JP2001322363A - Lithographic printing plate and method for preparing it and method for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing plate with good image reproducibility and plate wear and a method for preparing it and a method for printing. SOLUTION: The lithographic printing plate is characterized by containing a substance which generates an active species performing a bonding reaction with a substrate by light on the substrate and having a recording layer wherein hot-melt particles which are not capsule particles containing a substance which is liquid at room temperature in their cores are main ingredients.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate, a method for producing the lithographic printing plate, and a printing method.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 55-22791 describes a photosensitive composition containing a photosensitive diazonium salt and latex particles as main components, but these materials are simply mixed with a binder to coexist. And there is a problem with stability upon storage. Japanese Patent Application Laid-Open No. 9-290146 describes microcapsules containing an aqueous solution containing a water-soluble compound such as a diazonium salt. However, a configuration that does not contain a substance that is liquid at room temperature such as water is not described.

Japanese Patent No. 2938397 discloses that a lithographic printing plate having a recording layer provided on a hydrophilic layer is exposed, and the unexposed portion of the recording layer is treated with a treating agent (fountain solution or printing ink) used for printing. Although a method for removing the material is disclosed, since the material of the recording layer that cannot be removed by the processing agent for printing remains in the hydrophilic layer, there is a problem that stains in printing are likely to occur due to this. is there.

Further, Japanese Patent No. 2938397 also describes a lithographic printing plate in which a recording layer recordable with a laser is provided on the anodized surface of an aluminum plate. However, since the thermal conductivity of the aluminum plate is good, there is a problem that energy required for image recording is not sufficiently transmitted to the recording layer and sensitivity is extremely low.

JP-A-10-282679 discloses a lithographic printing plate in which a photopolymerizable recording layer is coated on a support using a silane coupling agent having an addition-polymerizable ethylenic double bond as an intermediate layer. Is described. However, among them, radically polymerizable cation silane coupling agents of different types and classifications are mixed, and there is no description of what is particularly good.

Japanese Patent Application Laid-Open No. 11-327157 discloses an example in which a lithographic printing plate having a recording layer containing a microgel and an infrared dye is exposed to light, and then a cover sheet is peeled and developed to be used as a printing plate. However, since the operation of peeling and developing the cover sheet is performed after the exposure, unlike the present application in which the cover sheet is attached to a printing cylinder of a printing machine without any processing and printing is performed, the number of operation steps is complicated.

JP-A-10-69089 discloses a first layer containing a water-soluble polymer, a photothermal conversion agent, a photoacid generator, a compound cross-linked by an acid such as a resol resin on a hydrophilic support,
Further, a lithographic printing plate is disclosed in which a second layer containing a compound crosslinked by an acid such as a novolak resin, a photothermal conversion agent, a photoacid generator, and a resol resin is provided thereon. Then, a method of attaching and printing to a printing machine without any processing after exposure is also disclosed, but there is a problem that if heat treatment is not performed after exposure, printing durability is insufficient.

Japanese Patent Application Laid-Open No. 11-30852 discloses a lithographic printing plate having a priming layer, a recording layer containing a sensitizing dye, and a silicone layer in this order, which is exposed to light and then subjected to a water development treatment to eliminate fountain solution. Although a plate is disclosed, there is no description about a method of performing printing by attaching to a printing cylinder of a printing press without any processing after exposure.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lithographic printing plate having good image reproducibility and printing durability, a method for producing the same, and a printing method.

[0010]

The above objects of the present invention have been attained by the following constitutions.

1. On the support, a recording layer mainly containing heat-meltable particles that are not capsule-shaped particles containing a liquid substance at room temperature and contain a substance that generates an active species that undergoes a binding reaction with the support by light on the core. A lithographic printing plate characterized by having:

2. A lithographic printing plate having a porous hydrophilic layer and a recording layer on a hydrophilic support is subjected to image recording with light, and then the non-image area of the porous hydrophilic layer and the recording layer are treated with a treating agent used during printing. A method for preparing a lithographic printing plate, comprising removing the surface of a hydrophilic support to expose the surface.

3. A support for a lithographic printing plate, characterized in that a pore of an anodized aluminum film contains a metal having absorption in the visible and infrared regions.

4. A lithographic printing plate comprising a silane coupling agent having a cationic polymerizable group between a support and a recording layer.

[0015] 5. 5. The lithographic printing plate as described in 4 above, wherein the recording layer contains a compound that generates an acid by light or heat.

6. A printing method characterized in that a lithographic printing plate having a recording layer containing a microgel and an infrared dye is exposed, attached to a printing cylinder of a printing machine without any treatment, and printing is performed.

[7] 7. The printing method according to the above item 6, wherein the microgel is a water-dispersible microgel having a quaternary salt structure.

[8] After exposing a lithographic printing plate having a water-soluble photosensitive material, a recording layer containing an infrared dye, and a water-permeable lipophilic layer on the support in this order, attached to a printing cylinder of a printing machine without any processing, A printing method characterized by performing printing.

9. After exposure of a lithographic printing plate having a primer layer, a recording layer containing an infrared dye, and a silicone layer on a support in this order, the lithographic printing plate is attached to a printing cylinder of a printing machine without any treatment, and printing is performed. Printing method.

Hereinafter, the present invention will be described in more detail. The support used in the lithographic printing plate precursor according to the invention preferably has hydrophilicity, and examples thereof include an aluminum plate that has been electrochemically and / or mechanically polished and anodized. Specifically, it is an aluminum plate whose surface is grained, anodized, and sealed. Examples of a method of graining an aluminum plate include a mechanical method and a method of etching by electrolysis. Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The above-mentioned various methods can be used alone or in combination depending on the composition of the aluminum material and the like. Preferred is a method by electrolytic etching. The electrolytic etching is performed in a bath containing one or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining treatment, if necessary, a desmut treatment is carried out with an aqueous solution of an alkali or an acid to neutralize and wash with water. The anodic oxidation treatment is performed by using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, or the like as an electrolytic solution and performing electrolysis using an aluminum plate as an anode. The formed anodized coating amount is 1
５０50 mg / dm ² is suitable, preferably 10-4
0 mg / dm ² . Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to an undercoating treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorozirconic acid. The hydrophilic support has a contact angle of water on its surface of 60 degrees or less, more preferably 40 degrees or less. A support having a hydrophilicity having a thickness in the range of 50 to 1000 μm, preferably 75 to 500 μm can be suitably used. The surface roughness is the center line surface roughness Ra.
In a range of 0.2 to 0.6 μm and a maximum roughness Rz of 3.0.
It is preferably in the range of 6.0 to 6.0 μm.

The inclusion of metal in the pores of the support according to claim 3 will be described. The metal is not particularly limited as long as it has absorption in the visible and infrared regions, and examples thereof include tin, indium, copper, zinc, bismuth, silver, lead, and iron.

The inclusion of metal in the pores of the support may be performed by a known method.
For example, AgX (X: Cl, Br,
I), Ag_TwoWO_Four, AgMoO_Four, Ag_ThreeN_Three, AgCN
O, CuX (X: Cl, Br, I), Cu_TwoC_Two, Pb
S, FeCl_Three, Fe_Two(C_TwoO_Four) _ThreeEtc. inside the pore
And irradiate it with light to precipitate the metal.
Can be

Silver halide is preferably used. First, when an aqueous solution of a halogen salt is impregnated in a pore and a silver nitrate solution is penetrated therein, hardly soluble silver halide fine particles are generated in the pore. When this is irradiated with light and treated with an aqueous solution of a reducing agent, metallic silver is formed in the pores.

In another embodiment, a hydrophilic binder and / or a phase composed of highly hydrophilic particles such as colloidal silica capable of self-enhancement can be crosslinked as necessary to form a hydrophilic support. One having a conductive layer formed thereon. Examples of the hydrophilic binder constituting the hydrophilic layer include hydrophilic (co) polymers such as vinyl alcohol, acrylamide, methylolacrylamide, methylolmethacrylamide,
A homopolymer or copolymer of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, or a maleic acid / vinyl methyl ether copolymer can be used. Examples of the highly hydrophilic particles capable of self-thickening include colloidal silica, alumina particles, particles of titanium oxide or other heavy metal oxides, and the like. As a crosslinking agent for crosslinking the hydrophilic binder, formaldehyde, glyoxal, polyisocyanate, hydrolyzed tetra-alkyl orthosilicate, and the like can be used. The hydrophilic layer has an average particle diameter of 0.1 to 5 μm for imparting mechanical strength, improving water retention, and imparting appropriate unevenness.
m may be contained. Known particles such as silica, alumina, calcium carbonate, titanium oxide, calcium alginate particles, and crosslinked particles of polymethyl methacrylate can be used as the particles.

As the flexible support, a plastic film, for example, a saturated polyethylene terephthalate film, a polyethylene naphthalate film, a cellulose acetate film, a polystyrene film, a polycarbonate film and the like, and a paper support can also be used. These flexible supports may be provided with an undercoat layer for improving the adhesion of the hydrophilic layer.

As the support of the second aspect, in addition to the above-mentioned support, a known material used as a substrate of a printing plate can be used. For example, a metal plate, a plastic film, paper treated with a polyolefin or the like, a composite base material to which the above materials are appropriately bonded, and the like can be given. The thickness of the support is not particularly limited as long as it can be attached to a printing machine, but a thickness of 50 to 500 μm is generally easy to handle.

Examples of the metal plate include iron, stainless steel, aluminum and the like, and aluminum is particularly preferable from the relationship between specific gravity and rigidity. As plastic films, polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate,
Examples thereof include polysulfone, polyphenylene oxide, and cellulose esters. Particularly, polyethylene terephthalate and polyethylene naphthalate are preferred.

In order to improve the adhesiveness of the plastic film to the coating layer, it is preferable to apply an easy-adhesion treatment or an undercoating layer to the coating surface. As easy adhesion processing,
Examples include corona discharge treatment, flame treatment, and ultraviolet irradiation treatment. Examples of the undercoat layer include layers containing gelatin and latex.

As the composite support, the above-mentioned materials may be used by appropriately bonding them together, but may be bonded before forming the image forming layer, or may be bonded after forming the image forming layer. Alternatively, they may be bonded just before being attached to a printing machine.

The photoacid generator, which is a substance that generates active species by light, used in the present invention is disclosed in JP-A-59-18.
0543, JP-A-59-148784, JP-A-60-148
Organic halogen compounds described in JP-B-138439, JP-B-60-27673, JP-B-49-21601, JP-A-63-58440, JP-B-57-1819 and the like; JP-B-54-14277. , Tokiko 54-1
No. 4278, JP-A-51-56885, U.S. Pat. No. 3,708,296, and U.S. Pat. No. 3,835,0.
A diazonium salt, an iodonium salt, and a sulfonium salt described in JP-A No. 02 and the like can be used. Of these photoacid generators, more preferred is JP-A-59-1984.
No. 180543, No. 59-148784, No. 60-1
No. 38539, Japanese Patent Publication No. 60-27673 and Japanese Patent Application Laid-Open No. Sho.
Trihaloalkyl compounds and halomethyltriazine compounds described in JP-A-3-58440.

Examples of the compound which generates a base by light or heat include salts of a carboxylic acid and an organic base. Base precursors comprising salts of carboxylic acids and organic bases are disclosed in U.S. Pat. No. 3,493,374, British Patent No. 998,949, and JP-A-59-1805.
No. 37, JP-A-61-51139, and U.S. Pat. No. 4,060,420 can be used. These base precursors composed of a salt of a carboxylic acid and an organic base are configured to release the organic base when used (when heated).

As the compound capable of generating a radical by light or heat, those conventionally known as photopolymerization initiators can be used.
For example, benzoin, benzoin alkyl ether, benzophenone, anthraquinone-based compounds, Michler's ketone, trihalomethyl-s-triazine compounds, oxadiazole-based compounds, biimidazole-based compounds, thioxanthone-based compounds, and aromatic tertiary amines are all suitable. Can be used. These radical generators can be used alone or in combination of two or more. For specific examples and preferred combinations of these radical generators, see "UV / EB Curing Handbook-
Raw Materials-pp. 67-73 of "Kato Kiyomi" (Polymer Publishing Association), "Applications and Markets of UV / EB Curing Technology", supervised by Yoneho Tabata, edited by Radotech Research Group (CMC), pp. 64-82. Page, JP-B-6-42074, JP-A-62-61044, JP-A-60-35
No. 725 and JP-A-2-28747.

The heat-fusible particles preferably used in the present invention which can be fused by heat include waxes, acrylic resins, ionomer resins, vinyl acetate resins, vinyl chloride resins, synthetic rubbers, polyurethane resins and polyesters. Examples thereof include those obtained from a latex or an emulsion dispersed in water such as a resin, a fluorine-based resin, and a silicone resin. Among them, the average particle size is 1.0 μm or less,
The melting point is preferably 70 to 180 ° C., and the hydrophilic component of the surface energy is preferably 1 × 10 ⁻⁴ N / cm ² or less. When the melting point is lower than this temperature, the performance during storage tends to deteriorate, and when it is higher than this temperature, the strength of the image cannot be obtained and the printing durability tends to deteriorate. Further, when the surface energy is within this range, the ink deposition property of the image area becomes good. The hot-melt particles of the present invention may be capsule-shaped particles or simple particles. However, in the case of capsule-like particles, the core does not contain a substance that is liquid at room temperature. In such a point, as the heat-fusible substance, waxes,
Acrylic resins and synthetic rubbers are particularly preferred.

The waxes usable in the present invention include carnauba wax, beeswax, whale wax, wood wax, jojoba oil,
Natural waxes such as lanolin, ozokerite, paraffin wax, montan waxes, candelilla wax, ceresin wax, microcrystalline wax, rice wax, polyethylene wax, Fischer-Tropsch wax, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, high-grade Fatty acids and the like. Further, these waxes may be oxidized to facilitate emulsification, and polar groups such as a hydroxyl group, an ester group, a carboxyl group, an aldehyde group and a peroxide group may be introduced.

Examples of the acrylic resin usable in the present invention include copolymers containing acrylate and methacrylic acid as essential components. Examples thereof include methyl methacrylate, butyl acrylate, octyl acrylate, and acrylic acid. Those obtained by copolymerizing at least one or more of 2-ethylhexyl, styrene and the like can be mentioned.

The synthetic rubbers usable in the present invention include:
Polybutadiene, polyisoprene, polychloroprene,
Styrene-butadiene copolymer, acrylate-
Butadiene copolymer, methacrylate-butadiene copolymer, isobutylene-isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, and styrene-isoprene copolymer.

The recording layer containing the heat-fusible particles which can be fused by heat is provided with a hydrophilic binder in order to impart the film properties of the recording layer within a range which does not hinder the fusion property of the particles during laser exposure. May be contained. Available hydrophilic binders include, for example, polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylamide, polyhydroxyethyl (meth) acrylate, polyvinyl methyl ether, or natural binders such as gelatin, polysaccharides Such as dextran, pullulan, cellulose, gum arabic,
Arginic acid. Further, the hydrophilic binder may be a water-insoluble, alkali-soluble or swellable resin having a phenolic hydroxy group and / or a carboxyl group. Various surfactants, colloidal silica, and the like can also be used.

As a substance which exhibits lipophilicity by heat, a heat-meltable substance having a melting point of 70 to 180 ° C. can be used. For waxes, carnauba wax, beeswax, whale wax, wood wax,
Natural waxes such as jojoba oil, lanolin, ozokerite, paraffin wax, montan waxes, candelilla wax, ceresin wax, microcrystalline wax, rice wax, polyethylene wax,
Fischer-Tropsch wax, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, higher fatty acids, etc., in the case of acrylic resins, for example, methyl methacrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, styrene, etc. Or those obtained by copolymerizing two or more kinds, and in synthetic rubbers, polybutadiene, polyisoprene, polychloroprene, styrene-butadiene copolymer, acrylate-butadiene copolymer, methacrylate-butadiene copolymer, Examples thereof include an isobutylene-isoprene copolymer, an acrylonitrile-butadiene copolymer, an acrylonitrile-isoprene copolymer, and a styrene-isoprene copolymer. In addition, an ionomer resin, a vinyl acetate resin, a vinyl chloride resin, a polyurethane resin, a polyester resin, a fluorine resin, a silicone resin and the like can be used. These lipophilic agents are preferably used in the form of an aqueous dispersion from the viewpoint of easy coating. Further, as another form, a thermal crosslinking agent covered with a heat-destructible hydrophilic coating material and a thermal crosslinking agent in which a functional group is blocked by a protective group dissociated by heat can be mentioned. These thermal crosslinking agents are described in JP-A-7-1849 and JP-A-7-1849.
No. 1850, No. 9-31443, No. 10-646
No. 8 and No. 10-1141168 are described as lipophilic components microencapsulated.

In the present invention, as a method for producing the heat-fusible particles, for example, there is the following method.

1) A hot-melt substance and a substance that generates active species or a developer are melt-mixed under heating, and the molten mixture is dropped into warm water, and then strongly stirred using a stirrer, a homogenizer, or the like. Or a method of reducing the particle size through a small-diameter hole.

According to these methods, since the solvent is water, the mixed hydrophilic agent is localized on the particle surface and fixed to the particles.

2) A substance capable of generating an active species or a color developer is dissolved and dispersed in warm water in advance, and the melted heat-meltable substance is dropped and stirred vigorously, and the heat-meltable substance simply coated with a hydrophilic agent is applied. After preparing an aqueous dispersion of the above, the surface of the heat-fusible substance was softened by further heating and stirring the hydrophilic dispersion.
A method of fixing a hydrophilic agent by causing mixing at the interface of hot-melt particles.

The average particle size of the heat-meltable particles is 0.1 to
It is preferably 10 μm, more preferably 0.1 to 1.5 μm.

The material constituting the hydrophilic layer is not particularly limited as long as it has sufficient ability to retain dampening water so as not to cause soiling at the time of printing. It is preferable that the porous layer is a porous hydrophilic layer formed by using metal oxide fine particles, a binder, an additive and the like.

Examples of the inorganic particles exhibiting hydrophilicity include:
Silica particles, aluminosilicate particles, zeolite particles, titanium oxide and kaolinite, halloysite, chrysotile, talc, smectite (montmorillonite,
Clay minerals such as beidellite, hectorite, savonite, etc.), vermiculite, mica (mica), chlorite, and layered mineral particles such as hydrotalcite, layered polysilicate (kanemite, macatite, aialite, magadiite, kenyaite, etc.) And among these, porous particles are preferably used.

The porous silica particles are generally produced by a wet method or a dry method. In the wet method, it can be obtained by drying and pulverizing a gel obtained by neutralizing a silicate aqueous solution, or by pulverizing a precipitate precipitated by neutralization. In the dry method, it is obtained by burning silicon tetrachloride together with hydrogen and oxygen to precipitate silica. The porosity and particle size of these particles can be controlled by adjusting the production conditions. As the porous silica particles, those obtained from a gel obtained by a wet method are particularly preferable.

The porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, it is an amorphous composite particle synthesized by a hydrolysis method using aluminum alkoxide and silicon alkoxide as main components. It is possible to synthesize the particles in a ratio of alumina to silica in the range of 1: 4 to 4: 1. Further, those prepared as composite particles of three or more components by adding an alkoxide of another metal during the production can also be used in the present invention. The porosity and particle size of these composite particles can also be controlled by adjusting the production conditions.

Zeolite is a crystalline aluminosilicate, and is a porous material having pores of a regular three-dimensional network structure having a pore diameter of 0.3 to 1 nm. The general formula combining natural and synthetic zeolites is as follows:

(M^I, M^II ₁/_Two)_m(Al_mSi
_nO_Two(_{m + n})) XH_TwoO where M^I, M^IIIs an exchangeable cation and M^IIs
Li⁺, Na⁺, K⁺, Tl⁺, Me_FourN⁺(TMA), Et
_FourN⁺(TEA), Pr_FourN⁺(TPA), C₇H _FifteenN_Two ⁺,
C₈H₁₆N⁺And M^IIIs Ca²⁺, Mg²⁺, Ba²⁺,
Sr²⁺, C₈H_{1 8}N_Two ²⁺And so on. Note that m is a positive number equal to or less than n.
N is a positive integer greater than or equal to m, that is, n ≧ m
And x represents any positive integer.

The porous particles can be used by being dispersed and crushed in advance, or crushed and used in the process of being dispersed simultaneously with other materials of the coating layer. Similarly, the layered mineral particles can be used after being dispersed and crushed / peeled, or crushed / peeled in the process of being dispersed simultaneously with other materials of the image forming layer.

The dispersion crushing or delamination of particles can be roughly classified into a dry type and a wet type. Dry dispersion crushing does not require a drying step, so the process is relatively simple, but dispersion crushing to the order of submicron and 100n
For delamination up to a layer thickness of less than m, the wet method is usually more advantageous.

Examples of the dry dispersing and crushing apparatus include a high-speed rotary shock-shear mill (for example, an annular type inomaizer), an air-flow crusher (jet mill), a roll mill,
A dry medium stirring mill (for example, a ball mill), a compression shearing type pulverizer (for example, an ang mill) and the like can be used.

As a wet dispersion and crushing apparatus, a wet medium stirring mill (for example, a ball mill and an aquamizer), a high-speed rotating shear friction type mill (for example, a colloid mill) and the like can be used.

The particle size of the porous particles after dispersion and crushing is preferably substantially 1 μm or less, more preferably 0.5 μm or less. If coarse particles remain, they may be removed by classification or filtration.

Further, in the above-mentioned dispersion crushing or dispersion layer peeling step, a surface treatment can be performed on the particles by adding a surface treatment agent. Further, in the dispersion crushing or dispersion layer peeling step, other components to be added to the coating solution may be added and dispersed simultaneously, or after the dispersion crushing or dispersion layer peeling step, the other components may be added to the coating solution. May be added and dispersed again. In the dispersion crushing or dispersion layer peeling step, it is considered that a mechanochemical reaction occurs at the same time, and when dispersed simultaneously with other components to be added to the coating liquid, an effect of improving strength when a coating film is obtained is obtained. There are cases.

The porosity of the particles is preferably 0.5 ml / g or more in terms of pore volume before dispersion.
0.8 ml / g or more, more preferably 1.0 ml / g or more.
More preferably, it is not more than 2.5 ml / g.

Although the pore volume is closely related to the water retention of the coating film, the larger the pore volume, the better the water retention, the less the stain during printing, and the wider the water latitude.
If it is larger than 5 ml / g, the particles themselves become very brittle and the durability of the coating film is reduced.

If the pore volume is less than 0.5 ml / g, it is difficult to stain during printing and the width of the water volume latitude is insufficient. The particle size is substantially 1 when contained in the image forming layer (including the case where the particles have undergone the dispersion crushing step).
μm or less, and more preferably 0.5 μm or less. When coarse particles are present, porous and steep projections are formed on the surface, and ink is likely to remain around the projections, thus deteriorating non-image area stains.

The content of the porous particles is 3% of the entire image forming layer.
It is preferably from 0 to 95% by mass, and more preferably from 40 to 80% by mass.

Examples of the metal oxide fine particles having an average particle diameter of 100 nm or less include colloidal silica, alumina sol, titania sol, and other metal oxide sols. The form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form. The average particle size is 3 to 1
It is preferably 00 nm, and several kinds of metal oxide fine particles having different average particle diameters can be used in combination. Further, the surface of the particles may be subjected to a surface treatment.

The metal oxide fine particles can be used as a binder by utilizing the film forming property. Of these, colloidal silica is particularly preferred because of its high film-forming properties even under relatively low-temperature drying conditions.

In the case of colloidal silica, the smaller the particle size, the stronger the bonding force. When the particle diameter is larger than 100 nm, the bonding force is greatly reduced, and when used as a binder, the strength is insufficient.

When these metal oxide fine particles are used together with the porous silica particles, it is preferable to use them in a state where the fine particles themselves have a positive charge. For example, it is preferable to use alumina sol or acidic colloidal silica. . When these metal oxide fine particles are used together with porous aluminosilicate particles and / or zeolite particles, it is preferable to use them in a state in which the fine particles themselves have a negative charge, for example, using alkali colloidal silica. Is preferred. When used together with the porous silica particles and the porous aluminosilicate particles and / or zeolite particles, it is preferable to use, for example, colloidal silica whose surface is treated with Al to provide stability in a wide pH range.

In addition to the above components, a binder or an additive may be contained. As the organic binder, those having hydrophilicity are preferred. For example, proteins such as casein, soy protein, and synthetic protein, chitins, starches, gelatins, alginates, polyvinyl alcohol, silyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, methyl cellulose, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose. , Polyethylene oxide, polypropylene oxide, polyethylene glycol, polyvinyl ether, styrene-butadiene copolymer, conjugated diene polymer latex of methyl methacrylate-butadiene copolymer, acrylic polymer latex, vinyl polymer latex, polyacrylamide, Polyvinylpyrrolidone and the like.

Further, a cationic resin may be contained. Examples of the cationic resin include polyalkylene polyamines such as polyethylene amine and polypropylene polyamine and derivatives thereof, acrylic resins having a tertiary amino group and a quaternary ammonium group, and diacrylamine. The cationic resin may be added in the form of fine particles. This includes, for example, a cationic microgel described in JP-A-6-161101.

Further, a crosslinking agent may be added. Examples of the crosslinking agent include melamine resins, isocyanate compounds, isoxazoles, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, and the like.

An aqueous silicate solution can also be used as the inorganic binder. Alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate are preferable, and the SiO ₂ / M ₂ O ratio thereof is in a range where the pH of the entire coating solution when the silicate is added does not exceed 13. It is preferable to select as follows (to prevent dissolution of the inorganic particles).

Further, as the binder, an inorganic polymer or an organic-inorganic hybrid polymer by a so-called sol-gel method can be used. The formation of the inorganic polymer or the organic-inorganic hybrid polymer by the sol-gel method is described in, for example, “Application of the Sol-Gel Method” (written by Shio Sakuhana / published by Agne Shofusha Co., Ltd.) or cited in this document. The known method described in the literature described can be used.

The silane coupling agent having a cationically polymerizable group which can be preferably used in the present invention includes:
For example, a compound represented by the following general formula (I) can be mentioned.

Formula (I) Ra (Rb) SiRc (Rd) In the formula, at least two of Ra to Rd represent an alkoxy group or a -OCOR 'group having 10 or less carbon atoms, and the others represent cationic polymerizable groups. , R 'represent an alkyl group.

The alkyl group represented by R 'in the formula (I) includes, for example, a methyl group, an ethyl group and a propyl group, and the addition-polymerizable reactive group includes an alkenyl group, an alkynyl group and the like. Various linking groups may be bonded between the Si element and the addition polymerizable reactive group. Examples of the alkenyl group include a vinyl group,
Examples include a propenyl group, an allyl group, a butenyl group, and a dialkylmaleimide group. Examples of the alkynyl group include an acetylene group and an alkylacetylene group.
Examples of the silane coupling agent include [Silane Co.
[uplingAgents] (Edwin P. Plu
eddemann, Pleum Press, 198
2) and the like. _{Specifically, CH 2 = CH-Si (} OCOCH 3) 3 CH 2 = CH-Si (OC 2 H 5) 3 CH 2 = CH-Si (OCH 3) 3 CH 2 = CHCH 2 -Si (OC 2 _{H 5) 3 CH 2 = CHCH} 2 NH (CH 2) 3 -Si (OCH 3) 3 CH 2 = CHCOO- (CH 2) 3 -Si (OCH 3) 3 CH 2 = CHCOO- (CH 2) 3 - _{Si (OC 2 H 5) 3} CH 2 = CHCOO- (CH 2) 4 -Si (OCH 3) 3 CH 2 = C (CH 3) COO- (CH 2) 3 -Si (OCH
₃ ) ₃ CH ₂ ＣC (CH ₃ ) COO— (CH ₂ ) ₃ —Si (OC _{2
H 5) 3 CH 2 = C} (CH 3) COO- (CH 2) 4-Si (OC
_{H 3) 3 CH 2 = C} (CH 3) COO- (CH 2) 5 -Si (OCH
_{3) 3 (CH 2 = C} (CH 3) COO- (CH 2) 3) 2 -Si
_{(OCH 3) 2 CH 2 =} C (CH = CH 2) -Si (OCH 3) 3 CH 2 = CH-SO 2 NH- (CH 2) 3 -Si (OC
_{H 3) 3 CH 2 = CH} -ph-O-Si (OCH 3) 3 (ph: shows a benzene _{ring) CH 2 = CH-ph-} CONH- (CH 2) 3 -Si (O
_{CH 3) 3 CH 2 = CH} -ph-CH 2 NH- (CH 2) 3 -Si (O
_{CH 3) 3 CH 2 = CH} -ph-CH 2 NH-C 2 H 4 NH (CH 2) 3
-Si (OCH ₃ ) ₃ .HCl HC≡C-Si (OC ₂ H ₅ ) ₃ CH ₃ C≡C-Si (OC ₂ H ₅ ) ₃ DMI- (CH ₂ ) m-CONH- (CH ₂ ) ₃ -Si
(OCH ₃ ) ₃ (DMI: represents a dimethylmaleimide group.
_{m = 1~20) CH 2 = CHCH} 2 O-Si (OCH 3) 3 (CH 2 = CHCH 2 O) 4 Si HO-CH 2 -C≡C-Si (OC 2 H 5) 3 CH 3 CH 2 CO—C≡C—Si (OC ₂ H ₅ ) ₃ CH ₂ ＣＨCHS— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ CH ₂ ＣＨCHCH ₂ O— (CH ₂ ) ₂ —SCH ₂ —Si (O
_{CH 3) 3 CH 2 = CHCH} 2 S- (CH 2) 3 -S-Si (OC
_{H 3) 3 (CH 3)} 3 CCO-C≡C-Si (OC 2 H 5) 3 (CH 2 = CH) 2 N- (CH 2) 2 -SCH 2 -Si (O
CH ₃ ) ₃ CH ₃ COCH ＝ C (CH ₃ ) —O—Si (OCH ₃ ) ₃ γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropylmethyldimethoxysilane γ-glycidoxypropyldimethylmethoxysilane γ -Glycidoxypropyltriethoxysilane

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The present invention is not limited to these. The silane coupling agent may be used by mixing several compounds in an arbitrary ratio.

The microgel used in the present invention is generally a polymer fine particle having a particle diameter in the range of 0.005 to 1 μm, and is insoluble in a solvent due to the polymer forming the particle having a crosslinked structure. Alternatively, it can be dispersed in an organic solvent, and when a film is formed on a film base together with a binder, it is almost transparent visually.

The microgel of the present invention is usually produced by emulsion polymerization or dispersion polymerization. Generally, it is formed from 99 to 99.5% by mass of a polymer component and 1.0 to 0.5% by mass of a crosslinking agent. The polymer component can be changed during the polymerization in order to form a microgel having a different composition between the inside and the outside of the particle.

When a latex dispersible in an organic solvent is used in the microgel contained in the photosensitive composition according to the present invention, the latex can be used for several hours without dissolving, coagulating or precipitating using a desired organic solvent as a dispersion medium. It is a dispersion system that can maintain a stable state.

The type of the dispersoid of the latex useful in the present invention is not particularly limited as long as it does not dissolve, aggregate or precipitate in a predetermined organic solvent. One type of the latex may be used, or two or more types may be used in combination.

Examples of the dispersoids of the latex include polyacrylate or copolymer thereof, polyacrylonitrile or copolymer thereof, polystyrene or copolymer thereof, polyethylene or copolymer thereof, polyvinyl chloride or copolymer thereof, polyvinylidene chloride or copolymer thereof. , Polyvinyl acetate or copolymers thereof,
Resole resins or copolymers thereof, ionomer resins,
Examples thereof include polymethyl methacrylate or a copolymer thereof, polybutadiene or a copolymer thereof, and the like.

The polymer compound forming a latex dispersible in an organic solvent which is preferably used in the present invention preferably has a quaternary nitrogen atom in the molecule, whereby the dispersibility in water is improved. And a physical bond with the polymer of the ethylenically unsaturated compound occurs. This quaternary nitrogen atom is preferably contained in the side chain of the polymer molecule.

Examples of the infrared dye that can be used in the present invention include cyanine dyes, squalium dyes, croconium dyes, azurenium dyes, phthalocyanine dyes, naphthalocyanine dyes, polymethine dyes, naphthoquinone dyes, and thiopyrylium dyes. Dyes, dithiol metal complex dyes, anthraquinone dyes, indoaniline metal complex dyes, and intermolecular CT dyes.

Representative examples of the infrared absorbing dye preferably used in the present invention are shown below, but are not limited thereto.

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The infrared absorbing dye preferably used in the present invention can of course be synthesized by a known method.
The following commercially available products can also be used.

Nippon Kayaku: IR750 (anthraquinone type); IR002, IR003 (aluminum type);
R820 (polymethine type); IRG022, IRG03
3 (diimmonium-based); CY-2, CY-4, CY-
9, CY-10, CY-20, Mitsui Toatsu: KIR10
3, SIR103 (phthalocyanine); KIR10
1, SIR114 (anthraquinone type); PA100
1, PA1005, PA1006, SIR128 (metal complex type), Dainippon Ink and Chemicals: Fastogen bl
ue8120, Midori Kagaku: MIR-101, 101
1,1021, and others, such as Nippon Kogaku Dye, Sumitomo Chemical, and Fuji Photo Film. In the present invention, it is optimal to use a cyanine dye.

Also, JP-A-63-139191, JP-A-64-139191.
-33547, JP-A-1-160683, 1-2
No. 80750, No. 1-293342, No. 2-2074
No. 3-26593, No. 3-30991, No. 3-
No. 34891, No. 3-36093, No. 3-36094
Nos. 3-36095, 3-42281, 3-
No. 103476 and the like.

The lithographic printing plate precursor according to the invention can be produced by providing a recording layer on the above-mentioned support.

The recording layer is kneaded with a binder resin, a colorant, and, if necessary, a lubricant, a dispersant, an antistatic agent, a filler, a filler, and a solvent to prepare a high-concentration recording layer forming composition. Then, this is diluted to obtain a recording layer forming composition for coating, which can be formed by coating and drying on a support.

The organic solvent used for the coating material for forming the recording layer is not particularly limited as long as it can dissolve or disperse the above-mentioned composition. Examples thereof include alcohols (ethanol, propanol, etc.) and cellosolves (methyl Cellosolve, ethyl cellosolve), aromatics (toluene, xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate,
Examples thereof include butyl acetate, ethers (tetrahydrofuran, dioxane, etc.), halogen solvents (chloroform, dichlorobenzene, etc.), amide solvents (eg, dimethylformamide, N-methylpyrrolidone, etc.). For the kneading and dispersing of the colorant layer components, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder,
Sqegvari Attritor, High Speed Impeller Disperser, High Speed Stone Mill, High Speed Impact Mill, Disper,
A high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader, or the like can be used.

The recording layer can be formed on the support by, for example, coating and drying with an extrusion-type extrusion coater. In order to obtain a high-resolution image, the recording layer is hardened. The surface may be calendered.

As the exposure light source for forming an image on the lithographic printing plate precursor, any light source capable of responding to the recording layer can be used without any particular limitation. Among them, in order to obtain high resolution, an electromagnetic wave whose energy application area can be narrowed down, in particular, ultraviolet light having a wavelength of 1 nm to 1 mm, visible light, and infrared light are preferable. As a light source to which such light energy can be applied, for example, a laser, Light-emitting diode, xenon flash lamp, halogen lamp, carbon arc lamp,
Examples include a metal halide lamp, a tungsten lamp, a quartz mercury lamp, a high-pressure mercury lamp, and the like. The energy applied at this time depends on the type of the image forming material.
By adjusting the exposure distance, time and intensity, it can be selected and used as appropriate.

As the laser light source used in the printing method of the present invention, generally known ruby laser, YA
Solid lasers such as G lasers and glass lasers; He
-Ne laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, the He-Cd laser, N ₂ laser, a gas laser such as an excimer laser; InGaP laser, AlGaAs laser,
GaAsP laser, InGaAs laser, InAs
A semiconductor laser such as a P laser, a CdSnP ₂ laser, or a GaSb laser; a chemical laser, a dye laser, or the like. Among them, in order to cause ablation efficiently, the wavelength is 600 to 1200 nm.
Is preferable in terms of sensitivity because the laser can convert light energy into heat energy.

The printing method of the present invention is characterized in that printing is performed without performing development processing after laser exposure based on image information.

The lithographic printing plate precursor thus image-exposed is directly mounted on a plate cylinder of a printing press without performing a developing process, and both of them supply dampening solution and printing ink to the plate surface.
Printing is possible by transferring the ink image on the plate surface to paper via a blanket.

[0105]

Example 1 A 0.24 mm thick aluminum plate (material 1050, tempered H16) was degreased with a 10% by mass aqueous solution of sodium hydroxide, and this was degreased in a 1.8% hydrochloric acid bath at 25 ° C. and 30 A. / Dm
^2. Electroetching was performed under a current density condition of 30 seconds, washed with water, and then anodized in a 30% sulfuric acid bath at 30 ° C. and 6.5 A / dm ² for 30 seconds. Next, a 1% by mass aqueous solution of sodium metasilicate was sealed at 85 ° C. for 30 seconds, washed with water and dried to obtain an aluminum plate as a lithographic printing plate support.

On the other hand, the following components were placed in a flask heated to 130 ° C. in an oil bath and melt-mixed for 30 minutes. The resulting molten mixture was dropped into 70 ° C. water adjusted to pH 12 and stirred vigorously for 2 hours, whereby water of hot-melt particles coated with a hydrophilic agent having an average particle size of 0.5 μm was added. A dispersion was obtained. Water was added to the resulting aqueous dispersion to adjust the solid content to 40%.

Carnauba wax (melting point: 80 ° C., crystallinity: 2%) 38.5 parts Polyvinyl alcohol having a saponification degree of 70% (acid value: 12 mg) 1.5 parts 3-methacrylamide-phenylazosulfonate 3.5 parts Next Then, a coating solution for a recording layer having the following composition was applied and dried on the support prepared above so that the film thickness after drying was 1 μm.

AMT-SILICA # 200B (high silica aluminosilicate, average particle size of primary particles 2.1 μm; manufactured by Mizusawa Chemical Co., Ltd.) 40 parts by mass Colloidal silica (Snowtex-OS; manufactured by Nissan Chemical Co., Ltd.) 180 parts by mass polyvinyl 36 mass parts of 10 mass% aqueous solution of alcohol Z-100 (manufactured by Nippon Synthetic Chemical Company) 4 mass parts of 10 mass% aqueous solution of melamine resin (Sumilezu Resin 613; manufactured by Sumitomo Chemical Co., Ltd.) Reaction accelerator (Sumilezu Resin ACX-P) ; 10 mass% aqueous solution of Sumitomo Chemical Co., Ltd. 0.4 mass part Titanium black 13M (manufactured by Mitsubishi Materials Corporation) 20 mass parts Carnauba wax aqueous dispersion prepared above (melting point 80 ° C, crystallinity 2%) 50 mass Part Pure water 720 parts by mass A lithographic printing plate precursor obtained is provided with a semiconductor laser light source (emission wavelength 830 nm, spot size). Using a 10 μm light source, a scanning speed of 2.2 m / sec and a resolution of 2,000 dpi in both the scanning direction and the sub-scanning direction (dpi indicates the number of dots per inch), exposing a halftone dot image and performing any processing. When printing was performed under the following conditions, 50,000 prints without stains and having good dot reproducibility were obtained.

Printing conditions Printing machine: Heidel GTO, coated paper, dampening solution: H-solution SG-51 concentration 1.5%, manufactured by Tokyo Ink Co., Ltd. Ink: Toyo King Hi-Echo M red manufactured by Toyo Ink Co., Ltd.

Example 2 A coating solution having the following composition was dispersed in a sand grinder for 180 minutes to prepare a coating solution for a porous hydrophilic layer, and the film was dried on the anodized aluminum support used in Example 1. Coating and drying were performed to a thickness of 2 μm.

AMT-SILICA # 200B (high silica aluminosilicate, average particle size of primary particles 2.1 μm; manufactured by Mizusawa Chemical Co., Ltd.) 40 parts by mass Colloidal silica (Snowtex-OS; manufactured by Nissan Chemical Co., Ltd.) 180 parts by mass polyvinyl 50% by mass of a 10% by mass aqueous solution of alcohol Z-100 (manufactured by Nippon Synthetic Chemical Company) 20 parts by mass of titanium black 13M (manufactured by Mitsubishi Materials Corporation) 720 parts by mass of pure water Next, the coating solution for the recording layer used in Example 1 was used. Prepared in the same manner as in Example 1, and the film thickness after drying was 1 μm on the hydrophilic layer.
And dried.

The obtained lithographic printing plate precursor was subjected to laser exposure and printing in the same manner as in Example 1. As a result, 70,000 printed materials having good halftone dot reproducibility and no background stain were obtained.

When the state of the lithographic printing plate was checked at the 200th printing from the start of printing, the recording layer and the hydrophilic layer were removed from the unexposed portions, and the surface of the anodized aluminum was exposed.

Example 3 An aluminum plate having a thickness of 0.24 mm (material: 1050, tempered H16) was degreased with a 10% by mass aqueous solution of sodium hydroxide, and was degreased in a 1.8% hydrochloric acid bath at 25 ° C. and 30 A / A. dm
^2. Electroetching was performed under a current density condition of 30 seconds, washed with water, and then anodized in a 30% sulfuric acid bath at 30 ° C. and 6.5 A / dm ² for 30 seconds.

Next, after immersion in an aqueous solution of bromkari,
Furthermore, it was immersed in an aqueous solution of ammoniacal silver nitrate, washed with water, and then dried. This was exposed to light using a halogen lamp, and developed and fixed using a commercially available photographic developer. Finally, sealing treatment was performed with a 1% by mass aqueous solution of sodium metasilicate at 85 ° C. for 30 seconds, followed by washing and drying to obtain a lithographic printing plate support in which blackened silver was formed in the pores.

The coating solution for the recording layer used in Example 1 was applied and dried in the same manner as in Example 1, and then exposed and printed in the same manner. A printed matter having no stain and excellent dot reproducibility was obtained. 70,000 sheets were obtained.

Example 4 On the anodized aluminum support prepared in Example 1,
A layer of a silane coupling agent having the following composition was applied and dried.

10 parts by mass of γ-glycidoxypropyltrimethoxysilane 100 parts by mass of ethyl methyl ketone Then, the following coating solution for a recording layer has a thickness of 1 μm after drying.
Was applied to the surface coated with the silane coupling agent and dried.

AMT-SILICA # 200B (high silica aluminosilicate, average particle size of primary particles 2.1 μm; manufactured by Mizusawa Chemical Co., Ltd.) 40 parts by mass Colloidal silica (Snowtex-OS; manufactured by Nissan Chemical Co., Ltd.) 180 parts by mass polyvinyl 36% by mass of 10% aqueous solution of alcohol Z-100 (manufactured by Nippon Gosei Kagaku) 20 parts by mass of titanium black 13M (manufactured by Mitsubishi Materials Corporation) Carnauba wax aqueous dispersion prepared above (melting point: 80 ° C., crystallinity: 2%) 50 parts by mass Sulfate of formaldehyde condensation product of diazodiphenylamine 1 part by mass 720 parts by mass of pure water The obtained lithographic printing plate precursor was subjected to laser exposure and printing in the same manner as in Example 1 to obtain a dot. 70,000 prints with good reproducibility and no background stain were obtained.

Example 5 A lithographic printing plate was prepared by applying and drying the following photosensitive solution on the anodized aluminum support used in Example 1 so that the film thickness after drying was 2 μm.

Microgel polymer represented by the following formula 14: 10 g Trimethylolpropane triacrylate 10 g Diethylthioxanthone 1 g Isoamyl dimethylaminobenzoate 1 g Methyl cellosolve 100 g Infrared absorbing dye CY-10 (manufactured by Nippon Kayaku Co., Ltd.) 2 g

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The obtained lithographic printing plate precursor was subjected to laser exposure and printing in the same manner as in Example 1. As a result, 60,000 printed materials having good halftone dot reproducibility and no background smear were obtained.

Example 6 The following photosensitive liquid was applied onto the anodized aluminum support used in Example 1 and dried so that the film thickness after drying was 0.2 μm.

Sulfate salt of formaldehyde condensation product of diazodiphenylamine 1 part by mass Infrared dye CY-10 (manufactured by Nippon Kayaku Co., Ltd.) 0.2 part by mass Methyl cellosolve 100 parts by mass A lithographic printing plate was prepared by applying and drying the coating solution so that the film thickness after drying was 1 μm.

2-Hydroxyethyl methacrylate, N- (4-hydroxyphenyl) methacrylamide, methacrylic acid Copolymer resin with a molar ratio of 40/55/5 (molecular weight 1.2 × 10 ⁴ ) 100 parts by mass propylene glycol methyl ether 100 parts by mass The obtained lithographic printing plate precursor was subjected to laser exposure and printing in the same manner as in Example 1. As a result, 70,000 printed materials having good halftone dot reproducibility and no background staining were obtained.

Example 7 A primer layer composition shown below was applied on a 0.24 mm thick degreased aluminum plate and dried at 100 ° C. for 2 minutes to provide a primer layer. The dispersion of the primer layer composition was performed by a high-pressure valve homogenizer.

[Primer Layer Composition] 100 parts by mass of a copolymer resin having a molar ratio of 2-hydroxyethyl methacrylate and methyl methacrylate of 34/66 (molecular weight 4.0 × 10 ⁴ ) 80 parts by mass pentaerythritol triacrylate 80 parts by mass diethylthioxanthone DETX ( Nippon Kayaku Co., Ltd.) 3 parts by mass Ethyl 2-ethoxybenzoate EPA (Nippon Kayaku Co., Ltd.) 3 parts by mass Ket Yellow 402 (Dainippon Ink Co., Ltd., yellow pigment) 8 parts by mass zinc oxide (Average particle size: 0.12 μm) 20 parts by mass Ethyl cellosolve 920 parts by mass After coating and drying, it is applied with Unicure (produced by Ushio Inc.).
Exposure was performed at 0 W and 4 m / min. Next, the following photosensitive composition was applied on the primer layer, and dried at 80 ° C. for 2 minutes to form a recording layer having a thickness of 0.3 μm.

[Photosensitive Composition] Sulfate of formaldehyde condensation product of diazodiphenylamine 100 parts by mass 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) methacrylamide, molar ratio of methacrylic acid 30/55 / No. 15 copolymer resin (molecular weight 4.2 × 10 ⁴ ) 100 parts by mass Infrared dye CY-10 (manufactured by Nippon Kayaku Co., Ltd.) 8 parts by mass Methyl lactate 900 parts by mass Next, the following silicone rubber composition was formed on the recording layer. It was applied to a thickness of 2.0 μm and dried at 90 ° C. for 10 minutes.

[Silicone Rubber Layer Composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight: 52,000) 100 parts by mass Triacetoxysilane 2.5 parts by mass Dibutyltin dilaurate 0.8 parts by mass Isopar E (manufactured by Esso Chemical Co., Ltd.) Next, a 6 μm-thick polypropylene film was laminated on the silicone rubber layer to obtain a photosensitive lithographic printing plate requiring no dampening water.

The lithographic printing plate precursor obtained was subjected to laser exposure similarly to the printing press used in Example 1 except that no dampening solution was supplied and the printing ink was changed to one for printing without dampening solution. As a result of printing, 50,000 sheets of printed matter having good halftone dot reproducibility and no background stain were obtained.

[0132]

According to the present invention, a lithographic printing plate having excellent image reproducibility and printing durability, a method for producing the same, and a printing method can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 503 503Z 505 505 7/032 7/032 7/075 501 7/075 501 521 521 7/11 503 7/11 503 F term (reference) 2H025 AA04 AA12 AB03 AB04 AC08 AD01 AD03 BC34 BC43 BE00 BE07 BE08 CA00 CA41 CC06 CC11 CC13 CC20 DA36 DA37 2H084 AA14 AA14 AA25 AA30 AE05 BB04 A03 BA05 A05 2 EA04 EA23 GA60 2H114 AA04 AA14 AA21 AA24 AA30 BA01 BA06 BA10 DA04 DA38 DA43 DA45 DA46 DA47 DA49 DA50 DA52 DA56 DA60 DA62 DA75 DA77 DA79 EA03 EA05 FA16 GA09

Claims (9)

[Claims] 1. A heat-fusible particle containing a substance which generates an active species which reacts with the support by light on a support and which is not a capsule-like particle containing a liquid substance at room temperature as a main component on a support. A lithographic printing plate comprising a recording layer having the formula: 2. A lithographic printing plate having a porous hydrophilic layer and a recording layer on a hydrophilic support is subjected to image recording by light, and then the porous hydrophilic layer and the recording layer in a non-image area are printed. A method for preparing a lithographic printing plate, comprising removing the surface of a hydrophilic support by removing it with a treating agent sometimes used. 3. Visible in pores of an anodized aluminum film;
A lithographic printing plate support comprising a metal having absorption in an infrared region. 4. A lithographic printing plate comprising a silane coupling agent having a cationically polymerizable group between a support and a recording layer. 5. The lithographic printing plate according to claim 4, wherein the recording layer contains a compound that generates an acid by light or heat. 6. A printing method, comprising: after exposing a lithographic printing plate having a recording layer containing a microgel and an infrared dye, attaching the lithographic printing plate to a printing cylinder of a printing machine without any treatment, and performing printing. 7. The printing method according to claim 6, wherein the microgel is a water-dispersible microgel having a quaternary salt structure. 8. A lithographic printing plate having a water-soluble photographic material, a recording layer containing an infrared dye, and a water-permeable lipophilic layer in this order on a support, is exposed to light without any treatment. A printing method, wherein the printing method is performed by attaching to a printing cylinder. 9. A lithographic printing plate having a primer layer, a recording layer containing an infrared dye, and a silicone layer on a support in this order, is exposed to a printing cylinder of a printing press without any treatment, and printing is performed. A printing method, characterized in that: