JP2002086945A - Original plate for thermal lithography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for thermal lithography which can be fitted for printing to a press as it is, without being processed, after scanning exposure based on digital signals and which is improved in plate wear. SOLUTION: The original plate for thermal lithography has on an aluminum substrate an ink receiving layer (1) and a hydrophilic layer (2) which contains a colloidal-particle-like oxide or a hydroxide of at least one element selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and a transition metal, and at least either the ink receiving layer or the hydrophilic layer contains a photothermal conversion agent. The ink receiving layer contains a phenoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive lithographic printing plate not requiring development. More specifically, an image can be recorded by infrared laser beam scanning exposure based on a digital signal, and the recorded image can be directly mounted on a printing machine and printed without going through a conventional developing process. The present invention relates to a lithographic printing plate that is capable of being excellent in sensitivity, printing start inking property, and printing durability.

[0002]

2. Description of the Related Art Various methods have been proposed for a lithographic printing plate precursor that can be mounted on a printing machine without any processing after exposure and printing can be performed. One of the promising methods is a method using ablation in which a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser is used for exposure, and the exposed portion is heated with a photothermal conversion agent that converts light into heat, thereby causing decomposition and evaporation. It is. That is, a hydrophilic layer is provided on a substrate having a lipophilic ink-receiving surface or a lipophilic ink-receiving layer, and the hydrophilic layer is ablated and removed.

[0003] WO 94/18005 discloses a printing plate in which a crosslinked hydrophilic layer is provided on a lipophilic laser light absorbing layer, and the hydrophilic layer is ablated. The hydrophilic layer is formed by cross-linking polyvinyl alcohol with a hydrolyzate of tetraethoxysilicon and containing titanium dioxide particles to improve the film strength of the hydrophilic layer. This technology improves press life. However, since it is mainly composed of polyvinyl alcohol having a hydrocarbon group and not necessarily having high hydrophilicity, the stain resistance is insufficient, and further improvement is required.

[0004] WO98 / 40212 and WO99
/ 19143 has an ink receiving layer and a hydrophilic layer mainly composed of a colloid such as silica cross-linked with a cross-linking agent such as aminopropyltriethoxysilane on a substrate. A lithographic printing plate that can be mounted is disclosed. The hydrophilic layer has reduced hydrocarbon groups as much as possible to enhance the resistance to printing stains, and improves the printing durability by crosslinking the colloid with a crosslinking agent. In addition, the ink receiving layer contains polycarbonate, polyester, polyvinyl butyral, polyacrylate, or a chemically modified cellulose derivative as a binder polymer in addition to the photothermal conversion agent.

[0005] WO99 / 19144 discloses a lithographic printing plate having a heat-insulating layer containing no light-to-heat converting agent instead of the ink-receiving layer.
It is described that cellulose acetate, polymethyl methacrylate, polystyrene, polyvinyl butyral, and polycarbonates are used.

[0006]

However, the above-mentioned technology has insufficient printing durability of several thousand sheets. Accordingly, it is an object of the present invention to solve this problem, and it is possible to mount and print directly on a printing press without performing post-exposure processing, and heat-sensitive lithographic printing with improved printing durability To provide a master plate.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that the above object can be achieved by including a phenoxy resin in the ink receiving layer. That is, the present invention is as follows.

[0008] 1. On a support, (1) an ink receiving layer, and (2) beryllium, magnesium, aluminum,
An ink receiving layer having a hydrophilic layer containing a colloidal particulate oxide or hydroxide of at least one element selected from silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metals; And a heat-sensitive lithographic printing plate, wherein at least one of the hydrophilic layers contains a light-to-heat conversion agent, and the ink-receiving layer contains a phenoxy resin.

[0009] 2. On a support, (1) an ink receiving layer,
(2) an ink receiving layer comprising: the hydrophilic layer according to the above (1); and (3) a hydrophilic overcoat layer removable on a printing press.
At least one of the hydrophilic layer and the hydrophilic overcoat layer is a heat-sensitive lithographic printing original plate containing a photothermal conversion agent, and the ink-receiving layer contains a phenoxy resin. Original plate.

[0010]

Embodiments of the present invention will be described below in detail. The ink receiving layer of the present invention is characterized by containing a phenoxy resin, and by including the phenoxy resin, the printing durability can be improved.

Here, the phenoxy resin is a high molecular weight resin obtained by reacting bisphenol with an equimolar amount of epichlorohydrin in the presence of an alkali catalyst. Examples of the bisphenol include 4,4'-dihydroxybiphenyl and 4,4'-dihydroxy- 3,3 ′, 5,5′-tetramethylbiphenyl; 4,4′-dihydroxydiphenyl sulfone;
4,4'-dihydroxydiphenyl ether; 2,2 '
-Dihydroxy-4,4'dimethoxybenzophenone;
2,2'-dihydroxydiphenyl;1,5-dihydroxynaphthalene; bis (4-hydroxyphenyl) methane; 2,2-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxy-3-methyl 1,2-bis (4-hydroxyphenyl) cyclohexanone; 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane; 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and the like.
Further, two or more of these bisphenols may be mixed and reacted with epichlorohydrin.

Particularly preferred phenoxy resins include:
Examples thereof include those obtained by reacting 2,2-bis (4-hydroxyphenyl) propane with an equivalent amount of epichlorohydrin, and those obtained by partially hydrogenating this product.

In the ink receiving layer of the present invention, a resin other than the phenoxy resin may be mixed and used. Examples of other resins that can be mixed include lipophilic organic polymers that are soluble in solvents capable of forming a film.

Examples of such organic polymers include polyester, polyurethane, polyurea, polyimide, polysiloxane, polycarbonate, low molecular weight epoxy resin, phenol / formaldehyde resin, alkylphenol / formaldehyde resin, polyvinyl acetate, acrylic resin and copolymers thereof, polyvinyl Phenol, polyvinylhalogenated phenol, methacrylic resin and its copolymer, acrylamide copolymer, methacrylamide copolymer, polyvinylformal, polyamide, polyvinylbutyral, polystyrene, cellulose ester resin, polyvinyl chloride and polyvinylidene chloride, etc. be able to.

Phenol, cresol (m-cresol, p-cresol, m / p mixed cresol), phenol / cresol (m-cresol, p-cresol, m / p mixed cresol), phenol-modified xylene, t-butylphenol, Octylphenol, resorcinol, pyrogallol, catechol, chlorophenol (m-Cl, p-Cl), bromophenol (m-
Novolak resins and resole resins for condensation with formaldehyde such as Br, p-Br), salicylic acid, and phloroglucinol, as well as condensation resins of the above phenolic compounds and acetone can be used as phenoxy resins and future resins.

Other suitable high molecular compounds to be mixed include copolymers having a molecular weight of usually 10,000 to 200,000 having the following structural units as monomers (1) to (12). . (1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, for example, N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacryl Amide, o
-, M- and p-hydroxystyrene, o-, m- and p-hydroxyphenyl acrylate or methacrylate, (2) acrylates and methacrylates having an aliphatic hydroxyl group, for example, 2-
Hydroxyethyl acrylate or 2-hydroxyethyl methacrylate,

(3) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid-2 (Substituted) acrylates such as -chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (4) methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, (Substituted) methacrylates such as glycidyl methacrylate and N-dimethylaminoethyl methacrylate;

(5) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
-Phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N
Acrylamide or methacrylamide such as -ethyl-N-phenylmethacrylamide,

(6) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as octyl vinyl ether and phenyl vinyl ether; (7) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (8) styrenes such as styrene, methyl styrene and chloromethyl styrene; 9)
Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (10) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (11) N
-Vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc.

(12) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) Naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonyl) Methacrylamides such as phenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate, m-amino Sulfo sulfonyl phenyl acrylate,
p-aminosulfonylphenyl acrylate, 1- (3
-Aminosulfonylphenylnaphthyl) unsaturated sulfonamides such as acrylates such as acrylate, o-aminosulfonylphenylmethacrylate, m
Unsaturated sulfonamides such as methacrylic esters such as -aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate and 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

The phenoxy resin is preferably contained in an amount of 50% by weight or more of the solid content of the ink receiving layer. Within this range, a good high printing durability effect can be obtained.

The ink receiving layer of the present invention further comprises a crosslinking agent,
An adhesion aid, a colorant, inorganic or organic fine particles, a coating surface condition improving agent, and a plasticizer can be added as necessary. In addition, the ink receiving layer may contain a light-to-heat conversion agent for increasing the sensitivity or a heat coloring or decoloring additive for forming a printed image after exposure.

Specific crosslinking agents for crosslinking organic polymers include diazo resins, aromatic azide compounds, epoxy resins, isocyanate compounds, blocked isocyanate compounds, initial hydrolysis condensates of tetraalkoxy silicon, glyoxal, aldehyde compounds and methylol. Compounds can be mentioned.

As the adhesion aid, the above diazo resin is excellent in adhesion to a substrate and a hydrophilic layer. In addition, a silane coupling agent, an isocyanate compound, and a titanium coupling agent are also useful.

As the coloring agent, ordinary dyes and pigments are used. In particular, rhodamine 6G chloride, rhodamine B chloride, crystal violet, malachite green oxalate, oxazine 4 perchlorate, quinizarin,
2- (α-naphthyl) -5-phenyloxazole and coumarin-4. Specifically, as other dyes,
Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black B
Y, oil black BS, oil black T-505
(The above are manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI4255)
5), methyl violet (CI42535), ethyl violet, methylene blue (CI52015), patent pure blue (manufactured by Sumitomo Sangoku Chemical Co., Ltd.), brilliant blue, methyl green, erythricin B, basic fuchsin, m-cresol purple, auramine, 4
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes such as -p-diethylaminophenyliminaphthoquinone and cyano-p-diethylaminophenylacetanilide; -293247, Japanese Patent Application No. 7-3351.
No. 45 can be mentioned. When the dye is added to the ink receiving layer, it is usually about 0.02 to 10% by weight based on the total solid content of the receiving layer.
More preferably, the proportion is from about 0.1 to 5% by weight.

Further, fluorine-based surfactants and silicon-based surfactants, which are well-known compounds as coating surface condition improvers, can also be used. Specifically, a surfactant having a perfluoroalkyl group or a dimethylsiloxane group is useful for preparing the coated surface.

The inorganic or organic fine particles which can be used in the present invention include colloidal silica and colloidal aluminum having a diameter of 10 nm to 100 nm, and inert particles having a particle diameter larger than those of these colloids, for example, silica particles, and surface hydrophobicizing. Silica particles, alumina particles, titanium dioxide particles, other heavy metal particles, clay and talc. The addition of these inorganic or organic fine particles to the ink receiving layer has the effect of improving the adhesion to the upper hydrophilic layer and increasing the printing durability in printing. The addition ratio of these fine particles in the ink receiving layer is 80% by weight or less of the total amount, preferably 40% by weight or less.

Further, a plasticizer may be added to the ink receiving layer of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid And polymers.

Further, it is preferable to add a coloring or decoloring compound to the ink receiving layer of the present invention in order to sharpen the image area and the non-image area when exposed. For example,
Leuco dyes (leucomalachite green, leucomalachite green, etc.) along with thermal acid generators such as diazo compounds and diphenyliodonium salts
Leuco crystal violet, lactone of crystal violet, etc.) and PH discoloration dye (eg, dye such as ethyl violet, Victoria Poor Blue BOH)
Is used. In addition, a combination of an acid coloring dye and an acidic binder as described in EP 897134 is also effective. In this case, the bond in the associated state forming the dye is broken by heating, and a lactone is formed to change from colored to colorless. The addition ratio of these coloring or decoloring systems is 10% by weight based on the total solids in the receiving layer.
It is preferably at most 5% by weight.

As the solvent for coating the ink receiving layer, alcohols (methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol,
Propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), ethers (tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.), ketones (acetone, methyl ethyl ketone, Acetylacetone, etc.), esters (methyl acetate, ethylene glycol monomethyl monoacetate, methyl lactate, ethyl lactate,
Gamma-butyrolactone), amides (formamide, N-methylformamide, pyrrolidone, N-methylpyrrolidone, etc.) and the like can be used. These solvents are used alone or in a mixed state. When preparing a coating solution, the concentration of the components of the ink receiving layer (total solids including additives) in the solvent is preferably 1 to 50% by weight. In addition, a film can be formed not only from the above-mentioned application from an organic solvent but also from an aqueous emulsion. In this case, the concentration is preferably 5% by weight to 50% by weight.

The thickness of the ink receiving layer in the present invention after coating and drying is not particularly limited, but is preferably 0.1 μm or more. It is more preferably at least 0.2 μm.

The hydrophilic layer used in the present invention is a layer which is insoluble in a fountain solution by lithographic printing using a fountain solution and ink, and is a layer of beryllium, magnesium, aluminum, silicon,
Titanium, boron, germanium, tin, zirconium,
It is formed by applying a solution containing colloidal particulate oxide or hydroxide of at least one element selected from iron, vanadium, antimony and transition metal, and polyacrylic acid. Aluminum, silicon, titanium and zirconium are particularly preferred among the elements constituting the colloidal particulate oxide or hydroxide used in the present invention.

The size of the colloid used in the present invention is as follows:
Spherical silica having a particle size of 5 to 100 nm is preferable. Spherical particles having a particle size of 10 to 50 nm are 50 to 400 nm
Can be used. Feathers such as 100 nm × 10 nm like aluminum oxide or hydroxide colloids are also effective.

These colloids can be prepared by various known methods such as hydrolysis of the halides or alkoxy compounds of the above elements or condensation of hydroxides. For example,
A sol can also be prepared by applying a hydrolysis / condensation reaction directly from di, tri and / or tetraalkoxysilane under an acid catalyst to apply. When this sol is applied, a stronger hydrophilic three-dimensional crosslinked film can be obtained. In addition, a commercially available product such as Nissan Chemical Industries, Ltd. may be selected and used as the colloid dispersion liquid.

The hydrophilic layer of the present invention can contain a hydrophilic resin. As the hydrophilic resin, those having a hydrophilic group such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl and the like are preferable.

Specific hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and their Na salts, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, Polyacrylic acids and their salts, polymethacrylic acids and their salts, hydroxyethyl methacrylate homopolymers and copolymers, hydroxyethyl acrylate homopolymers and copolymers, hydroxypropyl methacrylate homopolymers and copolymers, hydroxypropyl acrylate homopolymers and Copolymers, hydroxybutyl methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers, Lithylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and homopolymers and copolymers of hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, and acrylamide having a degree of hydrolysis of at least 60% by weight, preferably at least 80% by weight , Methacrylamide homopolymers and polymers, N-methylolacrylamide homopolymers and copolymers, and the like.

These hydrophilic resins are used together with a colloid. The proportion of the hydrophilic resin is as follows when the hydrophilic resin is water-soluble.
The total solid content of the hydrophilic layer is preferably 40% by weight or less, and in the case of a non-water-soluble hydrophilic resin, the total solid content is preferably 20% by weight or less.

The hydrophilic layer of the present invention may contain, in addition to the above-mentioned colloid and hydrophilic resin, a crosslinking agent for accelerating the crosslinking of the colloid. As such a colloid crosslinking agent, an initial hydrolysis condensate of tetraalkoxysilane, trialkoxysilylpropyl-N, N, N-trialkylammonium halide or aminopropyltrialkoxysilane is preferable. It is preferable that the addition ratio is 5% by weight or less of the total solid content of the hydrophilic layer.

Although the hydrophilic resin can be used as it is, it may be used together with a crosslinking agent for the hydrophilic resin other than the colloid as needed in order to increase the printing durability. Examples of such a crosslinking agent include initial hydrolysis and condensate of formaldehyde, glyoxal, polyisocyanate and tetraalkoxysilane, dimethylol urea and hexamethylol melamine.

The hydrophilic layer containing each of the above components is provided by preparing a solution in which each component is dissolved or dispersed in a solvent, and applying the solution. As the main solvent of the hydrophilic layer coating solution, water and low-boiling alcohols such as methanol, ethanol and propanol are used alone or as a mixture.

The hydrophilic layer of the present invention may further include a well-known fluorine-based surfactant for improving the surface condition of the coating.
A silicon-based surfactant, a polyoxyethylene-based surfactant, or the like may be added.

The coating thickness of the hydrophilic layer of the present invention is preferably from 0.1 μm to 3 μm. Within this range, ablation is good and printing durability is good.

In the heat-sensitive lithographic printing plate precursor of the present invention, a hydrophilic overcoat layer can be provided on the hydrophilic layer in order to suppress scattering of scum due to ablation and to prevent contamination of the hydrophilic layer by a lipophilic substance.

The hydrophilic overcoat layer used in the present invention is removable on a printing press, and is made of a resin selected from a water-soluble resin or a water-swellable resin obtained by partially crosslinking a water-soluble resin. contains.

Such a water-soluble resin is selected from a water-soluble natural polymer and a synthetic polymer, and is used together with a cross-linking agent.
Specific examples of the water-soluble resin preferably used in the present invention include, as natural polymers, gum arabic, water-soluble soybean polysaccharide, cellulose derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) Body, white dextrin, pullulan,
In synthetic polymers such as enzymatically degraded etherified dextrin,
Polyvinyl alcohol (Polyvinyl acetate hydrolysis rate 6)
5% or more), polyacrylic acid, its alkali metal salt or amine salt, polyacrylic acid copolymer, its alkali metal salt or amine salt, polymethacrylic acid, its alkali metal salt or amine salt, vinyl alcohol / acrylic Acid copolymer and its alkali metal salt or amine salt, polyacrylamide, its copolymer, polyhydroxyethyl acrylate, polyvinylpyrrolidone,
The copolymer, polyvinyl methyl ether, vinyl methyl ether / maleic anhydride copolymer, poly-2-acrylamido-2-methyl-1-propanesulfonic acid, alkali metal salt or amine salt thereof, poly-2-acrylamide- Examples thereof include 2-methyl-1-propanesulfonic acid copolymers, alkali metal salts and amine salts thereof. Further, according to the purpose, two or more of these resins can be used in combination. However, the invention is not limited to these examples.

When at least one kind of water-soluble resin is partially cross-linked to form an overcoat layer on the hydrophilic layer, the cross-linking is carried out by a cross-linking reaction using a reactive functional group of the water-soluble resin. . The cross-linking reaction may be covalent cross-linking or ionic cross-linking.

The crosslinking lowers the tackiness of the surface of the overcoat layer and improves the handleability. However, if the crosslinking proceeds too much, the overcoat layer changes to lipophilic, making it difficult to remove the overcoat layer on a printing press. Therefore, appropriate partial cross-linking is preferable. The preferred degree of partial crosslinking is 2
When the printing plate is immersed in 5 ° C. water, it takes 30 seconds to 10 seconds.
In minutes, the hydrophilic overcoat layer remains without being eluted, but is eluted in 10 minutes or more.

Examples of the compound used in the crosslinking reaction include known polyfunctional compounds having crosslinking properties, such as polyepoxy compounds, polyisocyanate compounds, polyalkoxysilyl compounds, polyvalent metal salt compounds, polyamine compounds, and aldehyde compounds. And hydrazine. The crosslinking reaction can be accelerated by adding a known catalyst.

Specific examples of known polyfunctional compounds having crosslinking properties include the following compounds.

Specific examples of the polyepoxy compound include glycerin polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether,
And polycondensates of bisphenols or hydrogenated products thereof with epihalohydrin.

Specific examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, propylenediamine, polyethyleneimine, and polyamidoamine.

Specific examples of the polyisocyanate compound include tolylene diisocyanate, diphenylmethane isocyanate, liquid diphenylmethane diisocyanate,
Aromatic isocyanates such as polymethylene polyphenyl isocyanate, xylylene diisocyanate, naphthalene-1,5-diisocyanate, cyclohexanephenylene diisocyanate, isopropylbenzene-2,4-diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate and decamethylene diisocyanate; Cyclohexyl diisocyanate, alicyclic diisocyanate such as isophorone diisocyanate,
Further, a polypropylene glycol / tolylene diisocyanate addition reaction product may, for example, be mentioned.

Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl)- γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, vinyltris (methylethylketoxime) silane, methyltris (methylethylketoxime) silane , Vinyltriacetoxysilane, etc.

Examples of the titanate compound include tetraethyl orthosilicate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyltriactanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl (dioctyl phosphate) titanate), isopropyl Tricumylphenyl titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, isopropyltriinstearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl phosphate) titanate , Tetraiso Ropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditrisyl phosphite) titanate, tetra (2,2 diallyloxymethyl-1-butyl) bis (ditridecyl phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate Titanates, bis (dioctyl pyrophosphate) oxyacetate titanates, and the like.

Examples of the aldehyde compound include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, glyoxal, glutaraldehyde, terephthalaldehyde and the like.

Examples of the polyvalent metal salt compound include water-soluble salts of metals such as zinc, calcium, magnesium, barium, strontium, cobalt, manganese and nickel.

These crosslinking agents can be used alone or in combination of two or more. Among these crosslinking agents, a particularly preferred crosslinking agent is a water-soluble crosslinking agent, but a water-insoluble one can be used by dispersing it in water with a dispersant.

Particularly preferred combinations of the water-soluble resin and the crosslinking agent include carboxylic acid-containing water-soluble resin / polyvalent metal compound, carboxylic acid-containing water-soluble resin / water-soluble epoxy resin, and hydroxyl group-containing resin / dialdehydes. .

A suitable amount of the crosslinking agent is 2 to 2 of the water-soluble resin.
-10% by weight. Within this range, good water resistance can be obtained without impairing the removability of the overcoat layer on a printing press.

Particularly preferred combinations of the hydrophilic resin and the crosslinking agent include carboxylic acid-containing hydrophilic resin / polyvalent metal compound, carboxylic acid-containing hydrophilic resin / water-soluble epoxy resin, and hydroxyl group-containing resin / dialdehydes. .

The preferable addition amount of the crosslinking agent is 2
-10% by weight. Within this range, good water resistance can be obtained without impairing the removability of the overcoat layer on a printing press.

In addition, a nonionic surfactant can be mainly added to the overcoat layer in the case of aqueous solution application for the purpose of ensuring uniformity of application. Specific examples of such a nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether, and the like. . The proportion of the nonionic surfactant in the total solid content of the overcoat layer is preferably 0.05 to 5% by weight, and more preferably 1 to 3% by weight.

When the water-soluble resin is not crosslinked, the thickness of the overcoat layer of the present invention is from 0.1 μm to 4.
0 μm is preferred, and a more preferred range is from 0.1 μm to 1.0 μm. When the water-soluble resin is partially crosslinked, the range is preferably 0.1 to 0.5 μm, and 0.1 to 0.3 μm.
μm is more preferred. Within this range, good scattering of ablation scum can be obtained without impairing the removability of the overcoat layer on the printing press.

In the present invention, a photothermal conversion agent having a function of absorbing infrared rays and generating heat is added to at least one of the ink receiving layer, the hydrophilic layer and the overcoat layer in order to increase the sensitivity to infrared rays. .

The photothermal conversion agent may be any substance that absorbs light of 700 nm or more, and various pigments and dyes can be used. Examples of pigments include commercially available pigment and color index (CI) handbook, “Latest Pigment Handbook” (edited by The Japan Pigment Technical Association, 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “printing”. Pigments described in "Ink Technology" (CMC Publishing, 1984) can be used.

The types of pigments include black pigments, brown pigments, red pigments, violet pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bound pigments. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like.

These pigments may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment. The method of surface treatment is a method of surface coating a hydrophilic resin or lipophilic resin,
A method of attaching a surfactant, a method of bonding a reactive substance (for example, silica sol, alumina sol, a silane coupling agent, an epoxy compound, an isocyanate compound, and the like) to the surface of the pigment are considered. The above surface treatment method,
It is described in "Properties and Applications of Metallic Soaps" (Koshobo), "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986). Among these pigments, those that absorb infrared rays are preferred because they are suitable for use in lasers that emit infrared rays. As such a pigment that absorbs infrared rays, carbon black is particularly preferred.

As the pigment to be added to the hydrophilic layer and the overcoat layer of the present invention, particularly, the surface is coated with a hydrophilic resin or silica sol so as to easily disperse with a water-soluble or hydrophilic resin and not to impair the hydrophilicity. Carbon black is useful.

The particle size of the pigment is preferably in the range of 0.01 μm to 1 μm, and more preferably in the range of 0.01 μm to 0.5 μm. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. As the disperser, an ultrasonic disperser,
Sand mills, attritors, pearl mills, super mills, ball mills, impellers, dispersers, KD mills, colloid mills, dynatrons, three-roll mills, pressure kneaders and the like can be mentioned. Details are described in “Latest Pigment Application Technology” (CMC Publishing, 1986).

As the dyes, commercially available dyes and literatures (for example, “Dye Handbook” edited by The Society of Synthetic Organic Chemistry, published in 1970,
"Chemical Industry", May 1986, p. 45-51 "Near-infrared absorbing dyes", "Development and market trends of functional dyes in the 1990s", Chapter 2, Section 2.3 (1990), or known dyes described in patents can be used. . Specifically, infrared absorbing dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, polymethine dyes, and cyanine dyes are preferred.

Further, examples of the infrared absorbing dye include, for example, JP-A-58-125246 and JP-A-59-84356.
Cyanine dyes described in JP-A-60-78787, JP-A-58-173696, JP-A-58-173696
181690, methine dyes described in JP-A-58-194595 and the like, JP-A-58-112793,
JP-A-58-224793, JP-A-59-48187
JP-A-59-73996, JP-A-60-5294
No. 0, naphthoquinone dyes described in JP-A-60-63744 and the like, squalilium dyes described in JP-A-58-112792 and the like, British Patent 434,8
No. 75, and US Pat. No. 4,756,9.
No. 93, a cyanine dye described in U.S. Pat. No. 4,973,572, a dye described in JP-A-10-268512, and a phthalocyanine compound described in JP-A-11-235883.

Further, US Pat.
No. 938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924;
No. 42645 (US Pat. No. 4,327,169)
Described in JP-A-58-18.
No. 1051, No. 58-220143, No. 59-413
No. 63, No. 59-84248, No. 59-84249
Pyrylium compounds described in JP-A-59-146063 and JP-A-59-146061;
Cyanine dyes described in U.S. Pat. No. 2,216,146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and Japanese Patent Publication Nos. 5-135514 and 5-19702.
Nos. 4,059,098, 4,098,098, 4,098,097, and 3,087,098. Also preferred are pyrylium compounds described in Japanese Patent Application Publication No. JP-A-2002-209, Epolite III-178, Epolite III-130, Epolite III-125 and the like. Among these, a particularly preferred dye to be added to the overcoat layer and the hydrophilic layer is a water-soluble dye, and specific examples are listed below by structural formulas.

[0073]

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[0074]

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The dye used in the ink receiving layer of the present invention may be the above-mentioned infrared absorbing dye, but is preferably a more lipophilic dye. More preferred dyes include the dyes exemplified below.

[0076]

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[0077]

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The addition ratio of the photothermal conversion agent is 1 to 50% by weight, preferably 2 to 20% by weight of the solid content in the hydrophilic layer. In the overcoat layer, 1 to 70% by weight of solids,
Preferably 2 to 50% by weight, when the photothermal conversion agent is a dye,
The proportion is particularly preferably 2 to 30% by weight, and when the photothermal conversion agent is a pigment, the proportion is particularly preferably 20 to 50% by weight. The addition ratio of the photothermal conversion agent to the ink receiving layer is preferably 20% by weight or less of the total solids of the ink receiving layer, and particularly preferably 15% by weight or less. Within these ranges, good sensitivity can be obtained without impairing the film strength of each layer.

As the support used in the present invention, a dimensionally stable plate is used. Paper, lipophilic plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate (eg, aluminum, zinc, copper, nickel, stainless steel plate, etc.),
Plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and the above metals are laminated or deposited Paper or plastic film etc. are included.

Preferred substrates are polyethylene terephthalate film, polycarbonate film, aluminum or steel plate, or aluminum or steel plate laminated with a lipophilic plastic film.

The aluminum plate used in the present invention is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and furthermore, a thin film of aluminum or an aluminum alloy laminated with plastic. It is. The foreign elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium,
There are chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Further, an aluminum plate from an aluminum ingot using the DC casting method or an aluminum plate from an ingot using the continuous casting method may be used. However, as the aluminum plate applied to the present invention, an aluminum plate of a conventionally known and used material can be appropriately used.

The thickness of the substrate used in the present invention is 0.05 mm to 0.6 mm, preferably 0.1 mm to 0.6 mm.
0.4 mm, particularly preferably 0.15 mm to 0.3 mm
It is.

Prior to using the aluminum plate, it is preferable to perform a surface treatment such as surface roughening and anodic oxidation. The surface treatment facilitates the adhesion to the ink receiving layer.

The surface roughening treatment of the aluminum plate surface is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. It is carried out by a method of selective dissolution. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. As a chemical method, a method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in JP-A-54-31187 is suitable. Further, as an electrochemical surface roughening method, there is a method of carrying out an alternating current or a direct current in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Also,
An electrolytic surface roughening method using a mixed acid as disclosed in JP-A-54-63902 can also be used.

The surface roughening by the above-mentioned method is performed when the center line average roughness (Ra) of the surface of the aluminum plate is from 0.2 to 1.0.
It is preferable that the coating be performed within a range of 0 μm. The roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide or sodium hydroxide as required, and further neutralized, and then anodized to enhance abrasion resistance if desired. Processing is performed.
As an electrolyte used for anodizing the aluminum plate, various electrolytes forming a porous oxide film can be used, and generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte. The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally, but generally the concentration of the electrolyte is 1 to 80% by weight.
Solution, liquid temperature is 5 to 70 ° C, current density is 5 to 60 A / dm ² ,
A voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are appropriate. The amount of the formed oxide film is 1.0-5.
0 g / m ^2, it is particularly preferably 1.5 to 4.0 g / m ^2.

The substrate used in the present invention may be a substrate having the above-mentioned surface treatment and having an anodized film as it is. However, it is necessary to further improve the adhesiveness with the upper layer and the heat insulation. Accordingly, Japanese Patent Application No. 2000-65219
And anodic oxide coating described in Japanese Patent Application No. 2000-14387, enlarging the micropores, sealing the micropores, and immersing the surface in an aqueous solution containing a hydrophilic compound. Can be done. Suitable hydrophilic compounds for the above-mentioned hydrophilization treatment include polyvinyl phosphonic acid, compounds having a sulfonic acid group, saccharide compounds, citric acid, alkali metal silicates, potassium zirconium fluoride, phosphates / inorganic fluorine compounds, and the like. Can be mentioned.

The heat-sensitive lithographic printing plate of the present invention forms an image by heat. Specifically, direct image-like recording using a thermal recording head or the like, scanning exposure using an infrared laser, high-intensity flash exposure such as a xenon discharge lamp, or infrared lamp exposure is used. Semiconductors that emit infrared light having a wavelength of 700 to 1200 nm are used. Exposure with a solid-state high-output infrared laser such as a laser or a YAG laser is preferable.

The image-exposed printing plate of the present invention can be mounted on a printing press without any further processing. Alternatively, it is also possible to attach a printing original plate to a printing press, perform laser exposure on the printing press, and then perform printing as it is. When printing is started using the ink and the fountain solution, the overcoat layer and the hydrophilic layer of the exposed area are removed by dissolution with the fountain solution, or transfer to a blanket, and further transfer to paper,
The ink is deposited on the exposed ink receiving layer, and a printed matter is obtained.

[0089]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 [Production Example of Aluminum Support] Aluminum 99.5
0.01% by weight of copper and 0.03% by weight of titanium
%, 0.3% by weight of iron and 0.1% by weight of silicon
0.24mm thickness of JISA1050 aluminum material
The rolled plate is made of 400 mesh pamistone (manufactured by Kyoritsu Ceramics).
Using a 20% by weight aqueous suspension and a rotating nylon brush
After graining the surface, it was thoroughly washed with water. this
15% by weight aqueous sodium hydroxide solution (aluminum 4.
5% by weight) to dissolve 5 g of aluminum
/ M^TwoAnd then rinse with running water
Was. Furthermore, neutralize with 1% by weight nitric acid aqueous solution, then 0.7 weight
In aqueous nitric acid solution (containing 0.5% by weight of aluminum)
A rectangle with a voltage of 10.5 V at the time of anode and a voltage of 9.3 V at the time of cathode
Wave alternating voltage (current ratio r = 0.90, Japanese Patent Publication No. 58-5)
796, the current waveform described in the embodiment).
160C / dm^TwoElectrolytic surface roughening treatment with the amount of electricity at the anode
went. After washing with water, 10% by weight of sodium hydroxide at 35 ° C
Immersion in aqueous solution, aluminum dissolution amount 1g / m ^Two
And then washed with water. Next, 50
Immersion in 30% by weight sulfuric acid aqueous solution
After that, it was washed with water. Further, a 20% by weight aqueous solution of sulfuric acid at 35 ° C.
DC current in liquid (containing 0.8% aluminum)
Then, a porous anodic oxide film forming treatment was performed. Sand
And a current density of 13 A / dm^TwoAnd electrolysis time
By adjustment, anodic oxide film weight 2.7 g / m^TwoSupport
Was prepared. After washing this support with water, sodium silicate at 70 ° C
Immersed in a 0.2% by weight aqueous solution of lithium, washed with water and dried
Was. 5mg / m as silicon^TwoMet. that's all
The support obtained as described above is a Macbeth RD920 counter
The reflection density measured by a densitometer is 0.30 and the center line average
The roughness Ra was 0.58 μm.

[Application of Ink Receiving Layer] On the above support,
An ink receiving layer coating solution (I) having the following composition was applied in an amount of 1
Coating was performed with a bar coater so as to be 1.25 ml / m ² . Thereafter, it was dried by heating at 100 ° C. for 1 minute to obtain an ink receiving layer having a dry coating amount of about 0.45 g / m ² .

(Ink Receiving Layer Coating Solution (I)) Phenotote YP-50 1.0 g Photothermal conversion agent (IR-24 described in this specification) 0.2 g Methyl ethyl ketone 13 g Propylene glycol monomethyl ether 12 g Here, phenothote YP -50 is a phenoxy resin manufactured by Toho Kasei Co., Ltd.

[Coating of hydrophilic layer] The following hydrophilic layer coating solution (1) was coated on the ink receiving layer thus formed with a bar, dried at 100 ° C for 1 minute, and dried at a dry coating amount of 0.1 µm. 39
g / m ² of the hydrophilic layer was obtained.

(Hydrophilic Layer Coating Solution (1)) Methanol silica (manufactured by Nissan Chemical Industries, Ltd .: colloid composed of a methanol solution containing silica having a particle size of 10 to 20 nm and 30% by weight) 3 g polyacrylic acid (weight average molecular weight 2. 50,000) 5% by weight methanol solution 2 g Methyl lactate 1 g Methanol 17.53 g

[Application of Overcoat Layer] On the hydrophilic layer, an overcoat layer coating solution having the following composition was applied by bar coating.
Dry at 100 ° C for 90 seconds, dry application weight 0.22g
A heat-sensitive lithographic printing plate having an overcoat layer of / m ² was prepared.

(Coating solution for overcoat layer) Gum arabic (28% by weight aqueous solution) 1.5 g Photothermal conversion agent (Dye IR-10 described in this specification) 0.042 g Polyoxyethylene nonylphenyl ether (containing 10% by weight) Aqueous solution) 0.168 g ion exchange water 22 g

The heat-sensitive lithographic printing plate was 240 m thick using a Trendsetter (a plate setter equipped with a 40 W 830 nm semiconductor laser) manufactured by Creo Corporation.
Exposure was performed with an energy of J / cm ² . The exposed original plate was attached to Komori Corporation's Lithrone printing machine without further processing, and the plate etch solution EU was used.
-3 (manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol (volume ratio 1/99/10) and a dampening solution using Geos G black ink manufactured by Dainippon Ink and Chemicals, Inc. When water and ink were operated at the same time and art-coated paper was supplied and printing was started, the ink was completely deposited on the fifth printout, and 20,000 good prints without stains were obtained thereafter. .

Example 2 Example 1 was repeated except that the ink receiving layer coating solution (II) having the following composition was used in place of the ink receiving layer coating solution (I) of Example 1.
In the same manner as in the above, a heat-sensitive printing original plate was produced.

(Ink Receiving Layer Coating Solution (I)) Phenotote YP-50 0.8 g Epicoat 1001 0.2 g Photothermal conversion agent (IR-24 described in this specification) 0.2 g Methyl ethyl ketone 13 g Propylene glycol monomethyl ether 12 g Here The Epicoat 1001 is an epoxy resin having a molecular weight of about 900 manufactured by Yuka Shell Epoxy Co., Ltd.

The heat-sensitive lithographic printing plate obtained as described above was exposed and printed in the same manner as in Example 1, and the ink was completely deposited on the fifth printout. Good printed matter without stain was obtained.

Example 3 A hydrophilic layer coating solution (2) having the following composition was coated on the ink receiving layer of Example 1 with a bar and dried at 100 ° C. for 1 minute.
A heat-sensitive lithographic printing plate precursor having a hydrophilic layer having a dry coating amount of 0.39 g / m ^{2 and} no overcoat layer was obtained.

(Hydrophilic Layer Coating Solution (2)) Methanol silica (same as in Example 1) 3 g Methanol solution containing 5% by weight of polyacrylic acid (weight average molecular weight: 25,000) 2 g Photothermal conversion agent (this specification) IR-10) 0.1 g methyl lactate 1 g methanol 17.53 g

The heat-sensitive lithographic printing plate thus obtained was exposed and printed in the same manner as in Example 1, and the ink was completely deposited on the fifth printing start. Good printed matter without stain was obtained.

[0104]

According to the present invention, it is possible to print by directly mounting on a printing machine without performing post-exposure processing.
A heat-sensitive lithographic printing plate having improved printing durability can be provided.

Continued on the front page F term (reference) 2H025 AA12 AB03 AC08 AD03 BH02 CB21 CB41 CB45 CB51 CC08 CC11 CC20 DA01 DA40 2H096 AA06 BA20 CA20 EA04 2H114 AA04 AA22 AA24 AA27 BA01 DA04 DA15 DA25 DA26 DA46 DA03 DA03 GA03 GA06 GA09 GA34 GA38

Claims (2)

[Claims] 1. On a support, (1) an ink receiving layer, and (2) a material selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony and transition metals. A heat-sensitive lithographic printing plate having a hydrophilic layer containing a colloidal particulate oxide or hydroxide of at least one element, wherein at least one of the ink-receiving layer and the hydrophilic layer contains a photothermal conversion agent. A heat-sensitive lithographic printing plate, wherein the ink receiving layer contains a phenoxy resin. 2. On a support, (1) an ink receiving layer,
(2) a hydrophilic layer according to claim 1, and (3) a hydrophilic overcoat layer removable on a printing press, wherein at least one of an ink receiving layer, a hydrophilic layer and a hydrophilic overcoat layer is provided. A heat-sensitive lithographic printing plate containing a light-to-heat conversion agent, wherein the ink-receiving layer contains a phenoxy resin.