
Examples of new dyes include those disclosed in JP-A-58-125246.
JP, 59-84356, JP 59-2028
29, JP-A-60-78787, etc.
Cyanine dyes, JP-A-58-173696, JP-A-5
No. 8-181690, Japanese Patent Laid-Open No. 58-194595, etc.
The methine dyes described, JP 58-112793
JP, 58-224793, JP 59-482
87, JP 59-73996, JP 60-52
940, JP-A-60-63744, etc.
Naphthoquinone dye, disclosed in JP-A-58-112792, etc.
The squarylium dye described, British Patent 434,
And cyanine dyes described in No. 875. US Pat. No. 5,156,938
The near-infrared absorption sensitizer described above is also preferably used.
Substituted aryl benzo described in allowed 3,881,924
(Thio) pyrylium salt, JP-A-57-142645
Trimethine described in (US Pat. No. 4,327,169)
Thiapyrylium salt, JP-A-58-181051, 5
8-220143, 59-41363, 59-
84248, 59-84249, 59-146
Nos. 063 and 59-146061
Lilium compound, described in JP-A-59-216146
Cyanine dye, described in US Pat. No. 4,283,475
The pentamethine thiopyrylium salt etc.
14 and 5-19702.
A palladium compound is also preferably used. Also preferred another
US Pat. No. 4,756,993 as an example of the above dyes
Near red as described in formulas (I) and (II)
Mention may be made of external absorption dyes. Of these dyes
Especially preferred are cyanine dyes and squarily.
Dyes, pyrylium salts, nickel thiolate complexes
It is done. As the pigment used in the present invention,
Commercial pigment and color index (CI) handbook,
"Latest pigment handbook" (edited by the Japan Pigment Technology Association, 1977)
Published), "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Published), "Printing Ink Technology" CMC Publishing, published in 1984)
Can be used. As a kind of pigment
Are black pigment, yellow pigment, orange pigment, brown pigment,
Red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment,
Examples thereof include metal powder pigments and other polymer-bonded dyes.
Specifically, insoluble azo pigments, azo lake pigments, condensation polymers
Zo pigment, chelate azo pigment, phthalocyanine pigment, a
Nthraquinone pigments, perylene and perinone pigments,
Oindigo pigment, quinacridone pigment, dioxazine
Pigment, isoindolinone pigment, quinophthalone face
Dyes, dyed lake pigments, azine pigments, nitroso pigments,
Toro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black
A rack or the like can be used. Preferred among these pigments
Is carbon black. These dyes or pigments contain a photothermal conversion agent.
0.01 to 50% by mass of the total solid content of the layer, preferably 0.1
-10% by weight, particularly preferably in the case of dyes 0.5-10
% By mass, particularly preferably in the case of pigments, 3.1 to 10% by mass
Can be used in proportions. Amount of pigment or dye added
Is less than 0.01% by mass, the sensitivity is low, and 5
If it exceeds 0% by mass, the film strength of the layer containing the photothermal conversion agent will be weak.
The <Pyrolytic sulfonic acid ester polymer
Or acid-decomposable carboxylic acid ester polymer and infrared absorption
Laser-sensitive positive composition containing a collecting agent>
10-282672, EP652483, JP
Sulfonic acid esters described in JP-A-6-502260
Use polymers and carboxylic acid ester polymers
Can. Specific polymers include polystyrene.
Cyclohexyl sulfonic acid ester, polystyrene
Isopropyl sulfonic acid ester, polystyrene sulfone
Secondary class such as acid 1-methoxy-2-propyl ester
Sulfonic acid ester polymer, polymethacrylic acid t-butyl
Ester, polytetrahydropyranyl ester polymethacrylate
Acrylic acid ester protected with acid-decomposable groups such as stealth
And so on. <Alkali solubility protected with an acid-decomposable group
Chemical enhancement comprising a combination of a compound and an acid generator
Width-type positive working photosensitive composition> A protected with an acid-decomposable group
Lucari-soluble compounds are decomposed by the action of acids,
It is a compound that becomes re-soluble. T- as an acid-decomposable group
Butyl ester, t-butyl carbamate, alkoxy
Use well-known protecting groups such as ethyl esters
Can do. <Acid generator> A positive action sensitive composition.
The acid generator used in the process generates acid by heat or light.
In general, photocationic polymerization of photocationic polymerization
Initiators, photoinitiators for photoradical polymerization, photodecolorants for dyes,
Known for use in photochromic agent, micro resist, etc.
Compounds that generate acid by light and their mixtures
That can be selected and used as appropriate.
it can. For example, diazonium salt, onium salt, halogen
And sulfonic acid esters.
In the present invention, the amount of the acid generator added is that of the photosensitive layer.
Is usually 0.001 to 40 quality with respect to the total solid content of the heat-sensitive layer
The amount is about 0.01% to 20% by mass,
0.1-5 mass% is further more preferable. (Negative Action Sensitive Composition) Negative Action Sensitive Composition
As a composition, the conventionally known negative action sensitivity shown below
Compositions ((g) to (j)) can be used. (G) including a polymer having a photocrosslinkable group and an azide compound
A negative action sensitive composition. (H) Negative action sensitive composition comprising a diazo compound
Stuff. (I) Light or thermal polymerization initiator, addition polymerizable unsaturated compound
Light, containing an alkali-soluble polymer compound
Or a heat-polymerizable negative action sensitive composition. (J) Alkali-soluble polymer compound, acid generator, acid crosslinking
A negative action sensitive composition comprising a functional compound. Used in the negative action sensitive composition shown in the above (g) to (j)
The compounds that can be used are described below. “Polymer having photocrosslinkable group” negative action
A polymer having a photocrosslinkable group used in a sensitive composition
Rimmer is a light that has an affinity for aqueous alkaline developers.
Polymers having crosslinkable groups are preferred, for example US5
In the main chain or side chain of the molecule described in No. 064747, -CH =
A polymer having a photocrosslinkable group such as CH—CO—;
Cinnamic acid groups and carboxy as described in JP-A-54-15711
A copolymer having a thio group; disclosed in JP-A-60-165646
The described phenylene diacrylic acid residue and carboxyl group
Polyester resin having; JP-A-60-203630
Phenylene diacrylic acid residue and phenolic water described in
Polyester resin having an acid group; Japanese Patent Publication No. 57-4285
The phenylene diacrylic acid residue and sodium described in No. 8
Polyester resin having iminodisulfonyl group;
An azide group and a cal chain on the side chain described in Sho 59-208552
A polymer having a boxyl group can be used. In the present invention
The content of the polymer having a photocrosslinkable group is photosensitive
About 5 to 100% by mass in the total solid content of the layer or heat-sensitive layer
10 to 95% by mass, preferably 20 to 90 quality
% By weight is preferred. “Azide compounds” in negative-sensitive compositions
As the azide compound used in the
(4-azidobenzal) -4-methylcyclohexano
4,4'-siazidodiphenyl sulfide, etc.
It is done. In the present invention, the content of the azide compound is
5 to 95% by mass in the total solid content of the light-sensitive layer or heat-sensitive layer
10 to 90% by mass is preferable, and 20 to 80% is preferable.
More preferred is mass%. “Diazo compounds” to negative working sensitive compositions
Examples of the diazo resin used in the
Salts of condensates of arylamines and active carbonyl compounds
There are diazo resins typified by
Those that are soluble in organic solvents are preferred. Particularly suitable diazo resin
For example, 4-diazodiphenylamine, 4-diazo
Azo-3-methyldiphenylamine, 4-diazo-4 '
-Methyldiphenylamine, 4-diazo-3'-methyl
Diphenylamine, 4-diazo-4'-methoxydiphe
Nylamine 4-diazo-3-methyl-4'-ethoxydi
Phenylamine, 4-diazo-3-methoxydiphenyl
Amines and formaldehyde, paraformaldehyde,
Acetaldehyde, benzaldehyde, 4,4'-bis
-Presence of condensates with methoxymethyl diphenyl ether, etc.
It is an acid salt or an inorganic acid salt. As an organic acid at this time
For example, methanesulfonic acid, benzenesulfonic acid,
Ruene sulfonic acid, xylene sulfonic acid, mesitylene
Sulfonic acid, dodecyl benzesisulfonic acid, naphthalene
Sulfonic acid, propylnaphthalenesulfonic acid, 1-naphtho
-5-sulfonic acid, 2-nitrobenzenesulfone
Acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-
4-methoxybenzophenone-5-sulfonic acid, etc.
Inorganic acids include hexafluorophosphoric acid, tetra
Examples thereof include fluoroboric acid and thiocyanic acid. Furthermore, it is described in JP-A-54-30121.
A diazo resin whose main chain is a polyester group;
The carboxylic anhydride residue described in 1-273538 gazette
Having polymer and diazo compound having hydroxyl group
Diazo resin obtained by reacting polyisocyanate compound; polyisocyanate compound
And a diazo compound having a hydroxyl group
A diazo resin or the like can also be used. In the present invention, diazo tree
The fat content is based on the total solid content of the photosensitive layer or heat-sensitive layer.
And about 0-40 mass% is preferable. Also if necessary
Two or more kinds of diazo resins may be used in combination. “Photo or thermal polymerization initiators and addition polymerization properties”
`` Unsaturated compounds '' containing ethylenic double bonds capable of addition polymerization
The compound comprising at least one terminal ethylenically unsaturated bond
Any number of compounds, preferably two or more.
Can be selected. For example, monomer, prepolymer,
Ie dimer, trimer and oligomer, or
Chemical forms such as mixtures of these and their copolymers
It has something. Examples of monomers and their copolymers and
Unsaturated carboxylic acids (eg acrylic acid,
Crylic acid, itaconic acid, crotonic acid, isocrotonic acid,
Maleic acid) and aliphatic polyhydric alcohol compounds
Steal, unsaturated carboxylic acids and aliphatic polyamine compounds
And amides. Aliphatic polyhydric alcohol compound and unsaturated cal
Specific examples of monomers of esters with boric acid include
Ethyl glycol diacrylate
, Triethylene glycol diacrylate, 1,3
-Butanediol diacrylate, tetramethylene glycol
Cold diacrylate, propylene glycol diacryl
Rate, neopentyl glycol diacrylate, tri
Methylolpropane triacrylate, trimethylol
Propanetri (acryloyloxypropyl) ate
, Trimethylolethane triacrylate, hexane
Diol diacrylate, 1,4-cyclohexanedio
Diacrylate, tetraethylene glycol diac
Relate, pentaerythritol diacrylate, pen
Taerythritol triacrylate, pentaerythritol
Tetraacrylate, dipentaerythritol dia
Chryrate, dipentaerythritol pentaacrean
Dipentaerythritol hexaacrylate, sol
Bitol triacrylate, sorbitol tetraacrylate
Rate, sorbitol pentaacrylate, sorbitol
Lehexaacrylate, Tri (Aglyroyl Okijie
L) Isocyanurate, polyester acrylate
There are gomers. Methacrylic acid esters include tetrameth
Tylene glycol dimethacrylate, triethylene glycol
Cold dimethacrylate, neopentyl glycol dimethyl
Tacrylate, trimethylolpropane trimethacrylate
, Trimethylolethane trimethacrylate, ethyl
Lenglycol dimethacrylate, 1,3-butanedio
Dimethacrylate, hexanediol dimethacrylate
, Pentaerythritol dimethacrylate, penta
Erythritol trimethacrylate, pentaerythritol
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, dipentaerythritol pentamethacrylate
Sorbitol trimethacrylate, sorbitol
Tetramethacrylate, bis [p- (3-methacrylo
Xy 2-hydroxypropoxy) phenyl] dimethyl
Methane, bis- [p- (methacryloxyethoxy) phenyl
Nenyl] dimethylmethane and the like. As the itaconic acid ester, ethylene glycol
Recall shitaconate, propylene glycol diita
Conate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethyle
Glycol diitaconate, pentaerythritol di
Itaconate, sorbitol tetritaconate, etc.
The As crotonic acid ester, ethylene glycol
Dicrotonate, tetramethylene glycol dicrotone
, Pentaerythritol dicrotonate, sorbite
And tetratetracrotonate. Isocrotonic acid
As stealth, ethylene glycol cisisocrotonate
, Pentaerythritol cyisocrotonate, sorbi
Examples include tall tetraisocrotonate. As the maleic acid ester, ethylene glycol
Recall dimaleate, triethylene glycol dimale
, Pentaerythritol dimaleate, sorbitol te
There are trauma rates. In addition, the ester monomers described above
-Can also be mentioned. In addition, an aliphatic polyvalent amine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylic
Amide, 1,6-hexamethylenebis-acrylamid
1,6-hexamethylenebis-methacrylamide,
Diethylenetriaminetrisacrylamide, Xylile
Bisacrylamide, Xylylenebismethacrylami
There are As another example, Japanese Patent Publication No. 48-417
As described in Japanese Patent No. 08, two or more per molecule
Polyisocyanate compound having an isocyanate group
In addition, a polymer containing a hydroxyl group represented by the following general formula (A):
Polymerization of 2 or more molecules in a molecule to which nyl monomer is added
Vinyl urethane compounds containing a functional vinyl group
It is. CH₂= C (R¹) COOCH₂CH (R²) OH
(A) (However, R¹And R²Is H or CH_ThreeShow
The ) Japanese Laid-Open Patent Publication No. 51-37193, Japanese Patent
Urethane action as described in No. 2-32293
Relates, JP-A-48-64183, JP-B-49-
43191 and Japanese Patent Publication No. 52-30490
Polyester acrylates, such as epoxies
Epoxy actives made by reacting a resin with (meth) acrylic acid
Polyfunctional acrylates and methacrylates such as relates
Can be mentioned. Furthermore, Journal of Japan Adhesion Association vo1.
20, no. 7, pages 300-308 (1984)
Introduced as photocurable monomers and oligomers
You can also use what you have. Use of these
The amount is 5 to 70% by mass (hereinafter abbreviated as%) with respect to all components.
The ), Preferably 10 to 50% by mass. Sensitivity of the photosensitive lithographic printing plate used in the present invention
Used as a photo (thermal) polymerization initiator contained in the light layer
Depending on the wavelength of the light source
Light (thermal) initiator, or a combination system of two or more initiators
(Initial system) can be appropriately selected and used. Visible light of 400 nm or more, Ar laser
-Second harmonic of semiconductor laser, SHG-YAG
Various light initiation systems have also been proposed when using a laser as the light source.
For example, as described in US Pat. No. 2,850,445
Certain photoreductive dyes listed, such as rose bengal,
Osin, erythrosin, etc. or dye and initiator
For example, a combination of dye and amine
Beginning system (Japanese Examined Patent Publication No. 44-20189), hexaarylbi
Combination system of imidazole, radical generator and dye
No. 45-37377), hexaarylbiimidazole
And p-dialkylaminobenzylidene ketone (special
JP 47-2528, JP 54-155292
No.), a system of cyclic cis-α-dicarbonyl compounds and dyes
(Japanese Patent Laid-Open No. 48-84183), cyclic triazine and melo
Cyanine dye system (Japanese Patent Laid-Open No. 54-151024), 3
-Ketocoumarin and activator system (Japanese Patent Laid-Open No. 52-11268)
1, No. 58-15503), biimidazole,
Styrene derivatives and thiol systems (Japanese Patent Laid-Open No. 59-1402)
03), organic peroxide and dye system (Japanese Patent Laid-Open No. 59-15)
04, JP 59-140203 A, JP 59-1
89340, JP-A 62-174203, JP 6
2-1641, US Pat. No. 4,766,055), dye
And active halogen compounds (Japanese Patent Laid-Open No. 63-258903)
No., JP-A-2-63054, etc.), borated with dyes
Compound system (JP-A-62-143044, JP-A-62-2)
150242, JP-A 64-13140, JP-A 6
No. 4-13141, JP-A 64-13142, JP-A
JP 64-13143, JP-A 64-13144, JP
Sho 64-17048, JP-A-1-229003,
Kaihei 1-298348, JP-A-1-138204
), A system comprising a dye having a rhodamine ring and a radical generator
(JP-A-2-179433, JP-A-2-244050)
No.), titanocene and 3-ketocoumarin dye system
63-221110), titanocene and xanthene dyes
Furthermore, addition polymerization containing amino groups or urethane groups is possible.
System combining various ethylenically unsaturated compounds
-221958, JP-A-4-219756), Chita
Nocene and specific merocyanine dye system (Japanese Patent Laid-Open No. 6-29)
5061), a color having a titanocene and a benzopyran ring
For example, an elementary system (JP-A-8-334897)
it can. In particular, an infrared laser is used as an exposure source.
A photothermal conversion agent and a radical generator as initiators
A combination of is used. The radical generator and
Preferred compounds include onium salts, specifically
Is iodonium salt, diazonium salt, sulfonium salt
is there. The amount of these polymerization initiators used is ethylene.
0.05 to 100 parts per 100 parts by mass of the unsaturated compound
Parts by weight, preferably 0.1 to 70 parts by weight, more preferably
Can be used in the range of 0.2 to 50 parts by mass. Book
In the invention, the content of addition polymerizable unsaturated compound
5 to 95 quality with respect to the total solid content of the light-sensitive layer or heat-sensitive layer
It is about the amount%, and 5-80 mass% is preferable. Also light
The content of the polymerization initiator is the total solidity of the photosensitive layer or heat-sensitive layer.
It is about 1 to 80% by mass with respect to the shape, and 5 to 50 quality
% By weight is preferred. "Acid crosslinkable compound" negative action sensitive composition
In the presence of an acid, an acid crosslinkable compound used in
Refers to a compound that crosslinks, for example, a hydroxymethyl group,
Acetoxymethyl group or alkoxymethyl group
Examples of aromatic compounds and heterocyclic compounds that are substituted
Among them, preferred examples include phenols.
And compounds obtained by condensing aldehydes under basic conditions.
I can get lost. Among the above compounds, preferred are:
For example, phenol and formaldehyde as described above
Compounds condensed under basic conditions, m-c
Bis, a compound obtained from resole and formaldehyde
A compound obtained from phenol A and formaldehyde,
Obtained from 4,4'-bisphenol and formaldehyde
And other compounds, and GB 2,082,339
Examples include compounds disclosed as sol resins. This
These acid crosslinkable compounds have a weight average molecular weight of 500 to 1.
00,000 and a number average molecular weight of 200-50,000
Those are preferred. As another preferred example, EP-A No. 0,
No. 212,482, alkoxymethyl or
Is an aromatic compound substituted with an oxiranylmethyl group, E
P-A 0,133,216, DE-A 3,63
Disclosed in US Pat. No. 4,671, DE 3,711,264
Monomers and oligomers, melamine-formaldehyde
Condensates and urea-formaldehyde condensates, EP-A
Alkoxy substitution disclosed in 0,212,482
There are compounds. Yet another preferred example is, for example, less
At least two free N-hydroxymethyl, N-alkoxy
Melamine having methyl or N-acyloxymethyl group
-Formaldehyde derivatives. In this, N-
Alkoxymethyl derivatives are particularly preferred. Also, small molecules
The amount or oligomeric silanol is used as a silicon-containing crosslinking agent.
Can be used. Examples of these are dimethyl- and diphenyl
Ru-silanediol, as well as already precondensed and
Oligomers containing these units, for example EP-
The one disclosed in A No. 0,377,155 can be used.
The “Photothermal conversion agent” in a negative action sensitive composition
The photothermal conversion agent used is the positive action sensitive composition.
It is the same as the photothermal conversion agent used in the product. "Acid generator" used in negative action sensitive compositions
The acid generator is an acid used in the positive action sensitive composition.
The same as the generator. “Alkali-soluble polymer compound” negative action
Alkali-soluble polymers used in sensitive compositions
The compound is an alcohol used in the positive action sensitive composition.
This is the same as the potash-soluble polymer compound. In addition, the next
A polymer such as can be used. Carvone on the side chain
Addition polymers having acid groups, for example, JP-A-59-4461
No. 5, No. 54-34327, No. 58-125
77, JP-B 54-25957, JP-A 54-92
723, JP 59-53836, JP 59-7
No. 1048, ie, methacrylate
Luric acid copolymer, acrylic acid copolymer, itaconic acid copolymer
Body, crotonic acid copolymer, maleic acid copolymer,
There are stearated maleic acid copolymers. Similarly, it has a carboxylic acid group in the side chain.
There are acidic cellulose derivatives. In addition to this, it has a hydroxyl group
Useful addition of cyclic acid anhydride to addition polymer
It is. Especially among these [benzyl (meth) acrylate
/ (Meth) acrylic acid / other additions as needed
Polymerizable vinyl monomer] copolymer and [allyl (meth)
Acrylate (meth) acrylic acid / others as required
The addition-polymerizable vinyl monomer] copolymer is preferred.
In addition, as a water-soluble organic polymer, polyvinylpyrrolide
Nylon and polyethylene oxide are useful. Also cure
Alcohol-soluble polyamide to increase film strength
And 2,2-bis- (4-hydroxyphenyl) -propa
And polyether of epichlorohydrin are also useful.
The Also, Japanese Patent Publication No. 7-120040 and Japanese Patent Publication No. 7-120
041, No. 7-120042, No. 8-12
424, JP-A 63-287944, JP-A 63-
No. 287947, Japanese Patent Laid-Open No. 1-271741, Japanese Patent Laid-Open No. 1
The polyurethane resin described in No. 1-352691 is also the present invention.
It is useful for applications. These high molecular polymers have a radical reaction in the side chain.
Improves the strength of the cured film by introducing a functional group
be able to. Ethylene as a functional group capable of addition polymerization reaction
Unsaturated unsaturated groups, amino groups, epoxy groups, etc.
Examples of functional groups that can become radicals upon irradiation include mercap
Group, thiol group, halogen atom, triazine structure,
The nium salt structure, etc. is also a carboxyl group,
And a mid group. Functional group capable of addition polymerization reaction
As acryl group, methacryl group, allyl group,
Particularly preferred is an ethylenically unsaturated bond group such as a tolyl group,
In addition, amino group, hydroxy group, phosphonic acid group, phosphoric acid group,
Rubamoyl group, isocyanate group, ureido group, urei
Functionality selected from a len group, a sulfonic acid group, and an ammonio group
Groups are also useful. In order to maintain the developability of the composition, the high
The molecular polymer preferably has an appropriate molecular weight and acid value.
Yes. In order to develop with the developer described above, the weight average molecular weight is
5000 to 300,000, acid value 0.2 to 5.0 meq / g
It is preferable to use a high molecular weight polymer. These organic high molecular polymers are entrusted to the whole composition.
Any amount can be mixed. But 90% by mass
In the case of exceeding, it is preferable in terms of formed image strength and the like
Give no results. Preferably 10-90%, more preferred
30 to 80%. Also photopolymerizable ethylenic
Unsaturated compound and organic high molecular weight polymer
A range of 9/1 is preferable. A more preferable range is
2/8 to 8/2, more preferably 3/7 to 7/3
It is. [Other components] Lithographic printing used in the present invention
Various lithographic plates are used for the photosensitive layer or heat-sensitive layer of the original plate.
Various other than the above as required to obtain printing plate characteristics
These compounds may be added. Photosensitivity of lithographic printing plate precursor used in the present invention
The layer or heat-sensitive layer has a large absorption in the visible light range
Dyes can be used as image colorants. Concrete
Oil yellow # 101, oil yellow # 10
3, Oil Pink # 312, Oil Green BG, Oy
Le Blue BOS, Oil Blue # 603, Oil Black
BY, Oil Black BS, Oil Black T-50
5 (made by Orient Chemical Co., Ltd.), Victoria Pi
Pure Blue, Crystal Violet (CI4255
5), methyl violet (CI42535), ethyl
Violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue
-(CI52015) etc., or JP-A-62-29
And dyes described in Japanese Patent No. 3247
Yes. These dyes are used for image and non-image areas after image formation.
Therefore, it is preferable to add them. still,
The amount added is relative to the total solid content of the photosensitive or heat-sensitive layer.
And a ratio of 0.01 to 10% by mass. Further, the lithographic printing plate precursor used in the present invention
Processing for development conditions on photosensitive layer or heat-sensitive layer
In order to broaden the stability of Japanese Patent Laid-Open No. 62-251740
And in Japanese Patent Application Laid-Open No. 3-208514
Una nonionic surfactant, JP 59-121044
It is described in Japanese Patent Laid-Open No. 4-13149
Such amphoteric surfactants can be added. Non-ion
Specific examples of surfactants include sorbitan tristeale
Sorbitan monopalmitate, sorbitan trio
Rate, stearic acid monoglyceride, polyoxyethylene
Examples include rennonyl phenyl ether. Amphoteric interface
Specific examples of activators include alkyl di (aminoethyl)
Glycine, alkylpolyaminoethylglycine hydrochloride,
2-alkyl-N-carboxyethyl-N-hydroxy
Ethyl imidazolinium betaine and N-tetradecyl-
N, N-betaine type (for example, trade name Amogen K, No.
Ichi Kogyo Co., Ltd.). Nonionic surface activity
And photosensitive layer of lithographic printing plate precursor for amphoteric surfactant
Or the ratio which occupies for a thermosensitive layer is 0.05-15 mass
% Is preferable, more preferably 0.1 to 5% by mass
The Further, the feeling of the lithographic printing plate precursor used in the present invention
For the light-sensitive layer or heat-sensitive layer, if necessary, the flexibility of the coating film
A plasticizer is added to impart the like. For example
Ruphthalyl, polyethylene glycol, tribute citrate
Chill, diethyl phthalate, dibutyl phthalate, phthalic acid
Dihexyl, dioctyl phthalate, tricresi phosphate
, Tributyl phosphate, trioctyl phosphate, olein
Tetrahydrofurfuryl acid, acrylic acid or methacrylic acid
Luric acid oligomers and polymers are used. In addition to these, the aforementioned onium salts and halos.
Alkyl-substituted s-triazines and epoxy compounds
Products, vinyl ethers, and Japanese Patent Application No. 7-18120
Phenolic compounds having a hydroxymethyl group
Products, phenol compounds having alkoxymethyl groups, etc.
It may be added. The photosensitive layer or the heat-sensitive layer is usually composed of each of the above.
Dissolve the components in a solvent and apply on the hydrophilic layer.
Formed. The solvent used here is ethylene
Dichloride, cyclohexanone, methyl ethyl keto
, Methanol, ethanol, propanol, ethylene
Glycol monomethyl ether, 1-methoxy-2-propyl
Lopanol, 2-methoxyethyl acetate, 1-meth
X-2-propyl acetate, dimethoxyethane, milk
Methyl acid, ethyl lactate, N, N-dimethylacetami
N, N-dimethylformamide, tetramethylurea
A, N-methylpyrrolidone, dimethyl sulfoxide,
Examples include ruphoran, γ-butyl lactone, toluene, water, etc.
However, the present invention is not limited to this. this
These solvents are used alone or in combination. In solvent
The concentration of the above components (total solid content including additives) is preferably
Is 1-50 mass%. Also obtained after coating and drying
The coating amount (solid content) on the hydrophilic layer varies depending on the application.
However, speaking of the lithographic printing plate precursor, generally 0.5 to
5.0 g / m²Is preferred. As a method of applying, seed
Various methods can be used, for example, bar coater
-Coating, spin coating, spray coating, curtain coating,
Coating, air knife coating, blade coating, roll coating
Cloth etc. can be mentioned. As application amount decreases
The apparent sensitivity increases, but the film characteristics of the image recording film
Will decline. Photosensitivity of lithographic printing plate precursor used in the present invention
The adhesive layer or the heat-sensitive layer has a field for improving the coating property.
Surfactant, for example, described in JP-A-62-170950
Add a fluorosurfactant as listed
Can do. Preferred addition amount is photosensitive layer or heat sensitive
In the total solid content of the layer, more preferably 0.01 to 1% by mass
0.05 to 0.5% by mass. A lithographic printing plate raw material obtained as described above
Plate making of exposure / development processing, post-processing, etc. according to conventional methods
Processing is performed. A general plate making process will be described below. [Exposure] Lithographic stamp obtained as described above
Image exposure of printing plate precursor, followed by development with developer
Process. As a source of actinic rays used for image exposure
For example, mercury lamp, metal halide lamp, xenon
There are lamps, chemical lamps, carbon arc lamps, etc.
Radiation includes electron beam, X-ray, ion beam, far infrared
There are lines. G-line, i-line, Deep-UV light, high
Density energy beam (laser beam) is also used
The Helium neon laser as the laser beam
ー, Argon laser, Krypton laser, Helium
・ Cadmium laser, KrF excimer laser, etc.
I can get lost. In the case of laser direct drawing printing plates, the near infrared
A light source with a light emission wavelength in the
A laser and a semiconductor laser are particularly preferable. [Developer] After the exposure process,
Development processing is performed. The general developer composition is as follows:
explain. These compositions can also be used in development replenishers.
Yes. The developer preferably contains an alkali metal silicate.
That's right. The lithographic printing plate precursor used in the present invention is polyester.
Since a non-metallic support such as a film can be used,
Aluminum silicate is a problem when using an aluminum substrate
Alkali metal because there is no need to consider the precipitation of nium
Silicate systems are preferably used. Such alkali gold silicate
Metal salts include sodium silicate, potassium silicate, and lithium silicate.
Can be used alone or in combination.
You can. SiO of alkali metal silicate₂/ M₂O mole
The ratio (M represents an alkali metal) is in the range of 0.3 to 3.0
Furthermore, the range of 0.5-2.5 is preferable. the above
Developability (especially negative lithographic printing plates)
Tends to decrease hydrophilicity due to lower development
Yes, a molar ratio of 3.0 or more is not preferred. In addition, molar ratio
As the value decreases, hydrophilicity is improved.
If the ratio is 0.3 or less, the hydrophilic layer may swell or peel off.
It ’s not good. SiO in developer or replenisher₂Concentration is
0.3 to 10% by mass, and 0.5 to 6% by mass
preferable. When it exceeds 10% by mass, precipitates and crystals are formed.
In addition, a large amount of silica
Since kagel is formed, it is difficult to treat waste liquid, which is preferable.
Yes. Moreover, when it becomes lower than 0.5% by mass, sufficient hydrophilicity is obtained.
I can't get it. In the developer, an alkali other than an alkali metal silicate is used.
Potassium can be used in combination. As an example, the third
Sodium nitrate, potassium, ammonium, secondary li
Sodium carbonate, potassium, ammonium, sodium carbonate
Thorium, potassium, ammonium, sodium bicarbonate
Lithium, potassium, ammonium, sodium borate
, Potassium, ammonium, sodium hydroxide,
No ammonium, potassium or lithium
An alkaline agent is mentioned. Monomethylamine,
Dimethylamine, trimethylamine, monoethylamine
, Diethylamine, triethylamine, monoisopropyl
Pyramine, diisopropylamine, triisopropyl
Amine, n-butylamine, monoethanolamine, di
Ethanolamine, triethanolamine, monoisotop
Ropanolamine, diisopropanolamine, ethyl
Organic imines such as nimine, ethylenediamine, pyridine
Potassium is also used. These alkaline agents can be used alone or
Can be used in combination of two or more. The developer has improved hydrophilicity and promoted developability.
For the purpose of improving the dispersion of development residue and ink affinity of the image area,
And as needed to improve the stability of the image area during development.
Various surfactants and organic solvents can be added. Favorable world
Surfactants include anionic, cationic and nonionic
System and amphoteric surfactants. These surface activities
Nonionic surfactants are preferred among the sexing agents.
Ethylene oxide addition compounds of alcohols are preferred.
These are 5 moles in a sugar alcohol having 4 or more hydroxyl groups.
It is a compound obtained by adding the above ethylene oxide.
As a specific example of sugar alcohol, D, L-Tre
It, Elite, D, L-Arabit, Libit
G, Xyrit, D, L-Sorbit, D, L-Manni
, D, L-Exit, D, L-Talit, Zulshi
, Allozulcit, etc.
Combined di, tri, tetra, penta and hexaglycerides
Can also be mentioned. These ethylene oxide compounds
If necessary, the solubility of propylene oxide is acceptable.
Block copolymerization may be performed to the extent possible. These
The lenoxide addition compounds may be used alone or in combination of two or more.
Used together. Ethylene oxide addition compounds are currently
In the image process, the developer adsorbs to the image area and
It is thought that it slows intrusion and has an effect on stabilization of development.
It is done. If the number of moles of ethylene oxide added is less than 5, this
Small development stabilization effect. With preferred ethylene oxide
The number of moles added is 5-50, more preferably 5-30 moles.
It is le. If it exceeds 50 moles, the development speed of the positive PS plate
Not only slows down, but also reduces the solubility in the developer.
Concentrate enough to promote development of negative PS plates
Cannot be added to the liquid. These water-soluble ethylene oxide addition compounds
The amount of product added is relative to the developer or replenisher (use solution)
0.0001-5% by mass is suitable, more preferably
0.001 to 2% by mass. The above surfactants are simple
Can be used alone or in combination of two or more.
0.001 to 10% by mass in the developer or replenisher
More preferably, it is added in the range of 0.01 to 5% by mass.
The If necessary, an organic solvent is added to the developer.
be able to. Organic solvents have water solubility
About 10% by mass or less is suitable, preferably 5 quality
It is selected from those having an amount of less than%. For example, 1-phenyl ether
Tanol, 2-phenylethanol, 3-phenyl-1
-Propanol, 4-phenyl-1-butanol, 4-
Phenyl-2-butanol, 2-phenyl-1-butano
, 2-phenoxyethanol, 2-benzyloxy
Ethanol, o-methoxybenzyl alcohol, m-me
Toxibenzyl alcohol, p-methoxybenzyl alcohol
Coal, benzyl alcohol, cyclohexanol, 2
-Methylcyclohexanol, 3-methylcyclohexa
And 4-methylcyclohexanol, N-Fe
Nylethanolamine and N-phenyldiethanol
An amine etc. can be mentioned. The organic solvent content is
It is 0.1-5 mass% with respect to the total weight of a use liquid. That
The amount used is closely related to the amount of surfactant used.
As the amount of solvent increases, the amount of surfactant may increase.
And are preferred. This is because the amount of surfactant is small and organic
If a large amount of the agent is used, the organic solvent will not completely dissolve.
This makes it difficult to ensure good developability.
The A reducing agent may be added to the developer.
preferable. To prevent these printing plates from being soiled,
In particular, a negative photosensitive flat plate containing a photosensitive diazonium salt compound.
This is effective when developing a printing plate. Preferred organic reduction
Agents include thiosalicylic acid, hydroquinone, metho
, Methoxyquinone, resorcin, 2-methyl resorci
Phenolic compounds such as ethylene, phenylenediamine, phenol
Examples include amine compounds such as nylhydrazine. More
Preferred inorganic reducing agents include sulfurous acid and hydrogen sulfite.
Acid, phosphorous acid, phosphorous acid, phosphorous acid dihydrogen,
Sodium of inorganic acids such as uric acid and dithionite
Salt, potassium salt, ammonium salt, etc.
Yes. Of these reducing agents, the dirt prevention effect is particularly excellent.
It is sulfite. These reducing agents are
Preferably 0.05 to 5 quality for the image or replenisher
It is contained in an amount range. For the purpose of further improving hydrophilicity in the developer
Organic carboxylic acids can also be added. Preferred organic mosquito
Rubonic acid is an aliphatic carboxylic acid having 6 to 20 carbon atoms and
And aromatic carboxylic acids. Specific of aliphatic carboxylic acid
Examples include caproic acid, enanthylic acid, capryl
Acid, lauric acid, myristic acid, palmitic acid and
There are the tea acids and the like, and particularly preferable is C8 to C1.
2 alkanoic acids. Also has a double bond in the carbon chain
Either unsaturated fatty acids or branched carbon chains
Yes. Aromatic carboxylic acids include benzene rings and naphthalene
A carboxyl group is substituted on the ring, anthracene ring, etc.
Compounds, specifically o-chlorobenzoic acid, p-chloro
B-benzoic acid, o-hydroxybenzoic acid, p-hydroxy
Benzoic acid, o-aminobenzoic acid, o-aminobenzoic acid,
p-iso-propylbenzoic acid, p-tert-butyl
Benzoic acid, p-sec-butylbenzoic acid, pn-buty
Benzoic acid, 2,4-hydroxybenzoic acid, 2,5-di
Hydroxybenzoic acid, 2,6-dihydroxybenzoic acid,
2,3-dihydroxybenzoic acid, 3,5-dihydroxy
Benzoic acid, gallic acid, 1-hydroxy-2-naphtho
Acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy
-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid
However, hydroxynaphthoic acid is particularly effective. Up
Aliphatic and aromatic carboxylic acids increase water solubility
Sodium salt, potassium salt or ammonium salt
Are preferably used. Organic developer of developer used in the present invention
The content of rubonic acid is not particularly limited, but 0.1% by mass
If it is lower, the effect is not sufficient, and if it is 10% by mass or more,
Not only can it not be improved further, but other additives
May interfere with dissolution when used in combination. Therefore, preferred
The new addition amount is 0. 0 with respect to the developer or replenisher at the time of use.
1 to 10% by mass, more preferably 0.5 to 4% by mass
%. In the developer, an antifoaming agent and an
In addition, a water softener and the like can also be contained. Hard water soft
Examples of the agent include polyphosphoric acid and its sodium
Salt, potassium salt and ammonium salt, ethylenediamine
Tetraacetic acid, diethylenetriaminepentaacetic acid, triethylene
Ethylenetetramine hexaacetic acid, hydroxyethyl ethyl
Range amine triacetic acid, nitrotriacetic acid, 1,2-dia
Minocyclohexanetetraacetic acid and 1,3-diamino
Aminopolycarbohydrate such as 2-propanoltetraacetic acid
Acids and their sodium, potassium and
Ammonium salt, aminotri (methylenephosphonic acid),
Tylenediamine tetra (methylenephosphonic acid), diethyl
Rentriamine penta (methylene phosphonic acid), trie
Tylene tetramine hexa (methylene phosphonic acid), hydride
Roxyethylethylenediaminetri (methylenephosphone
Acid) and 1-hydroxyethane-1,1-diphosphone
Acids and their sodium, potassium and ammoni salts
Um salts can be mentioned. Such a water softener has a chelating power.
And the optimum value depending on the hardness and amount of hard water used
However, if you show the general amount of use, development during use
0.01 to 5% by mass in the liquid, more preferably 0.01 to
The range is 0.5% by mass. Less than this range
However, the intended purpose is not fully achieved, and the amount added is within this range.
If there are more, there is an adverse effect on the image area such as color loss.
come. The remaining component of the developer used in the present invention is water.
There are various additions known in the art as needed.
An agent can be included. Use developer and replenisher.
Leave it as a concentrate with less water content than when using it,
It is advantageous for transportation to dilute with water at the time of use.
It is. In this case, the degree of concentration is such that each component is separated or precipitated.
The extent to which it is not appropriate is appropriate. Such developed lithographic stamp
The printing plate contains washing water, a surfactant, etc. if desired.
Rinse solution, plates containing gum arabic and starch derivatives
Post-treatment is performed with a protective agent, so-called gum solution. This
The post-treatment is performed by combining these treatment liquids in various ways.
be able to. Lithographic stamp obtained by such processing
The plate is placed on an offset press and the wetness described above.
It is used for printing on a large number of sheets using sewage. [0115] According to the lithographic printing method of the present invention, a hydrophilic group is obtained.
Support having a hydrophilic surface in which raft polymer chains are present
It is made from a lithographic printing plate precursor having an image forming layer thereon.
The lithographic printing plate is marked with a dampening solution containing a specific solvent.
By maintaining the hydrophilicity of the support hydrophilic layer high
And the bonding force between the hydrophilic layer and the support is also maintained.
High stain resistance, especially when multiple parts are printed
Continuously long-term printing with improved printing performance and good printing durability
However, printability does not deteriorate. Further, the planographic plate of the present invention
According to the printing method, it does not contain harmful components in the fountain solution.
Good printability over the period, safety and environmental friendliness
Excellent in properties. [0116] The present invention will be described in detail with reference to the following examples.
However, the scope of the present invention is limited by these.
There is no. [Example 1] Positive photosensitive lithographic printing plate precursor (Creation of hydrophilic layer) As support surface layer (also used as support)
Biaxially stretched polyethylene terephthalate with a film thickness of 188 μm
Using a film (A4100, manufactured by Toyobo Co., Ltd.)
Flat plate magnetron sputtering equipment for raw processing
(Used by Shibaura Eletech CFS-10-EP70)
Then, oxygen glow treatment was performed under the following conditions. (Initial true
Empty: 9X10E-6 torr, oxygen pressure: 6.8X10E
-3 torr, RF glow 1.5KW, processing time 60se
c) Next, the glow-treated film is a nitrogen bubbled acrylic film.
It was immersed in an aqueous solution of phosphoric acid (10 wt%) at 70 ° C. for 7 hours.
Acrylic by washing the immersed membrane with water for 8 hours
A hydrophilic layer having an acid graft polymerized on the surface was obtained.
Contact angle of the obtained hydrophilic layer (water droplets in the air, Kyowa Interface Science)
When CA-Z) was measured, it was 12 °.
It was. Positive photosensitivity on the hydrophilic layer thus prepared
The following image forming layer is applied as a layer, and a positive photosensitive lithographic plate
Prepare a printing plate precursor and perform exposure, development and printability evaluation.
went. (Image forming layer formulation) [0117]
The photosensitive solution 1 was applied, and the coating weight after drying was 2.5 g / m.
²A photosensitive layer was provided so that Photosensitive solution 1   1,2-diazonaphthoquinone-5-sulfonyl chloride and Pyrogallol-esterified product with acetone resin (US Pat. No. 3,635,709) 45 parts by mass)   110 parts by mass of cresol formaldehyde novolac resin   2- (p-methoxyphenyl) -4,6- 2 parts by mass of bis (trichloromethyl) -s-triazine   Oil blue-# 603 (made by Orient Chemical Co., Ltd.) 1 part by mass   MegaFuck F-177 (Fluorine surfactant manufactured by Dainippon Ink and Chemicals)                                                             0.4 parts by mass   1000 parts by mass of methyl ethyl ketone   1000 parts by mass of propylene glycol monomethyl ether On the surface of the photosensitive layer thus prepared,
Spray the mat layer forming resin solution as shown below.
A positive lithographic printing plate precursor provided with a coating layer was obtained. mat
Methyl methacrylate / ethyl acetate as a layer forming resin solution
Chrylate / Acrylic acid (Feed weight ratio 65: 20: 1
5) 12% aqueous solution in which a part of the copolymer is sodium salt
Is prepared, and the atomizing head rotation speed is 25,0 with the rotary atomizing electrostatic coating machine.
00 rpm, the amount of resin liquid delivered is 40 ml / min, to the atomization head
The applied voltage is -90kv, the ambient temperature during coating is 25 ° C,
Relative humidity is 50%, and vapor is applied to the coated surface 2.5 seconds after coating.
3 seconds after wetting, temperature 6
Blow hot air of 0 ° C and humidity 10% for 5 seconds to dry.
It was. The average mat height is about 6μm and the average size is about 30mm.
μm, coating amount is 150 mg / m²Met. in this way
The lithographic printing plate precursor obtained in this way is 1,003 mm × 80
Prepare a large number of sheets cut to 0mm
3kw metal from a distance of 1m through the original film
Exposure was performed for 60 seconds using a halide lamp. Next, the following developer stock solution 1 and developer replenisher
A stock solution 1 and a plate surface protecting agent stock solution 1 were prepared. Developer stock solution 1 [SiO₂] / [K₂O] molar ratio 1.2, SiO₂1000 mass parts of 12.2 mass% potassium silicate aqueous solution   Polyoxyethylene (added mole number n = 12) sorbitol 2 parts by mass Developer replenisher stock solution 1 [SiO₂] / [K₂O] molar ratio 0.8, SiO₂1000 parts by mass of 11.4% by mass potassium silicate aqueous solution   4 parts by mass of polyoxyethylene (addition mole number n = 12) sorbitol [0120] Plate protectant stock solution 1   619.9 parts by mass of pure water   200 parts by weight of cream dextrin   Gum arabic (contains 5.4 mg / g calcium) 150 parts by mass of 27% by weight aqueous solution of gum arabic)   Ribonox NC60 (HLB11) (polyoxyethylene nonylphenol) Ether (manufactured by Lion Corporation) 15 parts by mass   Lapisol B-80 (HLB11) (sodium dialkylsulfosuccinate (Nippon Yushi Co., Ltd.) 5 parts by mass   Octylene glycol 5 parts by mass   Tetrabutylammonium bromide 0.5 parts by mass   0.2 parts by mass of methyl benzoate   4-Isothiazolin-3-one derivative 1.0 part by mass   Phosphoric acid (85%) 3.0 parts by mass   0.4 parts by mass of ethylenediaminepenta (methylenephosphonic acid) Commercially available automatic processor P having an immersion type developing tank
In the developing tank of S-900NP (Fuji Photo Film Co., Ltd.)
A developer obtained by diluting the above developer stock solution 1 with tap water 9 times
22 liters, followed by 8 liters of tap water,
Then, in the third bath, dilute plate protectant stock solution 1 twice with tap water.
The solution was charged. Separately, the developer replenisher stock solution supply tank
Put 5 liters of the above replenisher stock solution and protect the plate
The plate surface protection agent stock solution 1 was placed in the agent replenishment tank. like this
Processing of the exposed lithographic printing plate precursor under the above conditions.
I did it. The lithographic printing plate thus obtained was dampened as follows:
Using Example 1, print on Heidel KOR-D press
It was. (Dampening water example 1)   Propylene glycol mono-n-butyl ether 1.0 part by mass   Propylene glycol 1.0 part by mass   2-Ethyl-1,3-hexanediol 0.2 parts by mass   Carboxymethylcellulose 0.01 parts by mass   0.01 parts by weight of primary ammonium phosphate   0.02 parts by mass of ammonium nitrate   0.01 parts by weight of diammonium citrate   0.01 parts by mass of sodium acetate   2,2-Dibromo-2-nitroethanol 0.002 parts by mass   2-methyl-5-chloro-4-isothiazolin-3-one 0.002 parts by mass   Add tap water to make 100 parts by mass. As a result, a good mark with no stains on the non-image area.
30,000 prints were obtained. Also, do not change the dampening water
Although used continuously for 14 days, deterioration in printing performance was observed.
There wasn't. [Example 2] The dampening used in Example 1
Exactly the same except that the water was changed to the dampening solution example 2 described below.
Then, plate making and printing were performed. (Dampening solution example 2)   Propylene glycol mono-n-propyl ether 0.6 parts by mass   0.4 parts by mass of ethylene glycol mono-t-butyl ether   Dipropylene glycol 1.0 part by mass   3,6-dimethyl-4-octyne-3,6-diol 0.2 parts by mass   Carboxymethylcellulose 0.01 parts by mass   0.01 parts by weight of primary ammonium phosphate   0.02 parts by mass of ammonium nitrate   0.01 parts by weight of diammonium citrate   0.01 parts by mass of sodium acetate   2,2-Dibromo-2-nitroethanol 0.002 parts by mass   2-methyl-5-chloro-4-isothiazolin-3-one 0.002 parts by mass   Add tap water to make 100 parts by mass. 30,000 good prints with no smudges on non-image area
It was. Moreover, it was used continuously for 14 days without changing the dampening water.
However, no deterioration was observed in printing performance. [Comparative Example 1] Wetness used in Example 1
Except for changing the fountain solution to the comparative fountain solution example 1 described below,
In the same manner, plate making and printing were performed. (Comparative dampening solution example 1)   Isopropyl alcohol 8.0 parts by mass   Carboxymethylcellulose 0.01 parts by mass   0.01 parts by weight of primary ammonium phosphate   0.02 parts by mass of ammonium nitrate   0.01 parts by weight of diammonium citrate   0.01 parts by mass of sodium acetate   2,2-Dibromo-2-nitroethanol 0.002 parts by mass   2-methyl-5-chloro-4-isothiazolin-3-one 0.002 parts by mass   Add tap water to make 100 parts by mass. As a result, a good print was obtained by printing,
When 5,000 sheets or more are printed, background stains occur in the non-image area.
did. [Example 3] Negative type heat-sensitive lithographic printing plate precursor Use the same support and hydrophilic layer as in Example 1.
It was. However, the heat-sensitive layer which is an image forming layer is a composition having the following formulation:
To prepare a negative photosensitive lithographic printing plate precursor
Light, development and printability were evaluated. [0127] (Image forming layer prescription) IRG22 (IR dye, Nippon Kayaku) 0.1g Cross-linking agent (1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [Α, α-bis (4-hydroxyphenyl) ethyl] benzene Hexamethoxymethyl ether 0.21g Phenol-formaldehyde novolak (weight average molecular weight 12000)                                                                 2.1g Diphenyliodonium-9,10-dimethoxyanthracenesulfonate                                                               0.02g MegaFuck F-176 (Fluorine surfactant manufactured by Dainippon Ink & Chemicals, Inc.)                                                               0.06g Methyl ethyl ketone 15g 2-Methoxy-1-propanol 12g The same composition as in Example 1 was used as a support.
To obtain a negative-type heat-sensitive lithographic printing plate precursor. Next
The following developer stock solution 2, replenisher stock solution 2 and plate surface protecting agent stock
Liquid 2 was prepared. Developer stock solution 2 [SiO₂] / [K₂O] molar ratio 1.1, SiO₂1000 parts by mass of 15.0% by mass potassium silicate aqueous solution   Polyoxyethylene (added mole number n = 12) sorbitol 2 parts by mass Developer replenisher stock solution 2 [SiO₂] / [K₂O] molar ratio 0.9, SiO₂1000 parts by weight of 17.4% by weight aqueous potassium silicate solution   4 parts by mass of polyoxyethylene (addition mole number n = 12) sorbitol [0129] Plate protectant stock solution 2   619.1 parts by mass of pure water   100 parts by mass of cream dextrin   Hydroxypropylating enzyme-degrading dextrin 100 parts by mass   Soybean-derived hemicellulose 150 parts by mass   Ribonox NC60 (HLB11) (manufactured by Lion Corporation, Polyoxyethylene nonylphenol ether) 12 parts by mass   Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycoloxy) Ethylene adduct) 4 parts by mass   Benzyl alcohol 8 parts by mass   Tetraphenylphosphonium bromide 0.5 parts by mass   0.2 parts by mass of methyl benzoate   4-Isothiazolin-3-one derivative 1.0 part by mass   Magnesium sulfate 5.0 parts by mass   0.2 parts by mass of ethylenediaminepenta (methylenephosphonic acid) The negative type lithographic printing plate precursor obtained above
A semiconductor laser (wave) as a heat mode laser
Long 825 nm, beam diameter: 1 / e²= 6 μm)
The plate speed is adjusted to 110 mW at a linear velocity of 8 m / sec.
Shined. After the exposure, heat treatment was performed at 110 ° C. for 1 minute. Immersion type
Commercial automatic processor PS-900NP with a developing tank
In the developer tank of Shishi Photo Film Co., Ltd., the above developer stock solution 2
22 liters of developer diluted 9 times with tap water, 2nd
8 liters of tap water in the bath, and plate protection agent stock solution in the third bath
A solution was prepared by diluting 2 with tap water twice. Apart from development
In the replenisher stock solution supply tank, the above-mentioned development replenisher stock solution 2 is 5
Prepared with a liter. Prepared automatic processor P
Pass the heat-treated negative lithographic printing plate through S-900NP.
And processed. Next, Gum G manufactured by Fuji Photo Film Co., Ltd.
Process the printing plate with U-7 (1: 1) to make a negative planographic printing plate
Got. The lithographic printing plate thus obtained is
Using the fountain solution example 2, the mark was printed on a Heidel KOR-D printing machine.
Printed. As a result, good printed matter with non-stained non-image areas
30,000 sheets were obtained. Also without changing dampening water 1
Although used continuously for 4 days, no deterioration in printing performance was observed.
won. [Example 4] PET base as a support
Instead, surface roughness Ra (centerline average roughness) 0.7μ
m, Ry (maximum height roughness) 7 μm thickness 188 μm
Sandblasted PET film (Panak Industry)
Used). On top of that, the optical graduation described below
Acrylic acid is grafted onto the surface using
A modified hydrophilic layer was provided. (Photografting method) 50 g of acrylic acid, sodium periodate
Photograft polymerization consisting of 0.03g of lithium and 200g of water
Place the solution in a Pyrex (registered trademark) glass container
The following PET film was immersed therein. Then container
Is replaced with Ar gas, and then a 400 W high-pressure mercury lamp (physical
Using the UVL-400P manufactured by Kogaku Kagaku Sangyo Co., Ltd.
Leave the container at a distance of 10 cm from the mercury lamp for 30 minutes.
Irradiated. Wash the reacted membrane with 40 ° C warm water for 8 hours.
It was. Contact angle of the obtained hydrophilic layer (aerial water droplet, Kyowa Interface Science)
Gaku Co., Ltd., CA-Z) is measured and is 10 °
It was. Except for using this hydrophilic layer as a support
When plate making and printing were performed in exactly the same way as in Example 3,
30,000 good prints with no smudges on the image area
It was. Also, it was used continuously for 14 days without changing the dampening water.
There was no deterioration in printing performance.

Claims (1)

What is claimed is: 1. A lithographic printing plate obtained by plate-making a lithographic printing plate precursor having an image forming layer on a support having a hydrophilic surface in which a hydrophilic graft polymer chain is present Is a lithographic printing method using a dampening solution, wherein the dampening solution is a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the number of carbon atoms A lithographic printing method comprising at least one selected from the group consisting of 6 or more diol compounds. (Wherein R ¹ represents an alkyl group having 1 to 8 carbon atoms,
R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 15, R ³ represents a methyl group or an ethyl group, and R ⁴ represents a hydrogen atom or a methyl group. )