JP2003316021A - Method for making planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easy developing method capable of efficiently and reliably removing a heat sensitive layer of a non-image area of a planographic printing plate precursor obtained by disposing a heat sensitive layer comprising a fine particulate polymer. <P>SOLUTION: An image is recorded in a planographic printing plate precursor obtained by disposing a heat sensitive layer comprising a fine particulate polymer on a support having a hydrophilic surface and the plate surface is rubbed with a rubbing member in an automatic processing machine in the presence of a processing solution to remove the heat sensitive layer of the non-image area. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to direct heat sensitivity.
Relates to a method for preparing a lithographic printing plate from a lithographic printing plate precursor
Is. More specifically, based on digital signals
Thermosensitive lithographic printing plate precursor capable of image recording by scanning exposure
Simple development process for making lithographic printing plates from plates
Regarding the law. [0002] 2. Description of the Related Art In general, a lithographic printing plate is inserted in the printing process.
Lipophilic image area that accepts water and hydrophilicity that accepts fountain solution
The non-image portion. Such as a lithographic printing plate
Conventionally, a lipophilic photosensitive resin layer on a hydrophilic support.
The PS plate provided with is widely used. To conventional PS version
In the plate making process, after exposure, the non-image area is treated with a high alkali.
It is necessary to dissolve and remove with a developing solution.
Simplifying or eliminating the need for additional wet processing,
One issue that has been desired to improve the conventional technology.
The Especially in recent years, along with wet processing due to consideration for the global environment.
Disposal of discharged liquid is a major concern for the entire industry.
Therefore, the demand for improvement in this aspect has become stronger.
ing. On the other hand, another trend in this field in recent years and
Therefore, image information is processed electronically using a computer.
Digitalization technology that stores, stores, and outputs
In response to such digitization technology,
Various new image output methods have come into practical use
Yes. Along with this, high-convergence radiation such as laser light
This line is used to carry digitized image information.
The plate is scanned and exposed directly, without going through the squirrel film.
Computer-to-plate technology to produce printing plates
Attention has been paid. Among these, recently, semiconductor lasers, YAG
High-power solid lasers such as lasers are available at low cost
Because it has become possible to use high power laser
The plate making method using high power density exposure
It has become so. In this method, the exposure area
During a long exposure time, a large amount of light energy is concentrated,
Light energy is efficiently converted into heat energy and the heat
Thermal changes such as chemical changes, phase changes, changes in morphology and structure
This change is used for image recording. Tsuma
The image information is generated by light energy such as laser light.
Although the image is input, the image recording is based on the reaction by thermal energy.
Is recorded. Usually for such high power density exposure
This recording method using heat generation is called heat mode recording.
And changing light energy to heat energy
This is called exchange. Such a heat mode recording lithographic printing plate
Promising method suitable for simple development processing
One is hydrophobic thermoplastic in hydrophilic binder polymer
The hydrophilic layer in which polymer particles are dispersed is used as an image-forming heat-sensitive layer.
This is a heat-sensitive lithographic printing plate precursor. When heat is applied to the heat sensitive layer
Hydrophobic thermoplastic polymer particles are fused and hydrophilic thermosensitive layer surface
This is a method that uses the conversion of the surface into a lipophilic image area.
The For example, Japanese Patent No. 2938397,
Kaihei 9-127683 and WO99-1018
No. 6 discloses thermoplasticity in a hydrophilic binder polymer.
Hydrophilic support for heat-sensitive layer in which fine particles of hydrophobic polymer are dispersed
A lithographic printing plate precursor provided on a body is disclosed. this
In these publications, the lithographic printing plate precursor contains an infrared ray recording plate.
-Thermal exposure of thermoplastic hydrophobic polymer particles by laser exposure
After image formation by merging, press, dampening water and / or
Develops by supplying ink (so-called printing press
Image). However, such thermoplastic hydrophobicity
A non-image part heat-sensitive layer containing fine particles is fountain solution or oil
Can be removed sufficiently by on-press development with water-based ink
It is difficult, and the heat sensitive layer component remains in the non-image area.
There was a problem of causing dirt. [0008] Accordingly, it is an object of the present invention.
Lithographic printing with heat mode recording and simple development processing
To provide a method for producing a lithographic printing plate from an original plate for printing
It is. Yet another object contains a particulate polymer.
A non-image area heat sensitive layer of a lithographic printing plate precursor provided with a heat sensitive layer
Simple development process that can be removed efficiently and reliably
Is to provide. [0009] The present inventor has found that the above-mentioned problems are solved.
Contains fine particle polymer provided on the support
The removal of the heat-sensitive layer is performed by an automatic processor equipped with a rubbing member
By rubbing the plate surface with a rubbing member in the presence of the treatment liquid.
Find that it can be implemented efficiently and reliably,
The present invention has been completed. That is, the present invention provides the following:
It is as follows. (1) On a support having a hydrophilic surface, fine
A lithographic printing plate precursor provided with a heat-sensitive layer containing a particle polymer
Automatic processing with scrubbing member after image recording on plate
By rubbing the plate surface with a rubbing member in the presence of a processing solution,
Including a step of removing the heat-sensitive layer in the image area
A method for preparing a lithographic printing plate. The following are further preferred embodiments of the present invention.
Geru. (2) Over which can be removed by the treatment liquid on the heat sensitive layer
-The use of a lithographic printing plate with a coating layer
The method for producing a lithographic printing plate as described in (1) above. Planographic printing plate precursor used in the method of the present invention
At least the fine particle polycrystal is applied to the heat sensitive layer on the hydrophilic support.
Based on digital signals from computers, etc.
By image-like heating or laser light scanning photothermal conversion
Due to the generated heat, fine particles are formed in the image recording part of the heat-sensitive layer.
Child polymer, preferably fine particles having a heat-reactive functional group
Polymer reacts and melts between fine polymer particles,
When fusion occurs and the thermosensitive layer contains a hydrophilic resin,
The resin becomes hydrophobic by crosslinking and water resistance. Book
The method for preparing a lithographic printing plate of the invention comprises the above heat mode image.
The lithographic printing plate precursor after image recording is rubbed in the presence of a processing solution.
By efficiently rubbing the plate surface with the material, the heat sensitive layer in the non-image area
It can be removed reliably and with a simple development processing method
In particular, excellent lithographic printing that can prevent smearing during printing
A printing plate can be obtained. [0013] BEST MODE FOR CARRYING OUT THE INVENTION Preparation of a lithographic printing plate of the present invention is described below.
The method will be described in detail. Production of planographic printing plate of the present invention
The lithographic printing plate precursor applied to the manufacturing method has a hydrophilic surface.
A heat-sensitive layer containing a fine particle polymer on a support having
It is characterized by having. For lithographic printing plates used in the present invention
The heat sensitive layer of the original plate contains fine particle polymer as described above.
As will be described later, the fine particle polymer
-Preferably, a fine particle polymer having a thermally reactive functional group
In addition to initiating or facilitating these reactions as needed
Containing compounds, hydrophilic resins, photothermal conversion agents, etc.
Further, it contains other components as necessary. The method for preparing a lithographic printing plate in the present invention is as follows:
Process after image recording on the above lithographic printing plate precursor
Non-image area by rubbing the plate surface with a rubbing member in the presence of liquid
And a step of removing the heat-sensitive layer. Main departure
The removal of the heat sensitive layer in the non-image area in
It is preferably carried out by an automatic processor equipped with steps and rubbing members.
Can be. The automatic processor is not particularly limited
However, automatic processing using a rotating brush roll as the rubbing member
A science machine is particularly preferred. FIG. 1 is suitable for the development processing of the present invention.
As shown in the layout of the automatic developing processor, the processing solution 10 is circulated.
It is sent to the spray pipe 5 by the ring pump 11 and showered.
Ring the rotating brush roll 1 and the printing plate 12 (lithographic mark)
Printing plate) and the surface 12 of the plate with the rotating brush roll 1
A process that removes the heat-sensitive layer from the non-image area using an automatic processor
According to the process, a lithographic printing plate is produced. Hereinafter, the method for preparing a lithographic printing plate according to the present invention is suitable.
Each configuration of the lithographic printing plate precursor used will be described. (Support having a hydrophilic surface) Hydrophilic used in the present invention
For a support having a conductive surface, the support itself is hydrophilic.
One, the surface of the support made hydrophilic, or
Including those provided with a hydrophilic layer on a support. Support used for the lithographic printing plate of the present invention
The body is a dimensionally stable plate-like material, for example,
Paper, plastic (eg, polyethylene, polypropylene)
Paper, metal plates, etc.)
(For example, aluminum, zinc, copper, etc.), plastic
Film (eg cellulose diacetate, cellulose triacetate
, Cellulose propionate, cellulose butyrate, dairy acetate
Acid cellulose, cellulose nitrate, polyethylene terephthalate
Rate, polyethylene naphthalate, polyethylene, polyethylene
Restyrene, polypropylene, polycarbonate, poly
Vinyl acetal, etc.)
Film, plastic film with cavities
The metal is laminated or vapor-deposited as above
Paper or plastic film. The support used for the lithographic printing plate precursor of the present invention
As the holder, polyester film or aluminum
A plate is preferred. Among them, dimensional stability is good and relatively low.
An aluminum plate which is a valence is particularly preferred. Suitable aluminum
The nickel plate is mainly pure aluminum plate and aluminum.
It is an alloy plate containing a small amount of foreign elements as a component.
Plastic laminated or vapor-deposited with minium
It may be a film. Foreign elements in aluminum alloys
Includes silicon, iron, manganese, copper, magnesium, black
, Zinc, bismuth, nickel, titanium, etc. Together
The content of foreign elements in gold is at most 10% by weight. Book
Particularly suitable aluminum in the invention is pure aluminum.
However, completely pure aluminum is manufactured by refining technology.
Because it is difficult to manufacture, even those that contain slightly different elements
Good. Thus, the aluminum plate applied to the present invention
The composition is not specified and is conventionally known
It is possible to use an aluminum plate of a public material as appropriate
Yes. The thickness of the aluminum plate used in the present invention is
About 0.1 mm to 0.6 mm, preferably 0.15 m
m to 0.4 mm, particularly preferably 0.2 mm to 0.3 m
m. Prior to roughening the aluminum plate,
If desired, for example, the surface activity to remove surface rolling oil
Degreasing with an organic agent, organic solvent or alkaline aqueous solution
Processing is performed. Surface roughening treatment of aluminum plate
Can be performed by various methods, for example, mechanically rough
Method of surface treatment, method of electrochemically dissolving and roughening the surface
And by chemically dissolving the surface selectively.
The Mechanical methods include ball polishing and brush polishing
A known method such as a polishing method, a blast polishing method, or a buff polishing method.
Can be. In addition, as an electrochemical roughening method
Is performed by alternating current or direct current in hydrochloric acid or nitric acid electrolyte
There is a way. Also disclosed in Japanese Patent Laid-Open No. 54-63902.
Use a combination of both as shown
be able to. The surface roughening by the above-described method is performed by using aluminum.
The center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0.
It is preferable to apply in the range of μm. Rough surface
Tempered aluminum plate is potassium hydroxide if necessary
Using an aqueous solution of sodium hydroxide or sodium hydroxide.
Chining is performed and neutralization is performed.
In order to increase wear resistance, anodization is performed. A
As an electrolyte used for anodizing of ruminium plates
Can use various electrolytes to form a porous oxide film
In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or
Those mixed acids are used. Their electrolyte concentration is
It is determined as appropriate depending on the type of solution. The treatment conditions for anodization depend on the electrolyte used.
Since it varies, it is not possible to specify it in general, but in general electrolytes
Concentration of 1-80 wt% solution, liquid temperature is 5-70 ° C., current
Density 5-60A / dm² , Voltage 1-100V, Electrolysis time
A range of 10 seconds to 5 minutes is appropriate. Anodized film
The amount of is 1.0-5.0 g / m², Especially 1.5-4.0 g /
m²It is preferable that 1.0 g / m² Fewer
Insufficient printing durability or non-image area of lithographic printing plate
It becomes easy to be scratched, and ink adheres to the scratched part during printing
The so-called “scratch stain” is likely to occur. Anodizing treatment
After being applied, the aluminum surface may be hydrophilized if necessary.
Reason is given. As the hydrophilization treatment used in the present invention
U.S. Pat. Nos. 2,714,066 and 3,18.
No. 1,461, No. 3,280,734 and No. 3,9
No. 02,734, an alkali metal
There is a silicate (for example, sodium silicate aqueous solution) method.
In this method, the support is an aqueous sodium silicate solution
Soaked or electrolyzed. Other special
Zirconyl fluoride disclosed in Japanese Patent Publication No. 36-22063
Potassium Conate and US Pat. No. 3,276,868
No. 4,153,461 No. 4,689,27
Treated with polyvinylphosphonic acid as disclosed in No. 2
Or the like. In addition, the support of the present invention has a polyester fiber.
When using non-conductive materials such as rum, the heat-sensitive layer of the support
An antistatic layer is provided on the side, opposite side, or both sides
Is preferred. An antistatic layer as a support and a hydrophilic layer described below;
If it is provided between the two, it also contributes to improved adhesion of the hydrophilic layer
To do. As the antistatic layer, metal oxide fine particles and mat
A polymer layer in which the agent is dispersed can be used. The metal oxide particles used in the antistatic layer
The material is SiO₂, ZnO, TiO₂, SnO₂,
Al₂O_Three, In₂O_Three, MgO, BaO, MoO_Three, V₂O
_FiveAnd their complex oxides and / or their metals
In addition to metal oxides containing different atoms in the oxide
it can. These may be used alone or in combination
Also good. As the metal oxide, SiO₂, ZnO, Sn
O₂, Al₂O_ThreeTiO₂, In₂O_Three, MgO is preferred
Yes. As an example containing a small amount of different atoms, A
l or In, SnO₂Sb, Nb or
Halogen element, In₂O_ThreeFor different atoms such as Sn
30 mol% or less, preferably 10 mol% or less
Can be mentioned. Metal oxide particles
It is contained in the range of 10 to 90% by weight in the antistatic layer.
It is preferable. The average particle size of the metal oxide particles
The range whose diameter is 0.001-0.5 micrometer is preferable. here
The average particle size is only the primary particle size of metal oxide particles
In addition, the value includes the particle diameter of the higher order structure. Matting agent that can be used in the antistatic layer
Preferably, the average particle size is 0.5 to 20 μm
More preferably, the average particle size is 1.0 to 15 μm.
Examples include inorganic or organic particles. As inorganic particles,
For example, silicon oxide, aluminum oxide, titanium oxide,
Metal oxides such as zinc oxide, calcium carbonate, barium sulfate
Gold, barium titanate, strontium titanate, etc.
A genus salt etc. are mentioned. Organic particles include polymethyl
Tacrylate, polystyrene, polyolefin and it
Examples thereof include crosslinked particles of these copolymers. Matting agent
It is contained in the electric prevention layer in the range of 1 to 30% by weight.
Is preferred. Polymers that can be used in the antistatic layer
For example, proteins such as gelatin and casein
Quality, carboxymethyl cellulose, hydroxyethyl cellulose
Roulose, acetylcellulose, diacetylcellulose
Cellulose compounds such as triacetyl cellulose,
Such as kisstran, agar, sodium alginate, starch derivatives, etc.
Saccharides, polyvinyl alcohol, polyvinyl acetate, polya
Krylate ester, polymethacrylate ester, police
Tylene, polyacrylamide, polyvinylpyrrolidone,
Polyester, polyvinyl chloride, polyacrylic acid, poly
Examples thereof include synthetic polymers such as methacrylic acid. Polymer
-Is included in the antistatic layer in the range of 10 to 90% by weight.
It is preferable. The thickness of the antistatic layer is 0.01
It is preferably ˜1 μm. In order to make the surface of the support hydrophilic, the present invention
As a hydrophilic layer that can be provided on a bright support,
For example, crosslink or pseudo-crosslink organic hydrophilic polymer
Organic hydrophilic matrix and poly
Alkoxysilane, titanate, zirconate or al
Sol-gel conversion consisting of hydrolysis and condensation reaction of minate
A layer having an inorganic hydrophilic matrix obtained by
Or an inorganic thin film having a surface containing a metal oxide
Inorganic hydrophilicity obtained by sol-gel conversion
With a surface containing a functional matrix or metal oxide
An inorganic thin film is preferred. Organic hydrophilic matrix of the hydrophilic layer of the present invention
The cross-linking reaction used to form the
Covalent bond formation or ionic bond formation with polyvalent metal salt
Is possible. As an organic hydrophilic polymer used in the present invention
For example, a polymer having a functional group that can be used for a crosslinking reaction.
Remers are preferred. Preferred functional groups include, for example,
-OH, -SH, -NH₂ , -NH-, -CO-NH
₂ , -CO-NH-, -O-CO-NH-, -NH-C
O—NH—, —CO—OH, —CO—O—, —CO—O
^- , -CS-OH, -CO-SH, -CS-SH, -S
O_ThreeH, -SO₂ (O^- ), -PO_Three H₂ , -PO (O^-
 )₂, -SO₂-NH₂ , -SO₂—NH—, —CH═C
H₂, -CH = CH-, -CO-C (CH_Three) = CH₂,
-CO-CH = CH₂, -CO-CH₂-CO-, -CO
-O-CO-, the following functional group, etc. are mentioned. [0027] [Chemical 1] In particular, hydroxyl group, amino group, carboxyl
Group and epoxy group are preferred. Such an organic hydrophilic polymer of the present invention and
It is possible to use a known water-soluble binder.
Yes, for example, polyvinyl alcohol (saponification degree 60%
Polyvinyl acetate), carboxy-modified polyvinyl
Modified polyvinyl alcohol such as nil alcohol, starch
And its derivatives, carboxymethylcellulose and
Salt, cellulose like hydroxyethyl cellulose
Derivatives, casein, gelatin, gum arabic, polyvinyl chloride
Rupyrrolidone, vinyl acetate-crotonic acid copolymer and
Salt, styrene-maleic acid copolymer and its salt, poly
Acrylic acid and its salts, polymethacrylic acid and its salts,
Polyethylene glycol, polyethyleneimine, polybi
Nylphosphonic acid and its salts, polystyrene sulfonic acid and
And its salt, poly (methacryloyloxypropanesulfone
Acid) and salts thereof, polyvinylsulfonic acid and salts thereof,
Li (methacryloyloxyethyltrimethylammonium
Chloride), polyhydroxyethyl methacrylate,
Polyhydroxyethyl acrylate, polyacrylamid
And the like. These polymers impair hydrophilicity
Unless otherwise specified, it may be a copolymer,
It may be used alone or in combination of two or more. So
The amount used is 20 wt.% With respect to the total solid weight of the hydrophilic layer.
% To 99% by weight, preferably 25% to 95% by weight,
More preferably, it is 30 to 90% by weight. In the present invention, the organic hydrophilic polymer
Crosslinking can be performed with a known crosslinking agent. Publicly known
As cross-linking agents, polyfunctional isocyanate compounds,
-Functional epoxy compounds, polyfunctional amine compounds, polyols
Compound, polyfunctional carboxyl compound, aldehyde compound,
Polyfunctional (meth) acrylic compounds, polyfunctional vinyl compounds,
Multifunctional mercapto compound, polyvalent metal salt compound, polyal
Coxisilane compounds and their hydrolysates, polyarco
Xititanium compounds and hydrolysates thereof, polyalkoxy
Si-aluminum compound and its hydrolyzate, polymethyl
Roll compounds, polyalkoxymethyl compounds, etc.
It is also possible to add a known reaction catalyst to accelerate the reaction.
Noh. The amount used is the total solid content in the coating liquid of the hydrophilic layer.
1% to 50% by weight, preferably triple
% To 40% by weight, more preferably 5% to 35% by weight
%. Inorganic hydrophilic matrix of the hydrophilic layer of the present invention
Sol-gel conversion that can be used for the formation of
In the system, the bonding group coming out of the polyvalent element is connected through the oxygen atom.
A network structure is formed, and at the same time, the polyvalent metal is an unbonded hydroxyl group.
And also has an alkoxy group, and these are mixed resinous
A polymer having a structure, which is an alkoxy group or water
At the stage with many acid groups, it is in a sol state, and ether linkage is
As it progresses, the network-like resin structure becomes stronger. Ma
In addition, a part of the hydroxyl group is bonded to the solid fine particles.
The function of modifying the surface of solid fine particles and changing the degree of hydrophilicity
Have both. Hydroxyl group and azo group that perform sol-gel conversion
The polyvalent binding element of the compound having a ruxoxy group is aluminum.
Such as um, silicon, titanium and zirconium.
Can be used in the present invention.
The siloxane bond that can be used most preferably
The sol-gel conversion system will be described. aluminum,
The sol-gel conversion using titanium and zirconium is
Replace the silicon described above with each element
be able to. That is, particularly preferably used is
At least one silanol capable of sol-gel conversion
This is a system including a silane compound having a group. The following
The system using the Rugel transformation will be further described. Z
Inorganic hydrophilic matrix formed by rugel transformation
Preferably have siloxane bonds and silanol groups
A resin having at least one silanol group.
Apply a coating solution that is a sol system containing the silane compound
Hydrolysis condensation of silanol groups during cloth, drying and aging
Progresses to form a siloxane skeleton structure, and gelation progresses.
Formed by running. In addition, the gel structure
Some of the tricks are physical properties such as film strength and flexibility.
For the purpose of improving, improving applicability, adjusting hydrophilicity, etc.
Add the above organic hydrophilic polymer or crosslinking agent
Is also possible. The siloxane resin that forms the gel structure
It is represented by the following general formula (I) and at least one sila
The silane compound having a nor group is represented by the following general formula (II):
Obtained by hydrolysis of the indicated silane compounds.
A partial hydrolyzate of the silane compound of general formula (II) alone
In general, silane compounds are not partially hydrolyzed.
It may consist of combined oligomers or
It may be a mixed composition of orchid compound and its oligomer
Yes. [0033] [Chemical 2] The siloxane resin of the general formula (I) is
At least of the silane compounds represented by the following general formula (II)
Formed by sol-gel conversion of one compound,
R in formula (I)⁰¹~ R⁰³At least one of them represents a hydroxyl group
Other than the above, the symbol R in the following general formula (II)₀ And Y
Represents an organic residue. General formula (II) (R₀)_n Si (Y)_4-n In the general formula (II), R₀Is a hydroxyl group, hydrocarbon
Represents a prime group or a heterocyclic group; Y is a hydrogen atom or halogen
Atom (fluorine atom, chlorine atom, bromine atom or iodine atom
Represents -OR₁ , -OCOR₂ Or -N (R
_Three ) (R_Four (R)₁ , R ₂Are each hydrocarbon groups
R_Three , R_Four May be the same or different and are hydrogen atoms
Or represents a hydrocarbon group), n represents 0, 1, 2 or 3
The R in the general formula (II)₀Hydrocarbon group or
A telocyclic group is, for example, a substituted group having 1 to 12 carbon atoms.
Good linear or branched alkyl groups (eg meth
Group, ethyl group, propyl group, butyl group, pentyl group,
Hexyl, heptyl, octyl, nonyl, decyl
Group, a dodecyl group, etc .;
Is a halogen atom (chlorine atom, fluorine atom, bromine atom
Child), hydroxy group, thiol group, carboxy group, sulfur
E group, cyano group, epoxy group, -OR 'group (R'
Til, ethyl, propyl, butyl, heptyl
Group, hexyl group, octyl group, decyl group, propenyl
Group, butenyl group, hexenyl group, octenyl group, 2-hydroxy
Droxyethyl group, 3-chloropropyl group, 2-cyano
Ethyl group, N, N-dimethylaminoethyl group, 1-bromide
Moethyl group, 2- (2-methoxyethyl) oxyethyl
Group, 2-methoxycarbonylethyl group, 3-carboxy
Propyl group, benzyl group, etc.), -OCOR '' group
(R ″ represents the same content as R ′), —COO
R ″ group, —COR ″ group, —N (R ′ ″) (R ′ ″) group
(R ′ ″ represents a hydrogen atom or the same content as R ′.
Each may be the same or different), -NHCONH
R ″ group, —NHCOOR ″ group, —Si (R ″)_ThreeGroup,-
CONHR ′ ″ group, —NHCOR ″ group and the like.
A plurality of these substituents may be substituted in the alkyl group.
I), Linear chain having 2 to 12 carbon atoms which may be substituted
Or a branched alkenyl group (eg, vinyl group, propylene group)
Nyl, butenyl, pentenyl, hexenyl,
Octenyl, decenyl, dodecenyl, etc.
The group substituted with the above is substituted with the above alkyl group
Group having the same contents as the group), C7-14
An optionally substituted aralkyl group (eg benzyl
Group, phenethyl group, 3-phenylpropyl group, naphthyl group
Methyl group, 2-naphthylethyl group, etc .; substituted for these groups
The group to be substituted is the same as the group substituted with the alkyl group.
One content may be listed, or multiple substitutions may be made.
I), C5-C10 optionally substituted alicyclic
Group (for example, cyclopentyl group, cyclohexyl group, 2
-Cyclohexylethyl group, 2-cyclopentylethyl
Group, norbornyl group, adamantyl group, etc.
The group to be substituted is the same as the substituent of the alkyl group.
The content may be listed, or more than one may be substituted), charcoal
An optionally substituted aryl group having a prime number of 6 to 12 (for example,
A phenyl group or a naphthyl group.
Of the same content as the group substituted by
A plurality of which may be substituted), or a nitrogen atom, an oxygen atom,
Contains at least one atom selected from sulfur atoms
A heterocyclic group which may be condensed (for example, the heterocyclic ring)
Pyran ring, furan ring, thiophene ring, morpholine
Ring, pyrrole ring, thiazole ring, oxazole ring, pyri
Gin ring, piperidine ring, pyrrolidone ring, benzothiazole
Ring, benzoxazole ring, quinoline ring, tetrahydride
A lofuran ring or the like may contain a substituent. As a substituent
Having the same content as the group substituted with the alkyl group.
And may be substituted in plural. -OR of Y in the general formula (II)₁ Group, -OC
OR₂Group or -N (R_Three) (R_Four) Group substituents include:
For example, the following substituents are represented. -OR₁ In the group R
₁ Is an optionally substituted aliphatic group having 1 to 10 carbon atoms (for example,
For example, methyl, ethyl, propyl, butyl, hep
Til, hexyl, pentyl, octyl, nonyl
Group, decyl group, propenyl group, butenyl group, heptenyl
Group, hexenyl group, octenyl group, decenyl group, 2-hydroxy
Droxyethyl, 2-hydroxypropyl, 2-methyl
Toxiethyl group, 2- (methoxyethyloxo) ethyl
Group, 1- (N, N-diethylamino) ethyl group, 2-methyl
Toxipropyl group, 2-cyanoethyl group, 3-methylo
Xapropyl group, 2-chloroethyl group, cyclohexyl
Group, cyclopentyl group, cyclooctyl group, chlorocycline
Rohexyl group, methoxycyclohexyl group, benzyl
Group, phenethyl group, dimethoxybenzyl group, methylben
A dil group, a bromobenzyl group, etc.). -OCOR₂ In the group R₂ Is R₁ When
Aliphatic groups having the same content or substituted with 6 to 12 carbon atoms
May be an aromatic group (the aromatic group is aryl
And the same as those exemplified with respect to the R group.
-N (R_Three ) (R_Four ) In the group R_Three  , R_Four
May be the same or different from each other, and each may be a hydrogen atom or
Is an optionally substituted aliphatic group having 1 to 10 carbon atoms (for example,
-OR₁ R of group₁ The same contents as
Represent). More preferably, R_Three And R_Four Carbon
The sum of the numbers is within 16 pieces. Shown by general formula (II)
Specific examples of silane compounds include the following:
However, the present invention is not limited to this. Tetrachlorosilane, tetrabromosila
Tetramethoxysilane, Tetraethoxysilane, Te
Trisopropoxysilane, tetra-n-propylsila
, Tetra-t-butoxysilane, tetra-n-butoxy
Orchid, dimethoxydiethoxysilane, methyltrichloro
Silane, methyltribromosilane, methyltrimethoxy
Silane, methyltriethoxysilane, methyltriisopropyl
Lopoxysilane, methyltri-t-butoxysilane, ethyl
Lutrichlorosilane, ethyltribromosilane, ethyl
Trimethoxysilane, ethyltriethoxysilane, ethyl
Lutriisopropoxysilane, ethyltri-t-butoxy
Silane, n-propyltrichlorosilane, n-propyl
Tribromosilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, n-propyltrii
Sopropoxysilane, n-propyltri-t-butoxy
Lan, n-hexyltrichlorosilane, n-hexyl
Librom silane, n-hexyltrimethoxysilane, n
-Hexyltriethoxysilane, n-hexyltriiso
Propoxysilane, n-hexyltri-t-butoxysila
N-decyltrichlorosilane, n-decyltribro
Musilane, n-decyltrimethoxysilane, n-decyl
Triethoxysilane, n-decyltriisopropoxy
Lan, n-decyltri-t-butoxysilane, n-octa
Decyltrichlorosilane, n-octadecyltribromo
Silane, n-octadecyltrimethoxysilane, n-o
Kutadecyltriethoxysilane, n-octadecyltri
Isopropoxysilane, n-octadecyltri t-but
Xysilane, phenyltrichlorosilane, phenyltri
Bromosilane, phenyltrimethoxysilane, phenyl
Triethoxysilane, phenyltriisopropoxysila
, Phenyltri-t-butoxysilane, dimethyl dichloro
Silane, dimethyldibromosilane, dimethyldimethoxy
Sisilane, dimethyldiethoxysilane, diphenyl dic
Lorsilane, diphenyldibromosilane, diphenyldi
Methoxysilane, diphenyldiethoxysilane, pheny
Rumethyldichlorosilane, phenylmethyldibromosila
, Phenylmethyldimethoxysilane, phenylmethyl
Diethoxysilane, Triethoxyhydrosilane, tribromhi
Drosilane, trimethoxyhydrosilane, isopropoxy
Sihydrosilane, tri-t-butoxyhydrosilane, vinyl
Lutrichlorosilane, vinyltribromosilane, vinyl
Trimethoxysilane, vinyltriethoxysilane, vinyl
Lutriisopropoxysilane, vinyltri-t-butoxy
Silane, trifluoropropyltrichlorosilane, tri
Fluoropropyltribromosilane, trifluoropro
Pyrtrimethoxysilane, trifluoropropyltrie
Toxisilane, trifluoropropyltriisopropoxy
Sisilane, trifluoropropyltri-t-butoxysila
Γ-glycidoxypropylmethyldimethoxysila
Γ-glycidoxypropylmethyldiethoxysila
Γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glyce
Sidoxypropyl triisopropoxysilane, γ-glycol
Sidoxypropyltri-t-butoxysilane, γ-metac
Liloxypropylmethyldimethoxysilane, γ-metac
Liloxypropylmethyldiethoxysila, γ-methacryl
Roxypropyltrimethoxysilane, γ-methacryloxy
Cypropyl triisopropoxysilane, γ-methacrylo
Xylpropyltri-t-butoxysilane, γ-aminopro
Pyrmethyldimethoxysilane, γ-aminopropylmethyl
Rudiethoxysilane, γ-aminopropyltrimethoxy
Silane, γ-aminopropyltriethoxysilane, γ-
Aminopropyltriisopropoxysilane, γ-amino
Propyltri-t-butoxysilane, γ-mercaptopro
Pyrmethyldimethoxysilane, γ-mercaptopropyl
Methyldiethoxysilane, γ-mercaptopropyltri
Methoxysilane, γ-mercaptopropyltriethoxy
Silane, γ-mercaptopropyl triisopropoxy
Lan, γ-mercaptopropyltri-t-butoxysila
Β- (3,4-epoxycyclohexyl) ethylate
Limethoxysilane, β- (3,4-epoxycyclohexane
Sil) ethyltriethoxysilane and the like. Inorganic hydrophilic matrix of the hydrophilic layer of the present invention
A silane compound represented by the general formula (II)
Both sol-gel such as Ti, Zn, Sn, Zr, Al, etc.
Used in combination with metal compounds that can be bonded to resin during conversion
can do. Examples of metal compounds used
Ti (OR_Five )_Four(R_FiveIs methyl, ethyl, pro
Pyr group, butyl group, pentyl group, hexyl group, etc.), Ti
Cl_Four , Ti (CH_ThreeCOCHCOCH_Three)₂ (OR_Five )
₂ , Zn (OR_Five )₂ , Zn (CH _Three COCHCOCH
_Three )₂ , Sn (OR_Five )_Four , Sn (CH_Three COCHCO
CH _Three )_Four , Sn (OCOR_Five)_Four, SnCl_Four , Zr
(OR_Five )_Four , Zr (CH_ThreeCOCHCOCH_Three)_Four , A
l (OR_Five )_Three , Al (CH_ThreeCOCHCOCH_Three )_Threeetc
Is mentioned. Further, the silane compound represented by the general formula (II)
And further the hydrolysis and heavy weight of the metal compound used in combination.
In order to accelerate the condensation reaction, an acidic catalyst or a basic catalyst is added.
It is preferable to use together. Catalysts can be acid or basified
Leave the compound as it is or water or alcohol
Those dissolved in a solvent (hereinafter referred to as acidic
Medium and a basic catalyst). The concentration at that time
However, if the concentration is high, hydrolysis /
The polycondensation rate tends to increase. However, highly concentrated salt
When a basic catalyst is used, a precipitate is generated in the sol solution.
As a result, the degree of basic catalyst is 1N (concentrated in aqueous solution).
The following is desirable. The kind of acidic catalyst or basic catalyst is particularly
Although it is not limited, specifically, as an acidic catalyst, hydrochloric acid
Hydrogen halide such as nitric acid, sulfuric acid, sulfurous acid, sulfurized water
Hydrogen, perchloric acid, hydrogen peroxide, carbonic acid, formic acid, acetic acid, etc.
Rubonic acid, R in the structural formula represented by RCOOH
Substituted or substituted carboxylic acid substituted with elemental or substituent
As a basic catalyst such as sulfonic acid such as Zensulfonic acid
Ammonia base such as aqueous ammonia, ethyl acetate
Examples include amines such as min and aniline. More details of the above sol-gel method can be found in
Saio "Sol-Gel Science" Agne Jofusha (published)
(1988) Satoshi Hirashima “Functions of the latest sol-gel method
Thin Film Manufacturing Technology ”, General Technology Center (published) (1992)
Is described in detail in the book. The organic or inorganic hydrophilic matrix of the present invention.
In addition to the above, the hydrophilic layer of
Control, improvement of physical strength of hydrophilic layer, composition of the layer
Improvement of dispersibility between materials, improvement of coating properties, improvement of printability
Various objective compounds such as can be added. example
Plasticizers, pigments, dyes, surfactants, hydrophilic particles, etc.
Is mentioned. The hydrophilic particles are not particularly limited.
Are preferably silica, alumina, titanium oxide,
Gnesium, magnesium carbonate, calcium alginate
Etc. These can promote hydrophilicity or coat
It can be used for strengthening. More preferably,
Rica, alumina, titanium oxide or a mixture of these
The Parent of the organic or inorganic hydrophilic matrix of the present invention
In the aqueous layer, especially silica, alumina, titanium oxide
In a preferred embodiment containing metal oxide particles such as
is there. Silica has many hydroxyl groups on its surface,
Part constitutes a siloxane bond (-Si-O-Si-)
Yes. In the present invention, it can be preferably used.
Rika is also called colloidal silica.
Or a particle size of 1 to 100 nm dispersed in a polar solvent.
Rica ultra fine particles. Specifically, Toshiro Kaga, Director Hayashi Hayashi
Osamu “Applied Technology of High-Purity Silica” Volume 3, CM Co., Ltd.
See C. (1991). Alumina which can be preferably used
It has a colloidal size of 5 to 200 nm.
Mina hydrate (boehmite), anion in water (for example,
For example, halogen atom ions such as fluorine ions and chlorine ions
And carboxylate anions such as acetate ions)
And distributed. Also preferably used
Titanium oxide that can be produced has an average primary particle size of 50 to 500
nm anatase or rutile titanium oxide,
If necessary, use a dispersant in water or a polar solvent.
It is distributed. In the present invention, it can be preferably used.
The average primary particle size of the hydrophilic particles is 1 to 5000 nm
More preferably, it is 10 to 1000 nm.
In the hydrophilic layer of the present invention, these hydrophilic particles
May be used alone or in combination of two or more.
good. The amount used is based on the total solid weight of the hydrophilic layer.
5% to 90% by weight, preferably 10% to 70%
% By weight, more preferably 20% by weight to 60% by weight. The above organic or inorganic hydrophilic materials used in the present invention
The hydrophilic layer of the water-soluble matrix is, for example, water or methanol
Or a suitable solvent such as polar solvent such as ethanol or
Dissolve or disperse in these mixed solvents on the support
Applied, dried and cured. The coating weight is the weight after drying
And 0.1 to 5 g / m² Is suitable, preferably 0.
3 to 3 g / m² More preferably, 0.5-2 g / m²
It is. The coating weight after drying of the hydrophilic layer is 0.1 g / m.
² If it is too low, the retention of hydrophilic components such as fountain solution will be low.
Give rise to unfavorable results such as lowering or lowering of film strength
If it is too tight, the film becomes brittle and the printing durability is reduced.
Give a good result. Including the metal oxide used in the hydrophilic layer of the present invention.
An inorganic thin film having a surface has a hydrophilic surface.
It is not particularly limited as long as it is made of a metal oxide.
Of a metal or metal compound having an aqueous metal oxide on the surface
Includes a thin film. Metal or gold that can be used in the hydrophilic layer of the present invention
Genus compounds include d-block (transition) metals, f-
Rock (lanthanoid) metal, aluminum, indium
Lead, tin, silicon or alloys and their respective metals
Corresponding metal oxide, metal carbide, metal nitride, metal photo
Examples include ureides, metal sulfides, and metal halides.
They are mixed (uniform mixed film, non-uniform mixed film and laminated
(Including a film). Among them, metal acids
The compound thin film itself is particularly preferred, and the metal oxide thin film
Indium oxide, tin oxide, tungsten oxide
Manganese oxide, silicon oxide, titanium oxide, aluminum oxide
Thin films such as minium and zirconium oxide and mixed thin films
The membrane can be suitably used as the hydrophilic layer of the present invention.
The Metal and metal compound thin film surfaces are substantially
In the high oxidation state, the surface is a metal oxide
And can be used in the present invention
However, in the present invention, the hydrophilicity of the hydrophilic layer is ensured.
Therefore, the surface of the inorganic thin film, which is a hydrophilic layer, is made of metal oxide.
It is essential to be configured. For this reason, a thin film is formed
After heat treatment or humidification to promote surface oxidation
Processing such as processing and glow discharge processing may be performed. further
The metal oxide may be laminated on the thin film surface. Metal or metallization used in the hydrophilic layer of the present invention
For thin film formation of compounds, vacuum evaporation, sputtering, ion
PVD method (physical vapor deposition method) such as plating method
The CVD method (chemical vapor deposition method) or the like is appropriately used. example
In vacuum evaporation, the heating method is
Use heat, high frequency induction heating, electron beam heating, etc.
it can. In addition, oxygen and nitrogen are introduced as reactive gases.
Or using means such as ozone addition or ion assist
Reactive vapor deposition may be used. When sputtering is used, the target material
Use pure metal or the desired metal compound as a material.
When pure metal is used, oxygen or
Nitrogen etc. are introduced. As a sputtering power source, a DC power source,
A pulse type DC power source or a high frequency power source can be used. Prior to thin film formation by the above method,
In order to improve adhesion to the layer, the substrate is heated by heating the substrate
Degassing or vacuum glow treatment may be applied to the lower surface.
For example, in vacuum glow processing, 1 to 10 mtor
A glow discharge is formed by applying a high frequency to the substrate under a pressure of about r.
Substrate processing using the generated plasma.
it can. Also, increase the applied voltage, oxygen or nitrogen
Improving the effect by introducing reactive gas
Is also possible. The hydrophilic layer used in the hydrophilic layer of the present invention has a hydrophilic surface.
The thickness of the metal or metal compound thin film is 10 nm to 3
000 nm is preferred. More preferably 20-150
0 nm. If it is too thin, the dampening water retention
Gives unfavorable results such as reduced film strength and is too thick
And because it takes time to form a thin film,
Yes. The above hydrophilic layer is provided on the support of the present invention.
The surface of the support on the hydrophilic layer side of the hydrophilic layer
From the viewpoint of improving the surface area and adhesion with the upper layer,
Table with roughening or corona treatment by last treatment, etc.
Surface modification treatment may be performed. The lithographic printing plate precursor of the present invention is a parent of a support.
The heat-sensitive layer of the present invention is provided on an aqueous surface.
In the meantime, a water-soluble metal such as zinc borate
An inorganic undercoat layer such as salt or an organic undercoat layer may be provided.
it can. Various organic compounds are used as organic undercoat layer components
For example, carboxymethylcellulose, dex
Thrin, gum arabic, 2-aminoethylphosphonic acid
Any amino group-containing phosphonic acid or substituent
Good phenylphosphonic acid, naphthylphosphonic acid, alkyl
Ruphosphonic acid, glycerophosphonic acid, methylene diphospho
Organic phosphones such as acid and ethylene diphosphonic acid
Acid, phenylphosphoric acid optionally substituted, naphthyl
Organics such as acid, alkyl phosphate and glycerophosphate
Phosphoric acid, optionally substituted phenylphosphinic acid,
Naphthyl phosphinic acid, alkyl phosphinic acid and
Organic phosphinic acids, such as lysophosphinic acid, glycine
And amino acids such as β-alanine, and triethanol
Of amines with hydroxy groups, such as ruamine hydrochloride
It is selected from hydrochlorides, etc., but it may be used as a mixture of two or more.
Yes. This subbing layer is provided by the following method.
Can do. That is, water or methanol, ethanol,
Organic solvents such as tilethyl ketone or mixtures thereof
A solution in which the above organic compound is dissolved in a solvent is used as a parent of the support.
A method of coating and drying on an aqueous surface and water or
Organics such as ethanol, ethanol, methyl ethyl ketone
Dissolve the above organic compounds in a solvent or mixed solvent.
The above compound is adsorbed by immersing the support in the dissolved solution.
Then wash and dry with water etc. to dry the organic subbing layer.
It is a method of providing. In the former method, the above organic compound
Of 0.005 to 10% by weight solution in various ways
Can be applied. In the latter method, the concentration of the solution is 0.0.
1 to 20% by weight, preferably 0.05 to 5% by weight
The immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C.
The immersion time is 0.1 second to 20 minutes, preferably 2 seconds
~ 1 minute. The solution used for this is ammonia,
Basic substances such as ethylamine and potassium hydroxide, and salts
In the range of pH 1-12 by acidic substances such as acid and phosphoric acid
It can also be adjusted. The coating amount of the undercoat layer is 2 to 200
mg / m² Is suitable, preferably 5-100 mg /
m² It is. The support used in the present invention is blocking.
From the viewpoint of preventing the maximum depth of roughness (R
t) is preferably at least 1.2 μm or more.
Furthermore, the back surface of the support (that is, the planographic printing plate of the present invention)
On the surface of the lithographic printing plate precursor of the present invention
The coefficient of dynamic friction (μk) when sliding is 2.6 or less.
preferable. The thickness of the support used in the present invention is as follows:
Approximately 0.05 mm to 0.6 mm, preferably 0.1 mm
The thickness is 0.4 mm, particularly preferably 0.15 mm to 0.3 mm. (Thermosensitive layer) The thermosensitive layer of the present invention comprises fine particle poly
Contains mer. Fine particle poly which can be used in the present invention
Mer is a polymer that melts and coalesces by heat.
Preferably, its surface is hydrophilic and disperses in water
Are particularly preferred, for example, polyethylene, polystyrene.
, Polyvinyl chloride, polyvinylidene chloride, poly (medium
T) Methyl acrylate, poly (meth) acrylate
, Poly (meth) butyl acrylate, polyacrylonite
Latec of ril, polyvinyl acetate and their copolymers
And the like. In this way, the surface of the fine particle polymer
To make it water-based, polyvinyl alcohol, polyethylene
Hydrophilic polymers or oligomers such as glycols,
Or a hydrophilic low molecular weight compound is adsorbed on the surface of a fine particle polymer.
I'm fine, but the method is limited to these
is not. Further, only the fine particle polymer is applied and solidified.
Film contact when made by drying at a temperature lower than the temperature
The horns (water droplets) are dried at a temperature higher than the solidification temperature.
It becomes lower than the contact angle (water drop in the air) of the film when it is made
The solidification temperature of the fine particle polymer is preferably 70 ° C.
The above is preferable, but considering the stability over time, 100 ° C. or higher
Is more preferable. Further, the fine particle polymer of the present invention is an image.
The purpose is to improve the film strength of the
It preferably has a group. Fine with heat-reactive functional groups
Particulate polymers are present in other particulate polymers.
Existing in functional groups or other components in the heat sensitive layer
Particularly limited as long as it has a functional group capable of reacting with a functional group
Not such as latex containing these functional groups
Can be mentioned. These fine particles of polymer are bonded via a functional group.
May react with each other, and other additions in the heat sensitive layer
Contains the following hydrophilic resin or low molecular weight compound
You may react with them. 2 or more types
Heterogeneous functional groups that react with each other on the fine particulate polymer
May be allowed to react with each other. The above-mentioned thermoreactive functional group includes a polymerization reaction.
An ethylenically unsaturated group (e.g., an acryloyl group,
Methacryloyl group, vinyl group, allyl group, etc.), additional reaction
Isocyanate group or its block, and its reaction
A functional group having an active hydrogen atom as a counterpart (eg, an
Mino group, hydroxyl group, carboxyl group, etc.), same
Epoxy groups that undergo addition reactions, and the reaction partner amino
Group, carboxyl group or hydroxyl group, condensation reaction
Carboxyl group and hydroxyl group or amino
Group, acid anhydride and amino group or hydrogen
A droxyl group etc. can be mentioned. But chemical
Functional group that performs any reaction if a bond is formed
But it ’s okay. Heat-reactive functional group used in the heat-sensitive layer of the present invention
Examples of the fine particle polymer having acryloyl group,
Tacrylloyl group, vinyl group, allyl group, epoxy group,
Amino group, hydroxyl group, carboxyl group, isocyania
Having acid groups, acid anhydrides and groups protecting them
Things can be mentioned. Polymers of these functional groups
The introduction into the particles may be carried out at the time of polymerization, or high after the polymerization.
You may carry out using a molecular reaction. When introduced during polymerization, these functional groups
Emulsion polymerization or suspension polymerization of monomers having
Is preferred. Specific examples of monomers having such functional groups
Examples include allyl methacrylate, allyl acrylate
, Vinyl methacrylate, vinyl acrylate, grease
Sidyl methacrylate, glycidyl acrylate, 2-
Isocyanatoethyl methacrylate, its alcohol
Block isocyanate, 2-isocyanate, etc.
Brominated with toethyl acrylate and its alcohol
Ic isocyanate, 2-aminoethyl methacrylate
2-aminoethyl acrylate, 2-hydroxyethyl
Til methacrylate, 2-hydroxyethyl acrylate
, Acrylic acid, methacrylic acid, maleic anhydride
List of functional acrylates, bifunctional methacrylates, etc.
However, it is not limited to these. Thermal reaction copolymerizable with these monomers
Examples of monomers having no functional functional group include styrene
, Alkyl acrylate, alkyl methacrylate,
Acrylonitrile, vinyl acetate, etc.
However, if the monomer does not have a thermally reactive functional group,
It is not limited to these. Introduction of heat-reactive functional groups after polymerization
As the polymer reaction used in the case of carrying out, for example, WO9
The polymer reactions described in JP-A-6-34316 are listed.
I can make it. Fine particle poly having the above heat-reactive functional group
In the polymer, the fine particles of polymer melt and coalesce with heat
It is preferable, but the chemical reaction is caused by heat and fine particles
Hydrophilic added between child polymer or fine polymer
Chemical bonding with a functional resin or an added low-molecular compound
If a strong film can be formed, a fine polymer
It is preferable for image formation to melt and coalesce with heat.
Is not required. The average particle size of the fine particle polymer of the present invention is
0.01 to 20 μm is preferable, and among them, 0.05
-2.0 μm is more preferable, especially 0.1-1.0 μm
Is preferred. Within this range, good resolution and stability over time
can get. The amount of the fine particle polymer added is determined by the heat sensitive layer.
The solid content is preferably 50% by weight or more, and 60% by weight or more.
Further preferred. The heat sensitive layer of the present invention has the above thermal reactivity.
When using fine particle polymers with functional groups,
Adding compounds that initiate or accelerate these reactions
Also good. Compounds that initiate or accelerate the reaction include heat.
List compounds that generate more radicals or cations.
For example, lofine dimer, trihalo
Methyl compounds, peroxides, azo compounds, diazonium salts
Or onium containing diphenyliodonium salt
Salt, acylphosphine, imidosulfonate, etc.
It is done. These compounds have a heat-sensitive layer solid content of 1 to 20 times.
It can be added in the range of% by weight. Preferably 3-1
It is in the range of 0% by weight. Within this range, developability is impaired.
Therefore, a good reaction initiation or acceleration effect can be obtained. A hydrophilic resin is added to the heat-sensitive layer of the present invention.
Also good. Good developability by adding hydrophilic resin
In addition, the film strength of the thermosensitive layer itself is improved. parent
Examples of the aqueous resin include hydroxyl and carboxy.
, Hydroxyethyl, hydroxypropyl, amino,
Aminoethyl, aminopropyl, carboxymethyl, etc.
Those having a hydrophilic group are preferred. As a specific example of the hydrophilic resin, Arabico
, Casein, gelatin, starch derivatives, carboxymethyl
Cellulose and its sodium salt, cellulose acetate
Tate, sodium alginate, vinyl acetate-malein
Acid copolymers, styrene-maleic acid copolymers,
Polyacrylic acids and their salts, polymethacrylic acid
And their salts, hydroxyethyl methacrylate
Homopolymers and copolymers of hydroxyethyla
Acrylate homopolymers and copolymers, hydroxy
Cypropyl methacrylate homopolymer and copoly
, A homopolymer of hydroxypropyl acrylate
And copolymers of hydroxybutyl methacrylate
Homopolymers and copolymers, hydroxybutyl acetate
Relate homopolymers and copolymers, polyethylene
Glycols, hydroxypropylene polymers, polymers
Livinyl alcohols and less hydrolysis
60 wt.%, Preferably at least 80 wt.
Decomposed polyvinyl acetate, polyvinyl formal, poly
Livinyl butyral, polyvinyl pyrrolidone, acrylic
Amide homopolymers and copolymers, methacrylic
Homopolymers and polymers of imide, N-methylol
Examples include homopolymers and copolymers of chloramide
Can. The amount of hydrophilic resin added to the heat sensitive layer is the same as that of the heat sensitive layer.
5-40% by weight of solid content is preferred, 10-30% by weight
Is more preferable. Within this range, good developability and film
Strength is obtained. The lithographic printing plate precursor of the present invention has a heat sensitive layer.
Or adjacent layers (hydrophilic layer, subbing layer or
A photothermal conversion agent in the overcoat layer).
This makes it possible to record images using laser light irradiation, etc.
The As such a photothermal conversion agent, the wavelength of a laser light source is set.
Any substance that absorbs, various pigments, dyes and gold
Genus fine particles can be used. In particular, 700-120
A light-absorbing material having an absorption band at least in part of 0 nm.
Preferably there is. The types of pigments include black pigments, brown faces
Material, red pigment, purple pigment, blue pigment, green pigment, fluorescent face
Materials, metal powder pigments, and other polymer-bound dyes
The Specifically, insoluble azo pigments, azo lake pigments,
Compound azo pigment, chelate azo pigment, phthalocyanine face
, Anthraquinone pigments, perylene and perinone
Pigment, thioindigo pigment, quinacridone pigment, geo
Xazine pigment, isoindolinone pigment, quinophthalo
Pigment, dyed lake pigment, azine pigment, nitroso face
Materials, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, cars
Bon black or the like can be used. These pigments may be used without surface treatment.
Alternatively, a surface treatment may be applied. For surface treatment method
Is a method of surface coating with hydrophilic resin or lipophilic resin, interface
Methods of attaching activators, reactive materials (eg silica
Sol, alumina sol, silane coupling agent and epoxy
Compound, isocyanate compound, etc.)
A method of making it possible is conceivable. The above surface treatment method is “gold
Properties and applications of genus soaps "(Yokoshobo)," Printing ink technology "
(CMC Publishing, published in 1984)
Saku "(CMC Publishing, 1986).
Among these pigments, those that absorb infrared rays emit infrared rays.
This is preferable in that it is suitable for use with a laser that emits light. Red
Carbon black is the preferred pigment to absorb external lines
Yes. The pigment particle size should be in the range of 0.01 μm to 1 μm.
And preferably in the range of 0.01 μm to 0.5 μm.
More preferably. As the dye, commercially available dyes and literature (examples)
For example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, 1970
Published in “Chemical Industry”, May 1986, p. 45-51
“Near-infrared absorbing dyes”, “Development and market of functional dyes in the 1990s
Section 2. “Chapter 2. 2.3 (1990) CMC)
Can use known dyes described in patents. Concrete
Azo dyes, metal complex azo dyes, pyrazolone azo
Dye, anthraquinone dye, phthalocyanine dye, cal
Bonium dye, quinone imine dye, polymethine dye,
Infrared absorbing dyes such as anine dyes are preferred. Further, for example, Japanese Patent Laid-Open No. 58-12524.
6, JP 59-84356, JP 60
Cyanine dyes described in Japanese Patent No. 78787 /
JP-A-58-173696, JP-A-58-181
690, JP 58-194595, etc.
Published methine dyes, JP-A-58-112793
JP, 58-224793, JP 59-
48187, JP-A-59-73996,
Japanese Unexamined Patent Publication No. 60-52940, Japanese Unexamined Patent Publication No. 60-63744
Naphthoquinone dyes described in Japanese Patent Publication No.
Squaries described in Japanese Patent No. 58-112792
Lithium dye, cyanine described in British Patent 434,875
Dyes, dyes described in US Pat. No. 4,756,993, rice
Cyanine dyes described in Japanese Patent No. 4,973,572,
Japanese Patent Laid-Open No. 11-268512
Phthalocyanine compounds described in Japanese Patent No. 235883.
I can make it. Further, as a dye, US Pat. No. 5,156,
The near infrared absorption sensitizer described in No. 938 is also preferably used.
Substituted in U.S. Pat. No. 3,881,924
Arylbenzo (thio) pyrylium salt, JP-A-57-1
Trimethine thiapyrylium salt described in 42645, JP
Sho 58-181051 and 58-220143
Gazette, 59-41363, 59-84248
Gazette, 59-84249 gazette, 59-1460
No. 63 and No. 59-146061
Pyryllium compounds, JP-A-59-216146
Cyanine dyes described in the publication, US Pat. No. 4,283,47
The pentamethine thiopyrylium salt described in No. 5
Described in JP-A-5-13514 and JP-A-5-19702
Pyryllium compound, Epolite from Eporin
III-178, Epolite III-130, Epolite III
-125 etc. are also preferably used. Below are some ingredients
An example is shown. [0084] [Chemical Formula 3] [0085] [Formula 4][0086] [Chemical formula 5][0087] [Chemical 6][0088] [Chemical 7] [0089] [Chemical 8][0090] [Chemical 9] [0091] Embedded image The above organic photothermal conversion agent is contained in the heat sensitive layer.
It can be added up to 30% by weight. Preferably 5
25% by weight, particularly preferably 7 to 20% by weight
The Within this range, good sensitivity can be obtained. The heat-sensitive layer of the present invention contains gold as a photothermal conversion agent.
Genus fine particles can also be used. Many metal particles are light
Heat convertible and self-heating, but preferred
As metal fine particles, Si, Al, Ti, V, Cr, M
n, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo,
Ag, Au, Pt, Pd, Rh, In, Sn, W, T
e, Pb, Ge, Re, Sb alone or alloy,
These include fine particles of their oxides or sulfides
The Preferred among the metals that make up these metal particles
This type of metal is easy to coalesce with heat during light irradiation and has a high melting point.
Absorbed in the infrared, visible or ultraviolet region at about 1000 ° C or less
Metal with a yield, for example, Re, Sb, Te, Au, A
g, Cu, Ge, Pb and Sn. Also especially good
The best thing is that the melting point is relatively low, and the absorbance to infrared rays
Comparatively high metal fine particles, for example, Ag, Au, C
As u, Sb, Ge and Pb, the most preferred elements
Includes Ag, Au and Cu. Also, for example, Re, Sb, Te, Au, A
Fine particles of low melting point metals such as g, Cu, Ge, Pb, Sn
And Ti, Cr, Fe, Co, Ni, W, Ge, etc.
2 or more types such as mixed with self-heating metal fine particles
The photothermal conversion substance may be used. Ag,
Light absorption is particularly large when using small pieces such as Pt and Pd
Use a combination of metal species and other metal fragments
It is also preferable. The particle size of these particles is preferably 10 μm.
m or less, more preferably 0.003 to 5 μm, particularly preferred
It is 0.01-3 micrometers. Within this range, good
Sensitivity and resolution can be obtained. In the present invention, these fine metal particles are irradiated with light.
When used as a heat conversion agent, the amount added is preferably
10% by weight or more of the heat-sensitive layer solid content, more preferably
Used at 20% by weight or more, particularly preferably 30% by weight or more
It is done. High sensitivity is obtained within this range. In the heat-sensitive layer of the present invention, the thermal reaction as described above is used.
When using fine particle polymers with functional groups,
React with the thermally reactive functional group in the fine particle polymer
Functionalized molecule and its molecular weight reduction
Compounds can be included. Addition amount of these compounds
Is preferably 5 to 40% by weight in the heat-sensitive layer, particularly 5
% By weight to 20% by weight is preferred. Less than this crosslink
Less effective and printing durability is insufficient.
The developability after time will deteriorate. Can be used for the following
The active compounds are described. As the low molecular weight compound, polymerizable unsaturated
Group, hydroxyl group, carboxyl group, carboxylate
Group, acid anhydride group, amino group, epoxy group, isocyana
Group and blocked isocyanate group
Can be mentioned. As the compound having a polymerizable unsaturated group,
LA having at least one ethylenically unsaturated double bond
Dical polymerizable compound, terminal ethylenically unsaturated bond
A compound having at least one, preferably two or more
Chosen. Such a group of compounds
These are widely known, and in the present invention, these are special features.
It can be used without limitation. These are, for example, monomers
-Prepolymers, ie dimers, trimers and oligos
Gomer, or a mixture of them and their copolymerization
It has a chemical form such as the body. Monomers and their copolymerization
Examples of bodies include unsaturated carboxylic acids (e.g. acrylic
Acid, methacrylic acid, itaconic acid, crotonic acid, isochrome
Tonic acid, maleic acid, etc.) and their esters and amides
Preferably, unsaturated carboxylic acid and aliphatic
Esters with polyhydric alcohol compounds, unsaturated carboxylic acids
An amide of an aliphatic polyvalent amine compound is used.
In addition, hydroxyl group, amino group, mercapto group, etc.
Unsaturated carboxylic acid ester having a nucleophilic substituent, amino
And monofunctional or polyfunctional isocyanates, epoxy
Addition reaction product with moss, monofunctional or polyfunctional carbo
A dehydration condensation reaction product with an acid is also preferably used. Also,
Has an electrophilic substituent such as an isocyanate group or an epoxy group
Unsaturated carboxylic esters or amides
Functional or polyfunctional alcohols, amines and thios
Addition reaction products, and halogen groups and tosyl alcohol
Unsaturated carboxylic acid ester having a leaving substituent such as a xy group
Tellurium or amides and mono- or polyfunctional alcohols
Also preferred are substitution products with alcohols, amines and thiols.
Is suitable. Another example is the unsaturated carboxylic acid described above.
Replace with unsaturated phosphonic acid, styrene, etc. instead of acid.
It is also possible to use the obtained compound group. Aliphatic polyhydric alcohol compounds and unsaturated cal
Specific examples of radically polymerizable compounds that are esters with boronic acid
Examples include acrylic acid esters, ethylene glycol
Coal diacrylate, triethylene glycol diac
Relate, 1,3-butanediol diacrylate, te
Tramethylene glycol diacrylate, propylene glycol
Recall diacrylate, neopentyl glycol dia
Chlorate, trimethylolpropane triacrease
Trimethylolpropane tri (acryloyloxy)
Propyl) ether, trimethylol ethane triacryl
Rate, hexanediol diacrylate, 1,4-silane
Chlohexanediol diacrylate, tetraethylene
Glycol diacrylate, pentaerythritol dia
Acrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, dipentae
Lithritol diacrylate, dipentaerythritol
Hexaacrylate, sorbitol triacrylate,
Sorbitol tetraacrylate, sorbitol penta
Acrylate, sorbitol hexaacrylate, tri
(Acryloyloxyethyl) isocyanurate, poly
There are ester acrylate oligomers and the like. Examples of 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, pentaerythrito
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, sorbitol trimethacrylate, sorbite
Tetramethyl methacrylate, bis [p- (3-methacrylic
(Luoxy-2-hydroxypropoxy) phenyl] dimethyl
Tylmethane, bis- [p- (methacryloxyethoxy
B) Phenyl] dimethylmethane. Examples of itaconic acid esters include ethylene glycol.
Recall Diitaconate, Propylene Glycol Diita
Conate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethyle
Glycol diitaconate, pentaerythritol di
Itaconate, sorbitol tetritaconate, etc.
The Examples of crotonic acid esters include ethylene glycol.
Recall dicrotonate, tetramethylene glycol di
Crotonate, pentaerythritol dicrotonate,
Examples include sorbitol tetradicrotonate. As the isocrotonic acid ester, ethyl acetate is used.
Glycol diisocrotonate, pentaerythritol
Rudiisocrotonate, sorbitol tetraisocroto
There are nates. As the maleic ester, ethylene glycol is used.
Recall dimaleate, triethylene glycol dimale
, Pentaerythritol dimaleate, sorbitol te
There are trauma rates. Examples of other esters include, for example, special
Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-47334
Aliphatics described in JP-A-57-196231
Alcohol-based esters and JP-A-59-5240
, JP 59-5241, JP 2-2261
No. 49 having an aromatic skeleton, JP-A-1
Containing an amino group described in JP-A-165613
Are also preferably used. In addition, an aliphatic polyvalent amine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylic
Amide, 1,6-hexamethylenebis-acrylamid
1,6-hexamethylenebis-methacrylamide,
Diethylenetriaminetrisacrylamide, Xylile
Bisacrylamide, Xylylenebismethacrylami
There are Examples of other preferred amide monomers
As described in Japanese Patent Publication No. 54-21726
Mention may be made of those having a xylene structure. Also,
Manufactured using isocyanate and hydroxyl group addition reaction
Urethane addition polymerizable compounds are also suitable, such as
As a specific example, for example, Japanese Patent Publication No. 48-41708
2 or more isocyanates per molecule described in the report
In the polyisocyanate compound having a group,
Add the unsaturated monomer having a hydroxyl group shown in (A)
Contains two or more polymerizable unsaturated groups in one molecule
A urethane compound etc. are mentioned. Formula (A) CH₂= C (R_m) COOCH₂CH (R_n) OH (However, R_mAnd R_nIs H or CH_ThreeIndicates. ) Japanese Patent Laid-Open No. 51-37193, Japanese Patent
No. 2-332293, No. 2-16765
Urethane acrylate as described in
Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654
Gazette, JP-B 62-39417, JP-B 62-
It has an ethylene oxide skeleton described in Japanese Patent No. 39418.
Also suitable are urethane compounds. Furthermore, JP-A-6
Japanese Patent Publication No. 3-277653, Japanese Patent Laid-Open No. 63-260909
Published in Japanese Patent Application Laid-Open No. 1-105238.
Radical weight with amino or sulfide structure
Compatible compounds may also be used. Other examples include Japanese Patent Laid-Open No. 48-641.
83, JP-B-49-43191, 52-
Poly as described in each publication of the 30490 publication
Ester acrylates, epoxy resins and (meth) acrylic
Multifunctional such as epoxy acrylates reacted with rilic acid
Can mention acrylates and methacrylates
The Also, Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1
Specification of 40337 gazette and 1-40336 gazette
And unsaturated compounds described in JP-A-2-25493
The vinyl phosphonic acid compounds of
Can. In some cases, JP-A-61-2
Containing a perfluoroalkyl group described in Japanese Patent No. 2048
These compounds are also preferably used. Furthermore, the Japan Adhesion Association magazine,
20: 7, 300-308 (1984)
Introduced as curable monomers and oligomers
Things can also be used. The epoxy compound is preferably a grease.
Serine polyglycidyl ether, polyethylene glycol
Rudiglycidyl ether, polypropylene diglycidyl
Ether, trimethylolpropane polyglycidyl ether
Tellurite, sorbitol polyglycidyl ether, bisphe
Nords or polyphenols or their hydrogenation
Additive polyglycidyl ether and the like. As the compound having an isocyanate,
Preferably tolylene diisocyanate, diphenyl meta
Diisocyanate, polymethylene polyphenylpolyethylene
Socyanate, xylylene diisocyanate, naphthalene
Diisocyanate, cyclohexanephenylene diiso
Cyanate, isophorone diisocyanate, hexamethyl
Range isocyanate, cyclohexyl diisocyanate
Block them with alcohol or amines.
Can be mentioned. The amine compound is preferably ethylene.
Diamine, diethylenetriamine, triethylenetet
Lamin, hexamethylenediamine, propylene diamine
And polyethyleneimine. Hydroxy
As the compound having a thiol group, a terminal methylo is preferable.
Such as pentaerythritol
Such as polyhydric alcohols, bisphenols and polyphenols
Can be mentioned. Compound having carboxyl group
Preferably, the product is pyromellitic acid or trimellitic acid.
Aromatic polycarboxylic acids such as toic acid and phthalic acid, adipine
Examples include aliphatic polyvalent carboxylic acids such as acids. Acid free
As water, pyromellitic anhydride,
Nzophenone tetracarboxylic acid anhydride
The In the heat-sensitive layer of the present invention, if necessary,
In addition to the above, various compounds may be added. For example, a picture
To make it easier to distinguish between image and non-image areas after image formation
Therefore, dyes that have a large absorption in the visible light region are used as image colorants.
Can be used. Specifically, oil yellow
-# 101, Oil Yellow # 103, Oil Pink #
312, Oil Green BG, Oil Blue BOS, Oh
Ilblue # 603, Oil Black BY, Oil Bra
BS, Oil Black T-505 (orientated
Chemical Industry Co., Ltd.), Victoria Pure Blue, Chris
Tal violet (CI42555), methyl violet
(CI42535), ethyl violet, loader
Min B (CI145170B), Malachite Green
(CI42000), methylene blue (CI5201)
5) etc., and described in JP-A-62-293247
Can be mentioned. Also phthalocyanine
Pigments such as pigments, azo pigments and titanium oxide are also suitable
Can. The amount added is relative to the total solid content of the heat-sensitive layer coating solution.
0.01 to 10% by weight is preferable. Further, the feeling of the present invention
In the thermal layer, the image area and non-image area are sharpened when exposed.
Therefore, coloring or decoloring compounds may be added.
preferable. For example, diazo compounds and diphenyliodone
Leuco dyes (leucoma) with thermal acid generators such as um salt
Lakite green, leuco crystal violet, black
Listal violet lactones, etc.) and pH discoloring dyes
(Eg, ethyl violet, victoria pouble
-Dyes such as BOH). Further, in the present invention, the heat-sensitive layer coating solution
Failure of ethylenically unsaturated compounds during preparation or storage
A small amount of thermal polymerization inhibitor is added to prevent necessary thermal polymerization.
It is desirable to add. Suitable thermal polymerization inhibitors include
Idroquinone, p-methoxyphenol, di-t-butyl
Ru-p-cresol, pyrogallol, t-butylcateco
, Benzoquinone, 4,4'-thiobis (3-methyl
-6-tert-butylphenol), 2,2'-methylenebi
(4-methyl-6-tert-butylphenol), N-ni
Toroso-N-phenylhydroxylamine aluminum
Examples include salts. The amount of thermal polymerization inhibitor added is the total composition
About 0.01 to 5% by weight based on the weight of If necessary, the polymerization can be inhibited by oxygen.
High grades like behenic acid and behenamide to prevent
The process of drying after application by adding fatty acids and their derivatives
It may be unevenly distributed on the surface of the heat sensitive layer. Higher fatty acids and their
The amount of the derivative added is about 0.1 to about 10 times the solid content of the heat sensitive layer.
% By weight is preferred. Further, the heat-sensitive layer of the present invention can be provided as necessary.
Add plasticizers to provide flexibility, etc.
You can. For example, polyethylene glycol,
Tributyl acid, diethyl phthalate, dibutyl phthalate,
Dihexyl phthalate, dioctyl phthalate, triphosphate
Cresyl, tributyl phosphate, trioctyl phosphate, o
Tetrahydrofurfuryl oleate or the like is used. The heat-sensitive layer of the present invention dissolves the necessary components described above.
Prepare or apply a coating solution by dispersing or dissolving in the agent.
The The solvent used here is ethylene dichlorate.
, Cyclohexanone, methyl ethyl ketone, methanol
Ethanol, propanol, ethylene glycol
Nomethyl ether, 1-methoxy-2-propanol,
2-methoxyethyl acetate, 1-methoxy-2-propyl
Lopylacetate, dimethoxyethane, methyl lactate, milk
Acid ethyl, N, N-dimethylacetamide, N, N-di
Methylformamide, tetramethylurea, N-methyl
Pyrrolidone, dimethyl sulfoxide, sulfolane, γ-
Butyl lactone, toluene, water, etc.
However, the present invention is not limited to this. These solvents are
Used alone or in combination. Solid content concentration of coating solution
Is preferably 1 to 50% by weight. Furthermore, the feeling on the support obtained after coating and drying.
Thermal layer coating amount (solid content) varies depending on the application, but in general
0.4-5.0 g / m²Is preferred. From this range
As the amount applied decreases, the apparent sensitivity increases, but the image
The film properties of the heat-sensitive layer that performs the function of image recording are reduced. Painting
Various methods can be used as the method of cloth.
The For example, bar coater coating, spin coating, spray coating
Cloth, curtain coating, dip coating, air knife coating,
Examples include blade coating and roll coating. In the heat-sensitive layer coating solution, the coating property is improved.
Surfactants such as those disclosed in JP-A-62-170950
Add a fluorosurfactant as described in
Can be. The preferred addition amount is the total solid content of the heat-sensitive layer.
0.01-1% by weight, more preferably 0.05-0.
5% by weight. (Overcoat layer) Planographic printing plate of the present invention
The original plate is used to prevent contamination and scratches caused by lipophilic substances on the surface of the heat sensitive layer.
To prevent this, an overcoat layer should be provided on the heat sensitive layer.
You can. The overcoat layer used in the present invention is marked
Can be easily removed with a hydrophilic printing liquid such as fountain solution during printing
Selected from hydrophilic organic polymer compounds
Contains resin. The hydrophilic organic polymer compound used here
As a product, a film formed by drying is a film-forming ability.
Specifically, polyvinyl acetate (however,
Water decomposition rate of 65% or more), polyacrylamine salt, poly
Riacrylic acid copolymer, its alkali metal salt or
Min salt, polymethacrylic acid, its alkali metal salt or
Is amine salt, polymethacrylic acid copolymer, its alkali
Metal salt or amine salt, polyacrylamide, co-
Polymer, polyhydroxyethyl acrylate, polyvinyl
Lupyrrolidone, its copolymer, polyvinyl methyl ether
, Vinyl methyl ether / maleic anhydride copolymer,
Poly-2-acrylamido-2-methyl-1-propane
Sulfonic acid, its alkali metal salt or amine salt,
Ri-2-acrylamido-2-methyl-1-propanes
Sulfonic acid copolymer, alkali metal salt or amine thereof
Salt, gum arabic, fibrin derivatives (eg carboxy
Methyl cellulose, carboxyethyl cellulose, methyl
Rucellulose, etc.), modified products thereof, white dextri
, Pullulan, enzymatically degraded etherified dextrin, etc.
I can make it. Depending on the purpose, these resins
A mixture of two or more of these can also be used. In addition, the overcoat layer has the above hydrophilic properties.
A neutral photothermal conversion agent may be added. In addition, overcoat
In order to ensure the uniformity of coating,
In the case of polyoxyethylene nonylphenyl ether
Non-iodine such as polyoxyethylene dodecyl ether
A surfactant can be added. Overcoat
The dry coating amount of the G layer is 0.1 to 2.0 g / m²Is preferred
Yes. Within this range, developability is not impaired, and fingerprint adhesion is not dirty.
Good contamination prevention and scratches on the surface of the heat sensitive layer by any lipophilic substance
Can be prevented. (Image formation and plate making) Planographic printing plate of the present invention
The original plate is imaged by heat. Specifically, thermal recording
Direct image-like recording with a head, etc., with an infrared laser
High exposure flash exposure such as scanning exposure and xenon discharge lamp
Or infrared lamp exposure, etc.
YA, a semiconductor laser that emits infrared light of 1200 nm
Exposure by solid high power infrared laser such as G laser
Is preferred. Image-recorded lithographic printing plate precursor of the present invention
Next, the plate surface is rubbed with a rubbing member in the presence of the treatment liquid.
By removing the heat-sensitive layer in the non-image area (overcoating
If there is a coat layer, remove the overcoat layer at the same time.
Left. ), Hydrophilic support surface in non-image area
To expose a lithographic printing plate. As a rubbing member usable in the present invention,
For example, non-woven fabric, cotton fabric, cotton pad, molton, rubber
Examples include blades and brushes. As a processing solution used in the present invention,
Is suitable for hydrophilic treatment liquid, for example, water alone or
Is preferably an aqueous solution containing water as a main component.
Aqueous solutions and surfactants with the same composition as known fountain solutions (anio
Aqueous solutions containing nonionic, nonionic, cationic, etc.)
preferable. The treatment liquid of the present invention contains an organic solvent.
You may do it. Examples of the solvent that can be contained include aliphatic groups.
Hydrocarbons (hexane, heptane, “Isopar E,
H, G "(Esso Chemical Co., Ltd.) or gasoline, light
Oil), aromatic hydrocarbons (toluene, xylene, etc.),
Or halogenated hydrocarbons (trichlene, etc.)
The polar solvent is mentioned. Examples of the polar solvent include alcohols.
(Methanol, ethanol, propanol, isopropa
Nord, benzyl alcohol, ethylene glycol mono
Methyl ether, 2-ethoxyethanol, diethylene
Glycol monoethyl ether, diethylene glycol
Monohexyl ether, triethylene glycol monomer
Chill ether, propylene glycol monoethyl ether
, Dipropylene glycol monomethyl ether, poly
Ethylene glycol monomethyl ether, polypropylene
Glycol, tetraethylene glycol, etc.), ketone
(Acetone, methyl ethyl ketone, etc.), esters
(Ethyl acetate, methyl lactate, butyl lactate, propylene glycol
Recall monomethyl ether acetate, diethylene glycol
Recall acetate, diethyl phthalate, etc.), others
(Triethyl phosphate, tricresyl phosphate
And the like. In addition, when the organic solvent is insoluble in water,
It is also possible to use it by solubilizing it in water using a surfactant, etc.
If the processing liquid contains a solvent, safety
From the viewpoint of flammability, the solvent concentration is preferably less than 40% by weight.
That's right. As the surfactant used in the treatment liquid of the present invention,
Nonionic surfactant is preferably used from the viewpoint of foam suppression
it can. Nonionic field which can be used in the processing solution of the present invention
As the surfactant, a polyethylene glycol type high-grade surfactant is used.
Lucol ethylene oxide adduct, alkylphenol
Ruethylene oxide adduct, fatty acid ethylene oxide
Adduct, polyhydric alcohol fatty acid ester ethylene oxide
Side adduct, higher alkylamine ethylene oxide
Additives, fatty acid amide ethylene oxide adducts, fats and oils
Ethylene oxide adduct, polypropylene glycol
Diethylene oxide adduct, dimethylsiloxane
Tylene oxide block copolymer, dimethyl siloxane
Sun- (propylene oxide-ethylene oxide)
Block copolymer, etc. and polyhydric alcohol type glycero
Fatty acid esters of pentaerythritol
Esters, sorbitol and sorbitan fatty acid esters
Tellurium, fatty acid ester of sucrose, polyhydric alcohol
Kill ethers, fatty acid amides of alkanolamines, etc.
Is mentioned. These nonionic surfactants are used alone
Also, a mixture of two or more may be used. In the present invention
Is sorbitol and / or sorbitan fatty acid ester
Ethylene oxide adduct, polypropylene glycol
Diethylene oxide adduct, dimethylsiloxane
Tylene oxide block copolymer, dimethyl siloxane
Sun- (propylene oxide-ethylene oxide)
Block copolymer, fatty acid ester of polyhydric alcohol
Is more preferable. Also, stable solubility or mixing in water
From the viewpoint of turbidity, nonionic properties used in the treatment liquid of the present invention
As the surfactant, HLB (Hydrophile)
-Lipophile Balance) value is 6 or more
Preferably 8 or more.
Yes. Furthermore, nonionic surfactant contained in the treatment liquid
Is preferably 0.01 to 10% by weight,
More preferred is ˜5% by weight. In addition, an alkaline agent (for example,
Sodium carbonate, triethanolamine, diethanol
Amines, sodium hydroxide, silicates, etc.) or acid agents
(For example, phosphoric acid, phosphorous acid, metaphosphoric acid, pyrroline
Acid, oxalic acid, malic acid, tartaric acid, boric acid, amino acids
Etc.), preservatives (eg benzoic acid and its derivatives,
Sodium doroacetate, 3-isothiazolone compound, 2-
Bromo-2-nitro-1,3-propanediol, 2-
Pyridinethiol-1-oxide sodium salt)
Those added can also be used. Treatment liquid temperature is optional
Although it can be used at a temperature of
The Removal of heat-sensitive layer in non-image area in the present invention
Is an automatic processor equipped with a processing liquid supply means and a rubbing member
It can implement suitably. As an automatic processor
For example, do not transport the lithographic printing plate precursor after image recording.
Japanese Patent Application Laid-Open No. 22-220061, which performs a rubbing process,
An automatic processor described in JP-A-60-59351,
For lithographic printing plates after image recording set on a cylinder
Rub the original plate while rotating the cylinder, U
S5148746, US5568768, GB2297
And an automatic processor described in each item of 719. Inside
However, automatic using a rotating brush roll as a rubbing member
A processor is particularly preferred. FIG. 1 is suitable for the development processing of the present invention.
As an example of the automatic processing machine, the processing liquid 10 is supplied to the circulation pump 1
1 to spray pipe 5 and shower ring
Rotating brush roll 1 and plate surface 12 (lithographic printing plate
Self-rubbing the plate surface 12 with the rotating brush roll 1
A dynamic developing processor is exemplified. In the present invention, rubbing
The treated lithographic printing plate is then washed and dried.
It is also possible arbitrarily. The rotating brush roll that can be used is
Hardness of scratches, and the back of the lithographic printing plate precursor
Can be selected as appropriate in consideration of the strength of the material. Above times
As a rolling brush roll, the brush material is plastic or
Is a well-known material formed by planting on a metal roll.
Can be used. For example, JP-A-58-159533
And those described in Japanese Patent Laid-Open No. 3-100534,
As described in Sho 62-167253,
Metal or plastic with brush material implanted in rows
Gap mold material gaps in the core plastic or metal roll
A brush roll wound radially can be used. Ma
As the brush material, plastic fibers (for example,
Polyethylene terephthalate, polybutylene terephthalate
Polyesters such as cartons, nylon 6.6, nylon
6.10 polyamides, polyacrylonitrile, poly
Polyacrylic such as alkyl (meth) acrylate, and
And polyolefins such as polypropylene and polystyrene
Synthetic fibers), for example, of fibers
The diameter of the hair is 20 to 400 μm, and the length of the hair is 5 to 30
The thing of mm can be used conveniently. In addition, the rotating brush
The outer diameter of the tool is preferably 30 to 200 mm, and the plate surface is rubbed.
The peripheral speed of the brush tip is preferably 0.1-5 m / sec.
That's right. Rotating brush roll used in the present invention
The direction is the same as the transport direction of the lithographic printing plate precursor of the present invention.
It can be in one direction or in the opposite direction.
Two or more rotating brush rows, like the automatic processor shown
At least one rotating brush low
At least one rotating brush that rotates in the same direction
It is preferred that the roll rotates in the opposite direction. This
Therefore, the removal of the heat-sensitive layer in the non-image area is further ensured. The
In addition, rotate the rotating brush roll in the direction of the rotating axis of the brush roll.
It is also effective to make it swing. [0136] The present invention will be described more specifically with reference to the following examples.
Of course, the scope of the present invention is of course limited thereby.
Is not something [Example 1] (Preparation of aluminum support) 99.5 wt% aluminum
Um, 0.01 wt% copper, 0.03 wt% titanium,
JIS containing 0.3% by weight of iron and 0.1% by weight of silicon
A1050 aluminum material (thermal conductivity 0.48cal /
cm.sec..degree. C.) with a thickness of 0.24 mm rolled plate.
20% water of 0 mesh Pamiston (manufactured by Kyoritsu Ceramics)
Suspension and rotating nylon brush (6,10-Nairo
) And then use a water wash
Purified. This was mixed with 15% by weight aqueous sodium hydroxide solution (a
Aluminum immersed in 4.5% by weight of aluminum)
Dissolved in 5 g / m²After etching to be
Washed with water. Further neutralize with 1% by weight nitric acid and then add 0.0.
7 wt% nitric acid aqueous solution (containing 0.5 wt% aluminum)
Inside, anode voltage 10.5 volts, cathode voltage 9.3 volts
Rectangular wave alternating waveform voltage (current ratio r = 0.90, Shoko)
Current wave described in Example of Japanese Patent No. 58-5796
Shape) 160 clones / dm²The amount of electricity when the anode is
A de-roughening treatment was performed. After washing with water, 10 wt% water at 35 ° C
Immerse in aqueous sodium oxide to dissolve aluminum
Amount 1g / m²After etching so that it becomes
It was. Next, it is immersed in a 30% by weight sulfuric acid aqueous solution at 50 ° C.
Then, after desmutting, it was washed with water. Furthermore, sulfur at 35 ° C
Acid 20% by weight aqueous solution (containing 0.8% aluminum)
The porous anodic oxide film is formed by using direct current.
went. That is, a current density of 13 A / dm²Electrolysis is performed with
Anodized film weight 2.7g / m by adjusting time²It was.
After washing this support with water, a sodium silicate solution at 70 ° C.
It was immersed in a 2% by weight aqueous solution for 30 seconds, washed with water and dried. (Synthesis of Fine Particle Polymer 1) Glycidilme
Tacrylate 2.0g, methyl methacrylate 13.0
g, polyoxyethylene phenol aqueous solution (concentration 9.8
× 10^-3mol / liter) 200 ml is added and 250
While stirring at rpm, the system is replaced with nitrogen gas.
After the solution was brought to 25 ° C., cerium (IV) ammonium
Salt aqueous solution (concentration: 0.984 × 10^-3mol / liter)
10 ml is added. In this case, ammonium nitrate aqueous solution
(Concentration 58.8 × 10^-3mol / liter) and p
Adjust to H1.3-1.4. Stir this for 8 hours
did. The liquid thus obtained has a solid content concentration of 9.5.
%, And the average particle size was 0.4 μm. (Formation of heat-sensitive layer) On the above support, the following group
By applying and drying (90 ° C, 2 minutes)
Dry coating weight 1g / m²Form a heat sensitive layer with a lithographic seal
An original plate for printing plate was obtained. [0140] (Thermosensitive layer coating solution 1)       52.6 g of a dispersion of the fine particle polymer 1 synthesized above       Polyhydroxyethyl acrylate       (Weight average molecular weight 25,000) 0.5g       Photothermal conversion agent A (below) 0.3g       100g of water [0141] Embedded image (Preparation of planographic printing plate)
Planographic printing plate precursor, water-cooled 40W infrared semiconductor laser
-Trend setter 3 manufactured by Creo
Plate energy 200mJ / c at 244VFS
m²After exposure at a resolution of 2400 dpi, FIG.
Processing with two rotating brush rolls with the same mechanism
Development was performed using a machine. As a rotating brush roll
The first brush roll with polybutylene terephthalate
Rate fiber (hair diameter 200 μm, hair length 17 m
m) using a brush roll having an outer diameter of 90 mm,
200 revolutions per minute in the same direction as the transport direction (the tip of the brush
(Peripheral speed 0.94m / sec), the second brush roll
For polybutylene terephthalate fibers (hair diameter
200 μm, hair length 17 mm)
Using a brush roll of mm, every minute in the direction opposite to the transport direction
200 rotations (peripheral speed of brush tip 0.63 m / sec)
I let you. The transport of the planographic printing plate precursor is performed at a transport speed of 100c.
m / min. Use the following treatment liquid 1 as the treatment liquid.
A shower pump with a circulation pump
And supplied to the printing plate. [0143] (Processing liquid 1)   RHEODOL TW-O106 0.5g     (Manufactured by Kao Corporation, polyoxyethylene sorbitan monooleate,       HLB = 10.0)   EU-3 (Etch solution manufactured by Fuji Photo Film Co., Ltd.) 2.0 g   97.5g of water (Printing Evaluation) Next, the obtained lithographic plate
The printing plate is Sylin of the printing machine SOR-M manufactured by Heidelberg
Attached to the printer and printed (Dampening solution used: IF-1
02 volume (made by Fuji Photo Film Co., Ltd.) was added by 4% by volume.
Aqueous solution, ink used: TK High Echo SOYMZ Black
(Manufactured by Toyo Ink Co., Ltd.))
When the number of inks to be removed was evaluated, it was 10
Within the first sheet, the non-image area is free of dirt and the image area
A printed matter having good ki-thickness was obtained. [Comparative Example 1] Planographic printing plate precursor of Example 1
After the image exposure in the same manner as in Example 1, the automatic processor of Example 1
Example 1 except that the rotating brush roll was removed
Development processing was performed. That is, do not rub with a rubbing member
In addition, only the treatment solution was washed. Then obtained lithographic
The printing plate is Sylin of the printing machine SOR-M manufactured by Heidelberg
Attached to the printer, printed as in Example 1 and printed
When evaluating the number of non-image area ink to be removed
However, it takes 50 sheets until the non-image area is clean.
It was. [Comparative Example 2] Planographic printing plate precursor of Example 1
As in Example 1, no processing is performed after image exposure.
Cylinder of SOR-M printing machine made by Heidelberg
Attached to the printer, printed in the same manner as in Example 1, and printed out.
Evaluation of the number of inks to be removed from the non-image area
It took 50 sheets until the non-image area was clean. [Example 2] (Synthesis of Fine Particle Polymer 2) Allyl methacrylate7.
5 g and 7.5 g of styrene were synthesized for the fine particle polymer 1
Polymerization was conducted in the same manner as described above. Of the liquid thus obtained
The solid content concentration is 9.5% and the average particle size is 0.4 μm.
there were. (Formation of heat-sensitive layer) Heat-sensitive layer coating solution of Example 1
Is the same as in Example 1 except that the coating solution is changed to a coating solution having the following composition:
Thus, a thermosensitive layer was formed to obtain a lithographic printing plate precursor. [0149] (Thermosensitive layer coating solution 2)       52.6 g of dispersion of the fine particle polymer 2 synthesized above       Polyacrylic acid       (Weight average molecular weight 25,000) 0.5g       Sorbitol triacrylate 1.0g       Photothermal conversion agent A 0.3g       100g of water Next, the obtained lithographic printing plate precursor was carried out.
Perform image exposure, development, and printing in the same way as Example 1 and print
When evaluating the number of non-image area ink to be removed
There is no stain on the non-image area within the 10th print.
Prints with good ink fillability in the image area.
It was. [Example 3] (Synthesis of fine particle polymer 3) 15 g of styrene
Polymerization was carried out in the same manner as in the synthesis of the child polymer 1. like this
The solid content of the liquid obtained in this way is 9.0%, and the average grain
The diameter was 0.3 μm. (Formation of heat-sensitive layer) Heat-sensitive layer coating solution of Example 1
Is the same as in Example 1 except that the coating solution is changed to a coating solution having the following composition:
Thus, a thermosensitive layer was formed to obtain a lithographic printing plate precursor. [0153] (Thermosensitive layer coating solution 3)       Dispersion of the above synthesized fine particle polymer 3 52.6 g       Polyacrylic acid       (Weight average molecular weight 25,000) 0.5g       Photothermal conversion agent A 0.3g       100g of water Next, the resulting lithographic printing plate precursor was implemented.
Perform image exposure, development, and printing in the same way as Example 1 and print
When evaluating the number of non-image area ink to be removed
There is no stain on the non-image area within the 10th print.
Prints with good ink fillability in the image area.
It was. Example 4 On the heat sensitive layer, the following over
Except for forming the coat layer, the same procedure as in Example 1 was conducted.
An original plate for printing plate was obtained. (Formation of overcoat layer) On the heat-sensitive layer,
Apply the following overcoat layer coating solution, heat dry (100
, 2 minutes), the dry coating weight is 0.3 g / m²
An overcoat layer was formed. [0157] (Overcoat layer coating solution) ・ 1g gum arabic ・ EMALEX 710 0.025g (Nippon Emulsion Co., Ltd., polyoxyethylene lauryl ether) ・ Water 19g Next, in the same manner as in Example 1, the image exposure
Light, development processing, and printing are performed, and the non-image area is
When the number of inks to be removed was evaluated, it was 10
Within the first sheet, the non-image area is free of dirt and the image area
A printed matter having good ki-thickness was obtained. [0159] According to the present invention, a simple development processing method is achieved.
Non-image of lithographic printing plate that can be recorded in heat mode
The heat-sensitive layer in the image area can be removed efficiently and reliably.
In addition, it is possible to prevent contamination during printing.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a layout diagram showing the configuration of an automatic processor suitable for development processing of a lithographic printing plate preparation method of the present invention. [Explanation of Symbols] 1 Rotating brush roll 2 Receiving roll 3 Conveying roll 4 Conveying guide plate 5 Spray pipe 6 Pipe line 7 Filter 8 Plate feeding table 9 Discharging plate 10 Processing liquid (tank) 11 Circulating pump 12 Master plate for lithographic printing plate

Claims (1)

What is claimed is: 1. A lithographic printing plate precursor provided with a heat-sensitive layer containing a fine particle polymer on a support having a hydrophilic surface, and a rubbing member is provided after image recording is performed. A method for producing a lithographic printing plate, comprising a step of rubbing a plate surface with a rubbing member in the presence of a treatment liquid by an automatic processor to remove a heat-sensitive layer in a non-image area.