JP2003231369A - Original plate for thermal lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original plate for a thermal lithographic printing plate which can be manufactured by scanning and exposure based on a digital signal, can be fitted directly to a printing machine without being treated after the exposure, prevents the pollution of a laser and a light source by the scattering of abrasion gas, is high in sensitivity and excellent in fouling resistance, and has high printing resistance. <P>SOLUTION: In the original plate, an ink receiving layer (1), a hydrophilic layer (2) containing an oxide or a hydroxide of colloidal particles of at least one element selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, thin, zirconium, iron, vanadium, antimony, and transition metals, and a hydrophilic overcoat layer (3) removable on the printing machine are formed in turn on an aluminum substrate which is surface-roughened and has an anodically oxidized film. The amount of the dry application of the ink receiving layer is below 0.5 g/m<SP>2</SP>, and the amount of the anodically oxidized film is 3.0-5.0 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a computer tool.
Development-free lithographic stamp for C-plate (CTP) system
It relates to an original plate for printing plates. More specifically, based on digital signals
Image recording by infrared scanning exposure based on
The image recorded is subjected to a conventional liquid development process.
Without printing, install it in the printing machine as it is and print it.
The present invention relates to an original plate for a heat-sensitive lithographic printing plate that can be used. [0002] 2. Description of the Related Art Conventionally, lithographic printing plates have been manufactured using intermediate materials.
A system that exposes an original plate for printing plate through a squirrel film.
Has been done in the system. However, in the printing field in recent years
With the rapid progress of digitization, the printing plate making process
Print digital data entered and edited on a computer
Changing to a CTP system that outputs directly to the original plate
The Among them, aiming for further process rationalization, after exposure,
Installed in the printing machine without printing and printing
Development and development-free lithographic printing plate precursors have been researched and developed.
ing. For example, Journal of Japan Printing Society, Vol. 36, 148-16
On page 3 (1999), various development-free CTP plates are available.
A method is described. One promising method is a semiconductor laser, YA.
Exposure with a solid-state high-power infrared laser such as a G laser to heat the light
It generates heat with a photothermal conversion agent that converts it into an
This is a method using ablation. Snow
That has an oleophilic ink-receptive surface or ink-receptive layer
A hydrophilic layer is provided on the substrate, and the hydrophilic layer is ablated and removed.
It is a method to do. WO 94/18005 includes a lipophilic lei
This hydrophilic layer is provided with a crosslinked hydrophilic layer on the light absorption layer.
The printing plate which ablates is described. This parent
The water layer is made of polyvinyl alcohol and tetraethoxy silicon.
Cross-linked with hydrolyzate to contain titanium dioxide particles
This is intended to improve the film strength of the hydrophilic layer.
This technique improves printing durability. But hard to get dirty
Was insufficient and further improvements were needed. WO 98/40212 and WO 99/1
9143 includes an ink receiving layer on a substrate and silica.
Which colloids such as aminopropyltriethoxysilane
Having a hydrophilic layer whose main component is one crosslinked with a crosslinking agent
Describes a lithographic printing plate that can be mounted on a printing press without development
Has been. This hydrophilic layer has as few hydrocarbon groups as possible.
To increase resistance to printing stains and build a colloid with a cross-linking agent
The bridge is designed to improve printing durability. But
However, with this technology, the printing durability was insufficient, such as several thousand sheets. Further, a lithographic plate using conventional ablation
On the original plate for printing plates, ablation residue is scattered and
There is a problem of contaminating the exposure apparatus and the light source. That
Therefore, these devices are equipped with a device that captures ablation debris.
It was necessary to add a device, but the capture device
It was difficult to remove it sufficiently. On the other hand, Japanese Patent Application Laid-Open No. 2001-96936.
Have an ink receptive surface or have an ink receptive layer
On the coated substrate, the heating unit is dampening water or ink during printing.
Easily removed by the hydrophilic layer, and light if necessary
Sense of having a water-soluble overcoat layer containing a heat conversion agent
Good printing durability and stains due to the thermal lithographic printing plate
Difficulty, and by suppressing the scattering of ablation residue
This means that contamination of the laser exposure device and light source is prevented.
It is listed. [0008] However, the above modification
Even with good technology, there is no need for further high printing durability.
It was enough. The problem of the present invention is to solve this problem.
It is. In other words, direct printing without post-exposure processing.
It is possible to print by mounting on a printing press.
Contamination of laser exposure equipment and light source due to scattering of
Prevented, high sensitivity, excellent stain resistance, and high printing durability
The object is to provide a heat-sensitive lithographic printing plate precursor. [0009] The present invention solves the problems of the present invention.
Means are as follows. Roughened anodized film
(1) an ink receiving layer on an aluminum substrate having
(2) Beryllium, magnesium, aluminum, silicon
Elemental, titanium, boron, germanium, tin, zirconium
, Iron, vanadium, antimony and transition metals
Colloidal particulate oxide of at least one element selected
Or a hydrophilic layer containing a hydroxide and (3) a printing press
Has a hydrophilic overcoat layer that can be removed above in this order
A thermosensitive lithographic printing plate
Dry coating amount 0.5g / m²The amount of anodized film is less than
3.0g / m²Or more, 5.0 g / m ²That it is less than
A heat-sensitive lithographic printing plate. The base plate for a lithographic printing plate having the layer structure of the present invention
In order to achieve high printing durability, it is not compatible with the oleophilic ink receiving layer.
It was necessary to reinforce the adhesion with the hydrophilic layer. That
For this purpose, the ink receiving layer is 0.5 g / m.²In a thin layer of less than
To trace the roughness of the support surface.
The surface of the roughened ink receiving layer is formed and its anchor effect is achieved.
It was considered to be used. However, the ink receiving layer is thin
Layering weakens the heat-insulating properties of the ink-receiving layer and occurs upon exposure.
The generated heat can be easily diffused to the aluminum support to increase sensitivity.
A new problem has been created to reduce. The inventor
As a result of detailed examination, the anodized leather on the aluminum surface
The amount of film is 3.0g / m²5.0 g / m²Less than
Found that it has good heat insulation in a specific range, this
The above problems can be solved by utilizing the heat insulating property, and the present invention.
It came to. [0011] DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
Will be described in detail. % Means weight unless otherwise specified
%. The support of the present invention is roughened and anodized.
An aluminum substrate having a film. Raw material alumini
The aluminum plate is an aluminum plate made of a publicly known material.
It can be used as appropriate. That is, raw material alumini
Um plate is mainly pure aluminum plate or aluminum.
An alloy plate containing a small amount of different elements as a component. Armini
The different elements contained in the aluminum alloy include silicon, iron, and manga.
Copper, magnesium, chromium, zinc, bismuth, nickel
There are Kell and Titanium. The content of foreign elements in the alloy is 1
0% or less. Aluminum using DC casting method
Even aluminum plates from ingots are cast by the continuous casting method.
An aluminum plate from a lump may be used. The aluminum substrate used in the present invention
Has a thickness of 0.05 to 0.6 mm, preferably 0.1 to
0.4 mm, particularly preferably 0.15 to 0.3 mm
The Various roughening treatments can be applied to the surface of the aluminum plate.
It can be done by the method. For example, mechanically roughening
Method, electrochemically dissolving and roughening the surface, chemistry
To selectively dissolve the surface, or these methods
Can be done by combining two or more of
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. As the chemical method, JP-A-54-
Mineral acid aluminum as described in Japanese Patent No. 31187
A method of immersing in a saturated aqueous solution of a nium salt is suitable. Ma
Electrochemical roughening methods include hydrochloric acid and nitric acid.
There are methods that use alternating current or direct current in an electrolyte containing acid.
The Moreover, it is disclosed by Unexamined-Japanese-Patent No. 54-63902.
It is also possible to use an electrolytic surface roughening method using mixed acid
it can. The roughened aluminum plate can be used as needed.
To an aqueous solution such as potassium hydroxide or sodium hydroxide.
According to alkali etching treatment, further neutralization treatment
Then, anodization is performed. Used for anodizing of aluminum plates
Examples of electrolytes include various types of electrodes that form porous oxide films.
Degradation can be used, and in general, sulfuric acid, phosphoric acid, soot
Acid, chromic acid, sulfamic acid, benzenesulfonic acid,
Alternatively, a mixed acid thereof is used. These electrolytes
The concentration of is appropriately determined depending on the type of electrolyte. The treatment conditions for anodization depend on the electrolyte used.
However, in general, it cannot be specified.
Electrolyte concentration is 1-80% solution, liquid temperature is 5-70 ° C,
Current density 5-60A / dm2, voltage 1-100V, during electrolysis
It is suitable if it is in the range of 10 seconds to 50 minutes. these
Among the anodizing treatments, in particular, British Patent 1,412,7
Anode with high current density in sulfuric acid as described in JP 68
Method of oxidizing and in US Pat. No. 3,511,661
Method for anodizing phosphoric acid as an electrolytic bath
Is preferred. Amount of oxide film on aluminum substrate of the present invention
Is 3.0 g / m²Or more, 5.0 g / m²Is less than. Yo
More preferably 3.2 to 4.5 g / m²Most preferably
3.5-4.0 g / m²It is. Good disconnection within this range
Thermal effect is obtained. The amount of oxide film is 3.0g / m²Less than
Has insufficient heat insulation effect, while 5.0 g / m²that's all
But the insulation effect is insufficient. 5.0 g / m²That's it
The thermal effect is insufficient because the amount of oxide film increases.
As a result, the diameter at the opening of the oxide film pores increases,
The receptive layer enters the pores and heat insulation by the air in the pores
To prevent and promote the diffusion of heat to the support
Presumed. As the substrate used in the present invention, the above-mentioned substrate is used.
A substrate having an anodized film that has been surface-treated like that
It can be left as it is.
For improvement, if necessary, JP-A-2001-25318
Sealing of micropores in the anodized film described in No. 1
Hole treatment, described in JP-A-2001-322365
Surface hydrophilization immersed in an aqueous solution containing a hydrophilic compound
Processing etc. can be selected as appropriate. Suitable hydrophilic compound for the above hydrophilization treatment
As a product, it has polyvinyl phosphonic acid, sulfonic acid group
Compounds, saccharide compounds, citric acid, alkali metal silicates,
Zirconium fluoride potassium, phosphate / inorganic fluorination
Examples include compounds. Aluminum group obtained as described above
The surface roughness of the plate has a center line average roughness Ra of 0.45 μm or less.
Upper is preferable, 0.48 μm or more is more preferable.
52 μm or more is particularly preferable. The upper limit of Ra value is
It is also related to the coating thickness of the ink receiving layer applied to the
However, it is generally preferable to use up to about 0.7μm.
Yes. Within this range, the surface of the ink receiving layer is good with the hydrophilic layer.
It can be a rough surface showing adhesiveness. The ink receiving layer used in the present invention is an organic layer.
Contains polymer. Organic polymers are soluble in solvents
Thus, a lipophilic film can be formed. Moreover,
It should be insoluble in the coating solvent for the upper hydrophilic layer.
However, in some cases, it may swell in the upper coating solvent.
This is desirable because it has excellent adhesion to the hydrophilic layer.
In addition, organic polymers that are soluble in the coating solvent for the hydrophilic layer are used.
In some cases, add a cross-linking agent, etc.
It is desirable to cure the container layer. Useful organic polymers include polyester.
Polyurethane, polyurea, polyimide, polysil
Xan, polycarbonate, phenoxy resin, epoxy
Resin, novolac resin, resole resin, phenol compound
Resin and acetone condensation resin, polyvinyl acetate,
Kuryl resin and its copolymer, polyvinylphenol,
Polyvinyl halide phenol, methacrylic resin and
Its copolymer, acrylamide copolymer, methacrylate
Mido copolymer, polyvinyl formal, polyamide,
Polyvinyl butyral, polystyrene, cellulose es
Tellurium resin, polyvinyl chloride, polyvinylidene chloride, etc.
I can make it. Of these, more preferred compounds
Side chain with hydroxyl group, carboxyl group, sulfone
Resin having amide group or trialkoxysilyl group
Excellent adhesion to the plate and upper hydrophilic layer, sometimes cross-linked
It is desirable because it hardens easily with an agent. In addition, acrylonitrile copolymer, poly
Urethane, copolymer having sulfonamide group in the side chain,
A copolymer having a hydroxyl group in the side chain is converted into a diazo resin.
Therefore, what was photocured is preferable. Epoxy resin suitable for the ink receiving layer of the present invention
Examples of fats include bisphenol A / epichlorohis
Dorin polyadduct, bisphenol F / epichlorohydride
Polyadduct, Halogenated Bisphenol A / Epichloro
Hydrin polyadduct, biphenyl type bisphenol / epi
Chlorohydrin polyadduct, novolak resin / epichloro
Examples include hydrin polyadducts. Specifically
Is Japan Epoxy Resin Epicoat 1001
(Softening point 68 ° C., Mn about 900), Epicoat 1007
(Softening point 128 ° C., Mn about 2900), Epicoat 10
09 (softening point 144 ° C., Mn about 3750), Epicoat 1
010 (softening point 169 ° C., Mn about 5500), Epicoat
1100L (softening point 149 ° C), Epicoat YX315
75 (softening point 130 ° C.). As novolak resin and resol resin
Is phenol, cresol (m-cresol, p-
Resole, m / p mixed cresol), phenol / cres
Zole (m-cresol, p-cresol, m / p mixed
Cresol), phenol-modified xylene, t-butyl fluoride
Enol, octylphenol, resorcinol, pyro
Gallol, catechol, chlorophenol (m-Cl,
p-Cl), bromophenol (m-Br, p-B)
r), salicylic acid, phloroglucinol and the like, and alde
Hydrides such as formaldehyde, paraformaldehyde
Addition condensates with aldehydes and the like can be mentioned. Other suitable polymer compounds are as follows:
The monomer shown in (1) to (12) is the structural unit.
Name a copolymer with an average molecular weight of usually 1 to 200,000
You can. (1) Acrylic having an aromatic hydroxy group
Luamides, methacrylamides, acrylic esters
, Methacrylates and hydroxystyrene
Such as N- (4-hydroxyphenyl) acrylic
Mido or N- (4-hydroxyphenyl) methacrylate
Imide, o-, m- and p-hydroxystyrene, o-,
m- and p-hydroxyphenyl acrylate or meta
Krillate, (2) Acryl having an aliphatic hydroxy group
Luric acid esters and methacrylic acid esters, for example
2-hydroxyethyl acrylate or 2-hydroxy
Ethyl methacrylate, (3) Methyl acrylate, Ethyl acrylate
, Propyl acrylate, butyl acrylate, acrylic
Amyl acid, Hexyl acrylate, Cyclohexyl acrylate
Sil, octyl acrylate, phenyl acrylate, acrylic
Benzyl yllate, 2-chloroethyl acrylate,
4-hydroxybutyl toluate, glycidyl acrylate
And N, N-dimethylaminoethyl acrylate
Acrylic ester, (4) Methyl methacrylate, methacrylic acid
Ethyl, propyl methacrylate, butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, methacrylate
Cyclohexyl oxalate, octyl methacrylate, methacrylate
Phenyl lurate, benzyl methacrylate, methacrylic acid
2-chloroethyl, 4-hydroxybuty methacrylate
Glycidyl methacrylate, N, N-dimethylamino
Methacrylate esters such as noethyl methacrylate, (5) Acrylamide, methacrylamid
N-methylolacrylamide, N-methylolme
Tacrylamide, N-ethylacrylamide, N-eth
Methacrylamide, N-hexylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl aqua
Rilamide, N-cyclohexylmethacrylamide, N
-Hydroxyethylacrylamide, N-hydroxye
Tylacrylamide, N-phenylacrylamide, N
-Phenylmethacrylamide, N-benzylacrylic
Mido, N-benzylmethacrylamide, N-nitrofe
Nylacrylamide, N-nitrophenyl methacrylate
Nido, N-ethyl-N-phenylacrylamide and N
-Acryl such as ethyl-N-phenylmethacrylamide
Luamide or methacrylamide, (6) Ethyl vinyl ether, 2-chloro
Ethyl vinyl ether, hydroxyethyl vinyl ether
, Propyl vinyl ether, butyl vinyl ether,
Octyl vinyl ether, phenyl vinyl ether, etc.
Vinyl ether, (7) Vinyl acetate, vinyl chloroa
Vinyl acetate, vinyl butyrate, vinyl benzoate, etc.
Nyl ester, (8) Styrene, methylstyrene, chloro
Styrenes such as methylstyrene, (9) Methyl vinyl ketone, ethyl vinyl
Ketone, propyl vinyl ketone, phenyl vinyl ketone
Vinyl ketone, (10) Ethylene, propylene, isobuty
Olefins such as lene, butadiene and isoprene, (11) N-vinyl pyrrolidone, N-vinyl
Lucarbazole, 4-vinylpyridine, acrylonitrile
Ru, methacrylonitrile, etc. (12) N- (o-aminosulfonylphenol)
Nyl) acrylamide, N- (m-aminosulfonyl)
Enyl) acrylamide, N- (p-aminosulfonyl)
Phenyl) acrylamide, N- [1- (3-aminos)
Sulfonyl) naphthyl] acrylamide, N- (2-amino
Nosulfonylethyl) acrylamide and other acrylics
Mides, N- (o-aminosulfonylphenyl) metac
Rilamide, N- (m-aminosulfonylphenyl) methyl
Tacrylamide, N- (p-aminosulfonylpheny
) Methacrylamide, N- [1- (3-aminosulfo
Nyl) naphthyl] methacrylamide, N- (2-amino
Sulfonyl such as sulfonylethyl) methacrylamide
Amide group-containing acrylamide or methacrylamide,
O-aminosulfonylphenyl acrylate, m-
Aminosulfonylphenyl acrylate, p-aminos
Sulfonylphenyl acrylate, 1- (3-aminosulfur
Phonylphenylnaphthyl) acrylate, o-aminos
Sulfonylphenyl methacrylate, m-aminosulfonate
Ruphenyl methacrylate, p-aminosulfonyl phen
Nyl methacrylate, 1- (3-aminosulfonylphenol
Nylnaphthyl) sulfonamide groups such as methacrylate
Containing acrylic acid ester or methacrylic acid ester. These organic polymers are dissolved in an appropriate solvent.
The ink receiving layer is applied on the substrate and dried.
Can Dissolve only organic polymer in solvent
It can be used, but it can be used as a crosslinking agent, adhesion aid, colorant,
Cloth surface condition improver and plasticizer can be added as needed.
Yes. In addition, a printout image after exposure is formed.
Heating coloring or decoloring additives are added for
Also good. As a crosslinking agent for crosslinking the organic polymer,
For example, diazo resin, aromatic azide compound, epoxy resin
Fat, isocyanate compound, blocked isocyanate
Compound, initial hydrolysis condensate of tetraalkoxysilicon,
Rioxar, aldehyde compounds and methylol compounds
Can be mentioned. As the bonding aid, the diazo resin is a substrate.
In addition to this, it has excellent adhesion to the hydrophilic layer.
Ring agent, isocyanate compound, titanium-based coupling
Glue is also useful. As the colorant, ordinary dyes and pigments are used.
In particular, rhodamine 6G chloride, rhodamine B salt
Chemical, Crystal Violet, Malachite Green
Oxalate, quinizarin, 2- (α-naphthyl) -5-fur
Examples include enyl oxazole. As other dyes
Specifically, oil yellow # 101, oil yellow
# 103, Oil Pink # 312, Oil Green B
G, oil blue BOS, oil blue # 603, oy
Le Black BY, Oil Black BS, Oil Black
T-505 (above, manufactured by Orient Chemical Co., Ltd.), Bi
Cutria Pure Blue, Crystal Violet (CI
42555), methyl violet (CI4253)
5), ethyl violet, methylene blue (CI52
015), Patent Pure Blue (Sumitomo Sangoku Chemical Co., Ltd.)
Made), brilliant blue, methyl green, erythri
Shin B, basic fuchsin, m-cresol purp
Ru, auramine, 4-p-diethylaminophenylimi
Naphthoquinone, cyano-p-diethylaminophenyla
Triphenylmethane series represented by cetanilide,
Diphenylmethane, oxazine, xanthene, a
Minonaphthoquinone, azomethine, or anthraquinone
Type dyes or JP-A-62-293247,
The dyes described in Kaihei 9-179290 are listed.
I can make it. The above dye is added to the ink receiving layer.
In this case, it is usually about 0.02 to 10 with respect to the total solid content of the receiving layer.
%, More preferably about 0.1-5%. Furthermore, it is well known as a coated surface condition improver.
Fluorine-based surfactants and silicon-based surfactants
Sex agents can also be used. Specifically perfluoroa
Surfactant with alkyl group or dimethylsiloxane group
It is useful by arranging the coated surface. Furthermore, it is necessary for the ink receiving layer of the present invention.
If necessary, add a plasticizer to give the coating film flexibility.
It is. For example, polyethylene glycol, tricitrate
Butyl, diethyl phthalate, dibutyl phthalate, fuckle
Dihexyl acid, dioctyl phthalate, tricresic acid phosphate
, Tributyl phosphate, trioctyl phosphate, olein
Tetrahydrofurfuryl acid, acrylic acid or methacrylic acid
Acid oligomers and polymers are used. Furthermore, it can be added to the ink receiving layer of the present invention.
Examples of additives for coloring or decoloring printing
Such as diazo compounds and diphenyliodonium salts
Thermal acid generator and leuco dye (leucomalachite green,
Leuco crystal violet, crystal violet
Lactones) and PH discoloring dyes (eg ethyl
Dyeing of iolet, Victoria pure blue BOH, etc.
Are used in combination. Others, EP8771
Acid coloring dye and acid as described in No. 34 specification
A combination of sexual binders is also effective. In this case, heating
As a result, the association state forming the dye is broken by
A kuton body is formed and changes from colored to colorless. these
The proportion of additive added is preferably the solid content of the ink receiving layer.
On the other hand, it is 10% or less, more preferably 5% or less. As a solvent for coating the ink receiving layer
Are alcohols (methanol, ethanol, propyl
Alcohol, ethylene glycol, diethylene glycol
, Propylene glycol, dipropylene glycol,
Ethylene glycol monomethyl ether, propylene glycol
Recall monomethyl ether, ethylene glycol mono
Ethyl ether, etc.), ethers (tetrahydrofurans)
, Ethylene glycol dimethyl ether, propylene
Glycol dimethyl ether, tetrahydropyran
Etc.), ketones (acetone, methyl ethyl ketone,
Tylacetone), esters (methyl acetate, ethyl acetate)
, Ethylene glycol monomethyl ether monoacetate
, Gamma-butyrolactone, methyl lactate, ethyl lactate
), Amides (formamide, N-methylformua)
Mido, pyrrolidone, N-methylpyrrolidone, etc.)
Can. These solvents can be used alone or in combination.
Used. Ink-receiving layer component (addition) in coating solution
The concentration of the total solid content including the agent is preferably 1 to 50%
is there. In addition, only application from organic solvents as described above
Not only to form a film from an aqueous emulsion
Can do. In this case, the concentration is preferably 5% to 50%.
Yes. The dry coating amount of the ink receiving layer of the present invention is:
0.5g / m²Is less than. Under the preferred dry coating amount
The limit is 0.2 g / m²And more preferably 0.3 g
/ M²It is. Within this range, the surface of the ink receiving layer is a hydrophilic layer.
A rough surface with good adhesion and good printing durability can be obtained.
It is. The hydrophilic layer of the present invention comprises beryllium and magnesi.
Um, aluminum, silicon, titanium, boron, germany
Um, tin, zirconium, iron, vanadium, antimony
Of at least one element selected from
Contains colloidal particulate oxide or hydroxide. Colloidal particulate oxides of these elements or
Hydroxides are halides and alkoxy compounds of the above elements.
Various public interests such as hydrolysis of products or condensation of hydroxides
The dispersed phase of the colloidal dispersion by known methods, ie,
Made as colloidal particles. Parent for providing a hydrophilic layer
When adding to the aqueous layer coating liquid, in the state of colloidal dispersion.
Can be added. Oxides or hydroxides of these elements
Particularly preferred are aluminum, silicon, and titanium.
At least one element selected from zinc and zirconium
Elemental oxide or hydroxide. An oxide or hydroxide roller of these elements
In the case of silica, the id particle has a colloidal particle size of 5 to 5.
A 100 nm spherical shape is preferred. 10-50nm
Of spherical particles of 50 to 400 nm in length
Lu Necklace colloidal particles can also be used.
Colloidal particles of aluminum oxide or hydroxide
It is also effective to use feathers like 100nm x 10nm
It is. These colloidal dispersions are manufactured by Nissan Chemical Industries.
Commercial products such as Co., Ltd. can also be purchased. As a dispersion medium for these colloidal particles,
In addition to water, methanol, ethanol, ethylene glycol
Such as methyl monomethyl ether and methyl ethyl ketone.
Organic solvents are also useful. In the hydrophilic layer of the present invention, the colloidal particles and
In both cases, a hydrophilic resin can be used. Hydrophilic resin
By using it, the film property of the hydrophilic layer is strengthened and printing durability is improved.
I can go up. Examples of hydrophilic resins include hydroxyl,
Carboxyl, hydroxyethyl, hydroxypropi
Amino, aminoethyl, aminopropyl, carboxy
Those having a hydrophilic group such as dimethyl are preferred. As a specific hydrophilic resin, Arabico
, Casein, gelatin, starch derivatives, carboxymethyl
Cellulose and their sodium salts, cellulose
Cetate, sodium alginate, vinyl acetate-male
Acid copolymer, styrene-maleic acid copolymer, polyester
Liacrylic acid and their salts, polymethacrylic acid and its
Homopoly of these salts, hydroxyethyl methacrylate
Polymers and copolymers, of hydroxyethyl acrylate
Homopolymers and copolymers, hydroxypropyl meta
Acrylate homopolymers and copolymers, hydroxy
Homopolymers and copolymers of propyl acrylate,
Homopolymers and copolymers of hydroxybutyl methacrylate
Polymer, hydroxybutyl acrylate homopolymer
-Copolymer, polyethylene glycol, polypro
Pyrene oxide, polyvinyl alcohol, and water
Degradation degree is at least 60%, preferably at least 80
% Hydrolyzed polyvinyl acetate, polyvinylformer
, Polyvinyl butyral, polyvinyl pyrrolidone,
Acrylamide homopolymers and copolymers,
Rilamide homopolymers and polymers, N-methylo
Examples include homopolymers and copolymers of ruacrylamide.
I can make it. The ratio of addition of these hydrophilic resins depends on the hydrophilic layer.
40% or less of solid content is preferable, and 20% or less is more preferable
That's right. The hydrophilic layer of the present invention has an aromatic hydroxyl group.
It is also possible to use a resin having Has aromatic hydroxyl group
When the resin used is used, it is possible to improve the film properties of the hydrophilic layer at the same time.
In addition, imprinting quality can be improved. Aromatic
As a resin having a hydroxyl group, methanol at 25 ° C.
% Or more soluble, for example, novolak tree
Fat, resole resin, polyvinylphenol resin, ketone
Examples include alkali-soluble resins such as pyrogallol resin.
The Preferred novolak resins include phenol.
, O-cresol, m-cresol, p-cresol
, 2,5-xylenol, and 3,5-xylenol
And at least one hydroxyl group selected from resorcin.
Aromatic compounds, formaldehyde, acetaldehyde
Selected from aldehydes such as
Novo that is addition-condensed under acidic catalyst with at least one kind
A rack resin is mentioned. Formaldehyde and aceto
Paraformaldehyde instead of aldehyde
And paraaldehyde may be used. Among them, m-cresol: p-crezo
2,5-xylenol: 3,5-xylenol:
The mixing ratio of resorcin is 40-100: 0 to 5 in molar ratio
A mixture of 0: 0-20: 0-20-20-0, or
Mixing ratio of enol: m-cresol: p-cresol
In a molar ratio of 1-100: 0 to 70: 0-60 and
Novolac resins, which are addition condensation products with aldehydes, are preferred.
That's right. Of the aldehydes, formaldehyde is particularly preferred.
Good. The weight average molecular weight of the novolak resin is preferably
Is 1,000 to 15,000, more preferably 1,5
00 to 10,000 are used. Preferred resole resins include phenol
M-cresol, o-cresol, p-cresol
2,5-xylenol, 3,5-xylenol, le
Zolcine, pyrogallol, bis- (4-hydroxyphenol
Nyl) methane, bisphenol-A, o-ethylpheno
, M-ethylphenol, p-ethylphenol,
Propylphenol, n-butylphenol, t-butyl
Water such as ruphenol, 1-naphthol, 2-naphthol
Acid group-containing aromatic hydrocarbons and other two or more hydroxyl groups
At least one polynuclear aromatic hydrocarbon having
Under a rutile catalyst, formaldehyde, acetaldehyde
, Propionaldehyde, benzaldehyde, furf
Aldehydes such as Lar, acetone, methyl ethyl ketone
T, methyl isobutyl ketone and other ketones
Addition condensation with at least one aldehyde or ketone
Can be mentioned. Of formaldehyde and acetaldehyde
Instead, paraformaldehyde and paraal, respectively
Dehydr may be used. Weight average molecule of resole resin
The amount is preferably 500 to 10,000, particularly preferably
Is 1,000 to 5,000. Preferred polyvinylphenol resin
Is o-hydroxystyrene, m-hydroxystyrene.
, P-hydroxystyrene, 2- (o-hydroxyphenyl)
Enyl) propylene, 2- (m-hydroxyphenyl)
Propylene, 2- (p-hydroxyphenyl) propylene
Hydroxystyrenes alone or in combination of two or more
A polymer is mentioned. Hydroxystyrenes are aromatic rings
And halogens such as chlorine, bromine, iodine and fluorine, or charcoal
It may have a substituent such as an alkyl group having 1 to 4 primes
Therefore, as the polyvinylphenols, aromatic rings
Has a halogen or an alkyl group having 1 to 4 carbon atoms.
There may be mentioned polyvinylphenol. In addition, o-hydroxystyrene, m
-Hydroxystyrene, p-hydroxystyrene, 2-
(O-hydroxyphenyl) propylene, 2- (m-hi
Droxyphenyl) propylene, 2- (p-hydroxy)
Phenyl) propylene and other hydroxystyrenes,
Methacrylic acid, acrylic acid, alkyl methacrylate
Some are copolymerized with tellurium or alkyl acrylate.
Useful. Polyvinylphenol resin is usually substituted
Hydroxystyrene which may have a group alone or
2 or more types, radical polymerization initiator or cationic polymerization opening
It can be obtained by polymerizing in the presence of an initiator. Take
Livinylphenol resin is partially hydrogenated
It's okay. In addition, t-butoxycarbonyl group, pyrani
Group, furanyl group, etc.
A resin in which some hydroxyl groups are protected may be used. Polyvinylfe
The weight average molecular weight of the nor resin is preferably 1,000.
~ 100,000, particularly preferably 1,500-50,
000. Examples of ketone pyrogallol resins include aceto
Nupirogallol resin is particularly useful. Addition of resins having these aromatic hydroxyl groups
The proportion is preferably 20% or less of the solid content of the hydrophilic layer, more preferably
Preferably it is 12% or less. The hydrophilic layer of the present invention contains a colloidal oxide or
May add a crosslinking agent that promotes the crosslinking of the hydroxide.
As such a crosslinking agent, tetraalkoxysilane
Initial hydrolysis condensate, trialkoxysilylpropyl-
N, N, N-trialkylammonium halide, or
Is preferably aminopropyltrialkoxysilane.
The addition ratio is preferably 5% or less of the solid content of the hydrophilic layer. Furthermore, the hydrophilic layer of the present invention has a resistance to printing during printing.
For the purpose of increasing printing force, the above hydrophilic resin or aromatic resin is used.
You may add the crosslinking agent of resin which has an aromatic hydroxyl group. This
Cross-linking agents such as formaldehyde and glyoxa
Of polyol, polyisocyanate, tetraalkoxysilane
Initial hydrolysis / condensate, dimethylol urea and hexame
Mention may be made of tyrolmelamine. In addition, the hydrophilic layer of the present invention has a coated surface shape.
Well-known fluorine-based surfactants,
Silicone surfactant, polyoxyethylene surfactant
An agent or the like may be added. The hydrophilic layer of the present invention has the above components dissolved in a solvent.
A solution that has been dissolved or dispersed is prepared and applied by coating.
As the main solvent of the hydrophilic layer coating liquid, water and methanol
Low boiling alcohols such as ethanol, ethanol and propanol
Are used alone or as a mixture. In the present invention, this main solvent is used for high printing durability.
Add solvent to dissolve lipophilic polymer in ink receiving layer
be able to. Such a solvent is disclosed in JP-A-2001.
The organic solvent as described in -180141 is mentioned. this
Good solvents of organic polymers are used for the ink receiving layer.
It is difficult to specify because it differs depending on the polymer, but generally
Are alcohols (ethylene glycol monomethyl ether
Tellurium, propylene glycol monomethyl ether, ethyl
Lenglycol monoethyl ether, etc.), ethers
(Tetrahydrofuran, ethylene glycol dimethyl ether
Ether, propylene glycol dimethyl ether, tet
Lahydropyran, etc.), ketones (acetone, methyl ethyl)
Luketone, methyl isobutyl ketone, acetylacetate
, Cyclohexanone, etc.), esters (methyl acetate,
Ethyl acetate, isobutyl acetate, ethylene glycol mono
Methyl monoacetate), amides (formamide,
N-methylformamide, pyrrolidone, N-methylpyro
Redone), gamma-butyrolactone, methyl lactate, milk
A solvent selected from ethyl acid and the like. A solution that dissolves the lipophilic polymer of the ink receiving layer.
The content of the agent is preferably 0. 0 of the total solvent of the hydrophilic layer coating solution.
4 to 40%. More preferably 0.4 to 20%
The The dry coating amount of the hydrophilic layer of the present invention is preferably
Is 0.2 to 0.8 g / m², More preferably 0.3 to
0.5g / m²It is. Within this range, low on-press developability
Good water retention of the hydrophilic layer without lowering or lowering sensitivity
Is obtained. The heat-sensitive lithographic printing plate precursor of the present invention is
Prevention, storage and handling
At times, the hydrophilic layer is contaminated or scratched by lipophilic substances or removed with bare hands.
Hydrophilic on the hydrophilic layer to prevent fingerprint traces when handling
An overcoat layer can be provided. Hydrophilic overcoat used in the present invention
The layer is removable on the printing press and is water soluble resin or
Is selected from water-swellable resins partially crosslinked with water-soluble resins
Contained resin. Such a water-soluble resin is a water-soluble natural polymer.
Selected from synthetic polymers and used with cross-linking agents
The dried film has a film forming ability. Specific examples of suitable water-soluble resins include natural
For polymers, gum arabic, water-soluble soybean polysaccharide, fiber
Derivatives (eg carboxymethylcellulose, carbo
Xylose cellulose, methyl cellulose, etc.)
Sexual body, white dextrin, pullulan, enzymatic degradation agent
For synthetic polymers such as tellurinated dextrin, polyvinyl
Lucol (polyvinyl acetate with a hydrolysis rate of 65% or more
), Polyacrylic acid, its alkali metal salts or
Min salt, polyacrylic acid copolymer, its alkali metal salt
Or amine salt, polymethacrylic acid, its alkali gold
Metal salt or amine salt, vinyl alcohol / acrylic acid
Copolymer and its alkali metal salt or amine salt,
Reacrylamide, its copolymer, polyhydroxyethyl
Acrylate, polyvinylpyrrolidone, and their copolymerization
Body, polyvinyl methyl ether, vinyl methyl ether
/ Maleic anhydride copolymer, poly-2-acrylamide
2-Methyl-1-propanesulfonic acid, its alkali
Metal salt or amine salt, poly-2-acrylamide
2-methyl-1-propanesulfonic acid copolymer,
You can list Lucari metal salt or amine salt.
The Depending on the purpose, two or more of these resins may be mixed
It can also be used. However, the present invention is not limited to these examples.
It is not limited to. Partially mount at least one water-soluble resin
When bridged and an overcoat layer is formed on the hydrophilic layer,
The bridge uses a reactive functional group of the water-soluble resin to crosslink the reaction.
It is done by responding. The cross-linking reaction is covalent
It may be cross-linked or ion-bonded cross-linked. Adhesion on the surface of the overcoat layer by crosslinking
But the handling is improved, but the crosslinking is too advanced
Then, the overcoat layer changes to oleophilic and appears on the printing press.
The overcoat layer is difficult to remove.
Partial crosslinking is preferred. The preferred degree of partial crosslinking is 25 ° C. in water.
When the plate for printing plate is immersed in 30 seconds to 10 minutes
Although the hydrophilic overcoat layer does not elute and remains, 1
Elution is observed at 0 minutes or longer. As the compound used for the crosslinking reaction,
Examples of known polyfunctional compounds having bridging properties include polyester
Poxy compounds, polyisocyanate compounds, polyarco
Xylyl compounds, polyvalent metal salt compounds, polyamine compounds
Products, aldehyde compounds, hydrazine, etc.
The crosslinking reaction may be promoted by adding a known catalyst.
it can. Ingredients of known polyfunctional compounds having crosslinkability
Examples of the body include the following compounds. Specific examples of the polyepoxy compound include
Resin polyglycidyl ether, polyethylene glycol
Diglycidyl ether, polypropylene glycol
Diglycidyl ether, trimethylolpropane polyg
Lysidyl ether, trimethylolpropane polyglycy
Dill ether, sorbitol polyglycidyl ether,
Bisphenols or their hydrogenated products and epiha
And polycondensates with rhohydrin. Specific examples of polyamines include ethylenediamine.
Amine, diethylenetriamine, triethylenetetrami
, Tetraethylenepentamine, hexamethylenediamine
, Propylenediamine, polyethyleneimine, polyamine
Examples include midamine. Specific examples of polyisocyanate compounds
Is tolylene diisocyanate, diphenylmethane iso
Cyanate, liquid diphenylmethane diisocyanate,
Polymethylene polyphenyl isocyanate, xylylene
Diisocyanate, naphthalene-1,5-diisocyanate
, Cyclohexane phenylene diisocyanate,
Sopropylbenzene-2,4-diisocyanate, etc.
Aromatic isocyanate, hexamethylene diisocyanate
Aliphatic isoforms such as sodium carbonate and decamethylene diisocyanate
Cyanate, cyclohexyl diisocyanate, isophor
Alicyclic diisocyanates such as long diisocyanate,
Polypropylene glycol / tolylene diisocyanate
And the like, and the like. As the silane compound, methyltrimethoxy
Sisilane, methyltriethoxysilane, ethyltriet
Xysilane, phenyltriethoxysilane, vinyltri
Ethoxysilane, γ-aminopropyltriethoxysila
N- (β-aminoethyl) -γ-aminopropyl
Limethoxysilane, γ-glycidoxypropyltrimeth
Xylsilane, γ-methacryloxypropyltrimethoxy
Silane, γ-mercaptopropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrime
Toxisilane, dimethyldimethoxysilane, dimethyldi
Ethoxysilane, diphenyldiethoxysilane, 3-chloro
Lolopropylmethyldimethoxysilane, vinyl tris
(Methylethylketoxime) silane, methyltris
(Methyl ethyl ketoxime) silane, vinyl triace
Toxisilane, etc. The titanate compound is tetraethyl.
Orthosilicate, Bis (dioctyl pyrophosphate)
G) Ethylene titanate, isopropyl reactor
Lucitanate, isopropyl dimethacryl isostearo
Il titanate, isopropyl isostaroyl diac
Ril titanate, isopropyl (dioctyl phosphate)
G) Titanate), Isopropyltricumylphenylthio
Titanate, isopropyltri (N-aminoethylamino)
Ethyl) titanate, dicumylphenyloxyacetate
To titanate, diisostearoyl ethylene titanate
, Isopropyl triinstearoyl titanate,
Sopropyltridodecylbenzenesulfonyl titanate
, Isopropyltris (dioctyl phosphate)
Titanate, tetraisopropylbis (dioctylphosphine
Wite) titanate, tetraoctylbis (ditridisi)
Rufosphite) titanate, tetra (2,2-diary)
Ruoxymethyl-1-butyl) bis (ditridecylphos)
Fight titanate, bis (dioctyl pyrophosphine
Oxyacetate titanate, bis (dioctyl)
Pyrophosphate) oxyacetate titanate
Do. As the aldehyde compound, formaldehyde
Hydride, acetaldehyde, propylaldehyde, butyl
Aldehyde, glyoxal, glutaraldehyde, te
Rephthalaldehyde, etc. Examples of polyvalent metal salt compounds include zinc and calcium
Um, magnesium, barium, strontium, edge
And water-soluble salts of metals such as
It is. These crosslinking agents may be used alone or in combination of two or more.
Can be used. Of these crosslinkers
Particularly preferred crosslinking agents are water-soluble crosslinking agents, but non-aqueous crosslinking agents.
Dissolve those that are soluble in water with a dispersant.
Can do. Particularly preferred combinations of water-soluble resin and crosslinking agent
As a combination, carboxylic acid-containing water-soluble resin / polyvalent metallization
Compound, carboxylic acid-containing water-soluble resin / water-soluble epoxy resin
Fats, hydroxyl group-containing resins / dialdehydes. The preferred addition amount of the crosslinking agent is that of the water-soluble resin.
0.5 to 10%. Within this range
Good water resistance without compromising the removability of the bar coat layer
Is obtained. In addition, uniform coating is applied to the overcoat layer.
In order to ensure the performance, it is mainly used for non-ionizing in the case of aqueous solution coating.
A surfactant can be added. Such non-i
Specific examples of on-surfactants include sorbitan tristearate.
Allate, sorbitan monopalmitate, sorbitant
Lioleate, stearic acid monoglyceride, polyoxy
Ethylene nonylphenyl ether, polyoxyethylene
A dodecyl ether etc. can be mentioned. Non-ionic surfactant overcoat
The proportion of the total solid in the layer is preferably 0.05 to 5%
That's right. Dry coating amount of the overcoat layer of the present invention
Is 0.1 to 4.0 g / m²Is preferable, 0.1-1.
0g / m²Is more preferable, 0.10 to 0.25 g / m²
Is particularly preferred. Within this range, over-press on the press
Ablation cartridges without impairing coat layer removal
Scratch prevention, good dirt and scratch prevention, and fingerprint marks
You can prevent wearing. Ink-receiving layer, hydrophilic layer and overcoat of the present invention
-At least one layer of the coat layer is used to increase sensitivity.
Therefore, it contains a photothermal conversion agent that converts light into heat.
The Photothermal conversion agents include infrared, especially near infrared (wave
Any material that absorbs 700-2000 nm in length)
Various known pigments, dyes or pigments, and metal fine particles
Can be used. For example, Japanese Patent Laid-Open No. 2001-301350,
Journal of Japan Society for Printing Science, 38 卷 35-40 (2001) “New
Imaging material, 2. `` Near infrared absorbing dye ''
Pigments, dyes or pigments, and fine metal particles are preferably used.
The Pigments and fine metal particles, if necessary, known surfaces
What gave the process can be used. More specifically, as a dye or pigment, rice
Japanese Patent Nos. 4756993 and 4975722, JP
10-268512, 11-235883, special public
JP-A-5-13514, JP-A-5-19702, JP-A-200
Cyanine dyes and polymethy described in No. 1-334765
Dye, azomethine dye, squarylium dye, piliri
Umum and thiopyrylium salt dyes, dithiol metal complexes
And phthalocyanine dyes. Especially preferred
Examples include cyanine dyes, squarylium dyes,
Examples include a lithium salt and a phthalocyanine dye. Examples of the pigment include insoluble azo pigments and azorays.
Pigment, condensed azo pigment, chelate azo pigment, phthalocyanine
Nin pigments, anthraquinone pigments, perylene and peri
Non pigment, thioindigo pigment, quinacridone face
, Dioxazine pigment, isoindolinone pigment, key
Nophthalone pigments, dyed lake pigments, azine pigments, ni
Toroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic face
Materials, carbon black, etc. can be used. Above all, carbon
Black is particularly preferred. As the metal fine particles, Ag, Au, Cu, S
Fine particles of b, Ge and Pb are preferred, Ag, Au and
Cu fine particles are more preferable. The addition ratio of the photothermal conversion agent is the parent ratio in the hydrophilic layer.
1-50% of solid content of water layer is preferable, overcoat layer
Then, the overcoat layer solid content is preferably 2 to 50%,
In the ink receiving layer, less than 20% of the solid content of the ink receiving layer
preferable. Within these ranges, the film strength of each layer must be impaired.
And good sensitivity can be obtained. [0103] The heat-sensitive lithographic printing plate precursor of the present invention is
More images are formed. Specifically, with a thermal recording head, etc.
Direct image-like recording, infrared laser scanning exposure,
High intensity flash exposure such as non-discharge lamps and infrared lamps
Exposure is used, but with a wavelength of 700-1200 nm
Solids such as semiconductor lasers and YAG lasers that emit infrared light
Exposure with a high-power infrared laser is preferred. The original plate for printing plate of the present invention which has been image-exposed is
Can be installed in a printing press without further processing.
When you start printing with ink and fountain solution,
The coating layer is removed by the fountain solution and at the same time the parent of the exposed area.
The water layer is also removed, and ink is deposited on the ink receiving layer below it.
Then printing starts. [0105] The present invention will now be described in detail with reference to examples.
However, the present invention is not limited to these. Example 1 [Production of aluminum substrate] Aluminum 99.5%
And 0.01% copper, 0.03% titanium and 0.3% iron.
%, JISA1050 aluminum containing 0.1% silicon
400mm mesh of 0.30mm thick rolled steel sheet
20% aqueous suspension and rotation of Pamiston (made by Kyoritsu Ceramics)
Using a nylon brush (6,10-nylon)
After the surface was grained, it was thoroughly washed with water. 15
% Sodium hydroxide aqueous solution (including aluminum 4.5%
So that the dissolution amount of aluminum is 8 g / m.²Nina
After etching so that it was washed with running water. In addition, 1
Neutralize with an aqueous solution of nitric acid followed by a 0.7% aqueous solution of nitric acid (Al
Minium 0.5%), anode voltage 10.5V,
Square wave alternating waveform voltage (current ratio r =
0.90, described in the example of Japanese Patent Publication No. 58-5796
240 C / dm using current waveform)²When anode
Electrolytic surface roughening treatment was performed with the amount of electricity. After washing with water, 1
Aluminum immersed in 0% sodium hydroxide aqueous solution
Dissolved amount is 0.9g / m²Etched to be
After washing with water. Next, in 50 ° C, 30% sulfuric acid aqueous solution
After soaking and desmutting, it was washed with water. Further, a sulfuric acid 9% aqueous solution (aluminum at 53 ° C.)
Porous anodic acid using DC current
Chemical film formation treatment was performed. That is, the electrolysis time is 33 seconds.
By adjusting the current density, the amount of anodized film 3.7g
/ M²It was. Then washed with water, dried and aluminum substrate
Got. The center line average roughness Ra of the obtained substrate was 0.53.
It was μm. [Preparation of heat-sensitive lithographic printing plate precursor] Methyl
Ethyl ketone 13.5g, propylene glycol monomer
A photothermal conversion agent in a mixed solvent of 27.0 g of tilether
(IR-1 below) 0.3 g, Epicoat 1009 (Epo)
1.2 g, Epi (resin made by Japan epoxy resin)
Coat 1001 (epoxy resin, Japan epoxy cash register
After dissolving 0.3 g, the above aluminum group
The amount of coating solution on the plate is 12cm^Three/ M²Bar coater to be
It was applied with. Then, heat dry at 100 ° C for 1 minute and dry
Dry coating amount 0.42 g / m²An ink receiving layer was obtained. Next, 19.4 g of methanol, methyl lactate
In a mixed solvent consisting of 0.1 g, methanol silica sol
(Methano containing 30% silica particles of 10-20 nm
3.0g
Followed by polyacrylic acid (weight average molecular weight 25
10,000, manufactured by Wako Pure Chemical Industries, Ltd.)
The amount of coating solution on the receiving layer is 12cm^Three/ M²Barco to be
It was applied with a filter. Then, heat drying at 100 ° C for 1 minute
The dry coating amount is 0.40 g / m²A hydrophilic layer was obtained. [0110] On the hydrophilic layer, 28% water of Arabica gum
1.5 g of solution, photothermal conversion agent (IR-2 below) 0.04
2 g and Emalex # 710 (surfactant, Nippon E
0.168 g of 10% aqueous solution of Marujon)
10% aqueous solution of nesium tetrahydrate (Wako Pure Chemical Industries)
An aqueous solution composed of 0.03 g and water 30.06 g
Is 12cm^Three/ M²10 after coating with a bar coater
Dry by heating at 0 ° C. for 1.5 minutes, dry coating amount 0.15 g /
m²An overcoat layer is provided for the heat-sensitive lithographic printing plate
A plate was made. [0111] [Chemical 1] [Exposure and Printing Evaluation] For the above-described planographic printing plate
Trend setter 3 made by CreoScitex
Attach to 244VX, 240mJ / cm²Energy of
A latent image was formed by irradiation. The plate surface after exposure is
There is almost no evidence of splattering
There wasn't. Next, the original plate on which the latent image is formed is Heidelberg.
Installed on a SOR-M printing machine manufactured by Co., Ltd., 4 volume% IF102
Dampening water and GEO (made by Fuji Photo Film)
Mark using S-G (N) black ink (Dainippon Ink Chemical)
When printed, overcoat with 20 prints
The layer and the exposed hydrophilic layer were removed. Continue printing 2
A good print with no smudges was obtained. Comparative Example 1 Anodized skin by adjusting the current density of the anodized film formation treatment
The film amount is 2.0 g / m²Using an aluminum substrate
Except for the above, as in Example 1, the production of a heat-sensitive lithographic printing plate
Made. Exposure / printing evaluation was performed in the same manner as in Example 1.
B) Ink on the image area even after 1000 sheets have been printed
Did not get meat. Scanning electron microscope for image area of printing plate
As a result of observation with the ink, the hydrophilic layer partially remains and the ink
It was found that the receptive layer was not sufficiently exposed. Imprint 2
In order to obtain a good print with about 0 sheets, the exposure energy must be
270 mJ / m²It was necessary to raise it. Comparative Example 2 Anodized skin by adjusting the current density of the anodized film formation treatment
The film amount is 6.0 g / m²Using an aluminum substrate
Except for the above, as in Example 1, the production of a heat-sensitive lithographic printing plate
After making and exposure / printing evaluation, 1
Even after passing 000 sheets, the ink did not adhere to the image area.
As a result of observing the image area of the printing plate with a scanning electron microscope,
The water layer remains partially and the ink receiving layer is fully exposed
I understood that it was not. Good mark with about 20 printed
To obtain a printed material, the exposure energy is 270 mJ / m.²In
It was necessary to raise. From the above results, the heat-sensitive lithographic printing of the present invention.
The original plate is highly sensitive and is free from scraps due to ablation.
Scattering is prevented, stain resistance in printing is good, and high printing durability
I understand that there is. [0117] According to the present invention, it is based on a digital signal.
Plate making by scanning exposure is possible.
It can be installed directly on the printing machine without any trouble and printed.
Laser exposure equipment and light by scattering of ablation residue
Source contamination is prevented, high sensitivity, excellent resistance to contamination, and
In addition, it is possible to provide a heat-sensitive lithographic printing plate precursor having a high printing durability.

Continued front page    F-term (reference) 2H025 AA01 AA12 AB03 AC08 AD01                       AD03 CC20 DA01 DA18 DA20                       DA36 DA37 FA10                 2H096 AA07 AA08 BA16 CA03 CA05                       CA20 EA04 LA16                 2H114 AA04 AA22 AA23 AA27 AA28                       AA30 BA02 BA10 DA04 DA08                       DA75 EA01 EA03 EA05 EA08                       FA01 GA01 GA09 GA34

Claims (1)

What is claimed is: 1. An aluminum substrate having a roughened anodized film, wherein (1) an ink receiving layer, (2) beryllium, magnesium, aluminum, silicon, titanium,
Hydrophilic layer containing colloidal particulate oxide or hydroxide of at least one element selected from boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metals, and (3) removable on printing press A heat-sensitive lithographic printing plate precursor having a hydrophilic overcoat layer in this order, and a dry coating amount of the ink receiving layer of 0.5
less than g / m ^2, the amount of anodized film 3.0 g / m ² or more, heat-sensitive lithographic printing plate original plate and less than 5.0 g / m ^2.