JPH11123884A - Manufacture of original plate for direct-description type waterless lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture an original plate for a direct-description type waterless lithographic printing plate, improved in a resistance to printing. SOLUTION: In the manufacturing method of an original plate for a direct- description type waterless lithographic printing plate, in which a heat insulating layer, a heat sensitive layer and a silicone rubber layer are laminated sequentially on a substrate, a heat insulating layer composition, consisting of a compound having an epoxy compound and a carboxyl group, is applied on the substrate, then, the heat sensitive layer or a metallic thin film is formed under a condition that the epoxy group of the heat insulating layer composition remains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterless planographic printing plate precursor which can be printed without using dampening water, and more particularly to a direct drawing type waterless planographic printing plate precursor which can be directly made by laser light. Things.

[0002]

2. Description of the Related Art Direct plate making, in which an offset printing plate is produced directly from an original without using a plate making film, is simple, does not require skill, is quick in obtaining a printing plate in a short time, Utilizing features such as rationality that can be selected according to quality and cost from the system,
In addition to the light printing industry, it has begun to enter the general offset printing and gravure printing fields.

In recent years, new types of various lithographic printing materials have been developed in recent years due to rapid advances in output systems such as prepress systems, imagesetters, and laser printers.

[0004] These lithographic printing plates can be classified according to plate making methods: a method of irradiating a laser beam, a method of writing with a thermal head, a method of partially applying a voltage with a pin electrode,
A method of forming an ink repellent layer or an ink deposited layer by ink jet is exemplified.

[0005] Above all, the method of irradiating a laser beam is superior to other methods in terms of resolution and plate making speed.
There are many types.

[0006] The lithographic printing plate using the laser beam is further classified into two types, a photon mode by a photoreaction and a heat mode in which photothermal conversion is performed to cause a thermal reaction.

As the photon mode type, (1) a high-sensitivity PS plate using a photopolymer (2) an electrophotographic lithographic plate using an organic photoconductor or zinc oxide (3) a silver salt lithographic plate (4) a silver salt composite System lithography (5) Direct drawing master etc., and the heat mode type includes (6) Thermal destruction system lithography.

[0008]

However, (1)
The method uses an argon ion laser as the laser light source, which makes the equipment large, and the printing plate uses high-sensitivity photopolymer. There is a drawback that the property is easily reduced.

The electrophotographic lithographic method (2) has an advantage that it can be handled in a bright room, but since the dark decay becomes large within 2 to 5 minutes after charging of the photosensitive layer, the exposure and development process is performed in a short time after charging. Therefore, it is difficult to output a large format with high resolution.

In the silver salt method (3), printing plates corresponding to lasers of various wavelengths have been developed. However, there is a problem that silver waste liquid comes out, and since the sensitivity is high, care must be taken when handling. There is also a problem that requires.

The silver halide composite lithographic plate (4) is provided with a high-sensitivity silver halide emulsion layer on a photosensitive layer, exposing the upper silver halide emulsion layer with an argon ion laser, developing it, and further using the mask as a mask. Exposure and development are performed with ultraviolet rays. However, since this printing plate has two exposure and development steps, there is a problem that the processing of the printing plate becomes complicated.

The direct drawing master (5) does not directly write on a printing plate with a laser, but transfers a toner image formed by a laser printer onto a printing plate as an ink-coated portion. However, the resolution of the printing plate is inferior to other methods.

For the above photon mode type,
The thermal destruction method (6) has an advantage that it can be handled in a bright room, and its usefulness has recently been reviewed due to the rapid progress of a semiconductor laser as a light source.

For example, JP-A-6-199064,
US Pat. No. 5,339,737, US Pat. No. 5,353,705, EP 0580393, JP-A-6-5572.
No. 3, EP0573091, USP 5378
No. 580 discloses a direct drawing type waterless planographic printing plate precursor using a laser beam as a light source.

The heat-sensitive layer of these heat-destructive printing plate precursors is composed of carbon black as a laser light absorbing compound and nitrocellulose as a thermal decomposition compound. It is converted into heat energy, and the heat energy destroys the heat-sensitive layer. Finally, by removing the portion where the heat-sensitive layer has been destroyed by development, the silicone rubber layer on the surface is simultaneously peeled off to form an ink-filled portion.

However, these printing plates have a problem that the absorptance of the laser beam is not sufficient and the sensitivity of the printing plate is low.

This is because the primary particle size of the carbon black used is not appropriate. That is, the primary particle diameters of the carbon blacks used in the above publication are all 30 μm or more, and they do not always efficiently absorb the light of the semiconductor laser (wavelength around 800 nm) used.

This is one measure of the absorption efficiency of the laser beam. The optical density of the printing plate at the above-mentioned particle diameter is:
It is clear from the fact that it does not reach the maximum. That is, the optical density is maximum when the particle diameter is around 20 μm, and when the particle diameter is larger than 30 μm, the reflection of light on the surface increases and the optical density decreases.

Even if the particle diameter is smaller than 15 μm, the optical density decreases. This is because the carbon black itself tends to have transparency when the particle diameter is small, and the dispersibility of the particles is low.

Further, in each of the above publications, carbon black has a high lubricating amount, that is, has a high-structure structure, so that particles are aggregated with each other, and the viscosity of the heat-sensitive layer solution becomes high, so that it can be handled. There were also problems such as inconvenience and a non-uniform coating film.

In addition, Japanese Patent Laid-Open No. 6-5572
No. 3, EP0573091, USP 5378
In Japanese Patent Publication No. 580, there is another problem that an exposure apparatus becomes considerably large because an Nd-YAG laser is used as a light source.

On the other hand, US Pat. No. 5,379,698 proposes a direct drawing type waterless lithographic printing plate using a metal thin film as a heat-sensitive layer.

Since this printing plate material has a very thin heat-sensitive layer, a very sharp image can be obtained, which is advantageous in terms of the resolution of the printing plate. However, there has been a problem that the heat-sensitive layer in the non-image area is peeled off and ink adheres to the print, resulting in a defect on printed matter. In addition, the adhesiveness with the silicone rubber layer, which is the upper layer of the heat-sensitive layer, is not sufficient, and insufficient printing durability due to insufficient adhesiveness between these layers is a fatal drawback of this printing plate. Needed to be resolved.

In order to improve the disadvantages of the prior art, the present invention has been studied by focusing on the adhesiveness between the heat-sensitive layer and the heat-insulating layer, particularly when a metal thin film is used as the heat-sensitive layer. It was found that printing durability was improved by forming a heat-sensitive layer on the heat-insulating layer under the conditions described in (1).

That is, an object of the present invention is to produce a direct-drawing waterless planographic printing plate having excellent printing durability by improving the adhesion between the heat-sensitive layer and the heat insulating layer.

[0026]

SUMMARY OF THE INVENTION An object of the present invention is to provide a direct-drawing waterless planographic printing plate precursor in which a heat insulating layer, a heat-sensitive layer, and a silicone rubber layer are sequentially laminated on a substrate. A direct drawing type waterless coating characterized in that a heat insulating layer composition comprising an epoxy compound and a compound having a carboxyl group is applied and a metal thin film as a heat sensitive layer is formed in a state where the epoxy group of the heat insulating layer composition remains. This is achieved by a method for producing a lithographic printing plate precursor.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, the direct drawing type refers to a type in which an image is formed directly from a recording head on a printing plate without using a negative or positive film at the time of exposure.

In the present invention, the substrate is not particularly limited as long as it is a dimensionally stable plate-like material, and known metals, films and the like can be used. Examples of such a dimensionally stable plate-like material include those conventionally used as a substrate of a printing plate, and they can be suitably used.
Specifically, paper, plastic (for example, polyethylene,
Paper laminated with polypropylene, polystyrene, etc.), for example, a metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., for example, cellulose, carboxymethylcellulose, cellulose acetate, polyethylene terephthalate, polyethylene, Polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetate
A plastic film such as a metal, a paper or a plastic film on which a metal is laminated or vapor-deposited as described above.

Of these substrates, the aluminum plate is particularly preferable because it is extremely stable in dimension and inexpensive. Also used as a substrate for light printing,
A polyethylene terephthalate film is also preferred.

In the present invention, a heat-insulating layer composition comprising an epoxy compound and a compound having a carboxyl group is applied onto the above-mentioned substrate, and the metal layer serving as the heat-sensitive layer is applied while the functional groups of the heat-insulating layer composition remain. It is important to form a thin film.

The functional groups of these compounds constituting the heat-insulating layer composition are such that the functional groups cross-link and cure by heating, and are cured. In the conventional method for producing a direct drawing type waterless planographic printing plate precursor, The heat-sensitive layer was formed after the heat-insulating layer composition was sufficiently crosslinked. However, in the present invention, before forming the heat-sensitive layer, only a part of the functional groups in the heat-insulating layer composition is crosslinked, and after forming the heat-sensitive layer of the metal thin film, the remaining functional groups undergo a cross-linking reaction. . During the crosslinking reaction of the remaining functional groups, at the same time, the heat-insulating layer composition and the metal constituting the heat-sensitive layer are chemically bonded to each other, and the adhesion between the heat-insulating layer and the metal thin film is strengthened. Is achieved.

The reaction of the functional group in the heat-insulating layer composition can be carried out at room temperature without heating, but a method of performing a crosslinking reaction by heating is preferred from the viewpoint of productivity and workability. There is also an advantage that the degree of crosslinking can be easily adjusted by heating conditions.

In particular, when the heat-sensitive layer is formed, if the surface to which the heat-insulating layer composition is applied has tackiness, the workability deteriorates. Is preferably subjected to a cross-linking reaction, followed by forming a heat-sensitive layer of a metal thin film, and then further heating to cross-link the remaining functional groups in the heat insulating layer composition.

The epoxy compound contained in the heat insulating layer composition includes an epoxy compound obtained by reacting a hydroxyl-containing compound with epihalohydrin.

The following are specific examples of the hydroxyl group-containing compound.

(1) Monofunctional hydroxyl group-containing compound Specific examples include methanol, ethanol, propanol, pentanol, cyclohexanol, octanol, undecanol, bornyl alcohol and the like.

(2) Polyfunctional hydroxyl group-containing compound Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 2,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-butene-1,4-diol, 5-hexene-
1,2-diol, 7-octene-1,2-diol,
3-mercapto-1,2-propanediol, hydroquinone, dihydroxyanthraquinone, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, bisphenol A, bisphenol S, phenol formaldehyde novolak resin, resole resin, resorcinbenzaldehyde resin,
Pyrogallol acetone resin, hydroxystyrene polymer and copolymer, glycerin, diglycerin, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, polyvinyl alcohol, cellulose and derivatives thereof And hydroxyethyl (meth) acrylate polymers and copolymers.

In addition, those obtained by adding ethylene oxide or propylene oxide to each of the hydroxyl groups of the above-mentioned hydroxyl group-containing compounds can also be used.

Each of these epoxy compounds can be used alone, or a plurality of them can be used as a mixture.

Further, as a crosslinking agent in the heat insulating layer composition,
It is preferable to contain at least one compound selected from the group consisting of an amine compound and an amine adduct compound, and to crosslink a functional group from this, from the viewpoint of solvent resistance during printing and printing durability.

Here, the amine compound and the amine adduct compound will be described.

Examples of the amine compound include polyamines represented by the following general formula (1).

[0043]

Embedded image (Wherein R ¹ and R ² are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an aryl group, etc. Preferably, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and isopropyl Group, n-butyl group, sec-butyl group, hydroxymethyl group, hydroxypropyl group, chloromethyl group, bromomethyl group, phenyl group, p-hydroxyphenyl group, p
-Bromophenyl group, p-tolyl group, o-tolyl group, benzyl group and the like.

A represents a divalent linking group, and is specifically represented by the general formula-(A ¹ ) _p- (A ² ) _q- . Where A
¹ is a substituted or unsubstituted cyclic or acyclic alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted phenylene, and the substituent is an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an aryl group. And the like. A ² is,
-O-B ^1- , -SB ^2- , -NH-B ^3- , -CO
—O—B ⁴ —, —SO ₂ —NH—B ⁵ —, wherein B ¹ ,
B ² , B ³ , B ⁴ and B ⁵ are the same as A ¹ described above. p represents an integer of 1 or more, and q represents 0 or an integer of 1 or more. As specific examples of the divalent or higher valent amine compound represented by the general formula (1), dioxyethylene diamine, trioxyethylene diamine, tetraoxyethylene diamine, pentaoxyethylene diamine, hexaoxyethylene diamine, peptaoxyethylene diamine, octaoxyethylene diamine, Nonaoxyethylenediamine, decaoxyethylenediamine, tritriacontaoxyethylenediamine, monooxypropylenediamine, dioxypropylenediamine, trioxypropylenediamine, tetraoxyethylenediamine, pentaoxypropylenediamine, hexaoxypropylenediamine, heptaoxypropylenediamine, octaoxy Propylene diamine, nonaoxypropylene diamine,
Decaoxypropylenediamine, tritriacontaoxypropylenediamine, polymethylenediamine, polyetherdiamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropyl Amines, diethylaminopropylamine, aliphatic polyamine compounds such as substituted polyamines, m-xylylenediamine, aliphatic polyamine compounds having an aromatic ring such as tetrachloro-p-xylylenediamine, menthanediamine,
Alicyclic polyamines such as N-aminoethylpiperazine, 1,3-diaminocyclohexane, and isophoronediamine;
m-phenylenediamine, diaminodiphenyl ether, 4,4'-methylenedianiline, diaminodiphenylsulfone, benzidine, 4,4'-bis (o-toluidine), 4,4'-thiodianiline, o-phenylenediamine, dianisidine, methylenebis (O-chloroaniline), 2,4-toluenediamine, bis (3,4-diaminophenyl) sulfone, diaminoditrisulfone,
4-chloro-o-phenylenediamine, 4-methoxy-
Examples thereof include aromatic polyamine compounds such as 6-methyl-m-phenylenediamine and m-aminobenzylamine, dicyandiamide, and adipic dihydrazide.

Further, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole and the like can also be mentioned.

Further, there may be mentioned a polyamidoamine obtained by reacting the above-mentioned polyamine compound with a carboxylic acid so that both terminals become amino groups.

Further, amino group-containing resins such as urea resins and melamine resins may be used.

Further, examples of the amine adduct compound include those obtained by reacting the above-mentioned polyamine compound with an epoxy compound. Here, the epoxy compound means the same as the epoxy compound described above.

These amine compounds and amine adduct compounds may be used alone or in combination of two or more.

Among the above crosslinking agents, storage stability of the solution,
From the viewpoint of curing speed, amine adduct compounds, imidazoles, aromatic amines, and alicyclic amines are preferred.

In the present invention, the compounds having a carboxyl group contained in the heat insulating layer composition include the following.

(1) Compound wherein the above-mentioned amine compound and carboxylic acid are reacted at a ratio at which at least one terminal is a carboxyl group. Specific examples of carboxylic acid include the following. Not limited.

Malonic acid, succinic acid, malic acid, thiomalic acid, racemic acid, citric acid, glutaric acid, adipic acid,
Pimelic acid, spearic acid, azelaic acid, sebacic acid,
Divalent organic carboxylic acids such as maleic acid, fumaric acid, itaconic acid and dimer acid; trivalent organic carboxylic acids such as trimellitic acid; and 3,9-bis (2-carboxyalkyl)
2,4,8,10-tetraoxaspiroundoundane and the like.

Further, a carboxy-modified unvulcanized rubber can be used. Specifically, natural rubber, butadiene,
Isoprene, styrene, acrylonitrile, carboxy-modified homopolymer or copolymer selected from acrylates, such as carboxy-modified polybutadiene, carboxy-modified styrene-butadiene copolymer, carboxy-modified acrylonitrile-butadiene copolymer,
Examples include carboxy-modified methyl methacrylate-butadiene copolymer.

Further, a compound obtained by subjecting the above polyvalent carboxylic acid to an esterification reaction with polyethylene glycol or polypropylene glycol can also be used. The compound preferably has carboxyl groups at both ends.

(2) α, β-Unsaturated Compound Having One or Two Carboxyl Groups in the Molecule Specific examples thereof include acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, maleic acid, Maleic amide, maleic imide, itaconic acid, crotonic acid, fumaric acid, mesaconic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl Examples include phthalic acid and 2-acryloyloxyethyl hexahydrophthalic acid.

In addition, these carboxyl groups are added to the molecule
Polymers of α, β-unsaturated compounds having one or two and crosslinked products thereof can also be preferably used.

Examples of other copolymerizable monomer components include known α-olefins, vinyl compounds, and vinylidene compounds. Specific examples include ethylene, propylene, isobutylene, 1-butylene, and diisobutylene. , Methyl vinyl ether, styrene, vinyl acetate, acrylate, methacrylate, acrylonitrile, and the like.

Further, it is more preferable that the heat insulating layer composition contains a phosphorus-containing compound from the viewpoint of solvent resistance and printing durability during printing. The preferred phosphorus-containing compounds in the present invention include the following. That is, phosphoric acid, alkyl phosphoric acid,
Aryl phosphoric acid, alkyl phosphite, aryl phosphite, unsaturated alkyl phosphite, unsaturated allyl phosphite,
Unsaturated alkyl phosphate, unsaturated allyl phosphate and the like.

Of these, unsaturated alkyl phosphates are particularly preferred. Specific examples of these unsaturated alkyl phosphates include those represented by the following general formula (2).

[0061]

Embedded image (Wherein R represents a hydrogen atom or an alkyl group, n represents an integer of 0 or more, and a and b each represent an integer of 1 or more.) In particular, R in the general formula (2) is a methyl group. It is preferable that n is 0 or 1, and a and b are each 1 or 2.

In the present invention, in addition to the epoxy compound, the crosslinking agent, the compound having a carboxyl group, and the phosphorus-containing compound, a binder polymer, a coloring agent,
A dispersant, a leveling agent, an adhesive and the like can be appropriately contained as needed.

Examples of the binder polymer include polyolefins, polystyrenes, (meth) acrylate polymers, unvulcanized rubbers, polyoxides, polyesters, polyurethanes, polyamides and the like. Among these, polyesters and polyurethanes are preferred.

As the coloring agent, known organic and inorganic pigments, dyes, metal powders and the like can be used.

Known adhesives such as silane coupling agents and organic titanates can be used as the adhesive.
Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-glycidoxytrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.

The above heat insulating layer composition is prepared as a composition solution by dissolving in a suitable organic solvent such as dimethylformamide (DMF), methyl ethyl ketone, methyl isobutyl ketone, dioxane, toluene, xylene, tetrahydrofuran (THF). The heat insulating layer composition solution can be applied on a substrate by a known method.

Thereafter, the solvent is volatilized, and only a part of the functional groups in the heat insulating layer composition undergoes a crosslinking reaction. At this time, it is preferable to crosslink by heating to 60 to 120 ° C at the temperature reached by the substrate, and more preferably 60 to 100 ° C.

After forming a heat-sensitive layer, which will be described later, on the heat-insulating layer in which a part of the functional groups is cross-linked as described above, heating is further performed to cause a cross-linking reaction of the remaining functional groups in the heat-insulating layer. The temperature at this time is preferably in the range of 150 to 260 ° C. as the ultimate temperature of the substrate, and more preferably in the range of 180 to 240 ° C.

The thickness of the heat-insulating layer is preferably 0.5 to 50 g / m ² , more preferably 1 to 10 g / m ² , as a coating layer after the evaporation of the solvent. When the thickness is less than 0.5 g / m ² , the effect of blocking morphological defects and chemical adverse effects on the substrate surface is inferior, and when the thickness is more than 50 g / m ^2, it is disadvantageous from an economic point of view.

Preferred examples of the composition of the heat insulating layer in the present invention are shown below.

(1) 50 to 100 parts by weight of an epoxy compound (2) 10 to 50 parts by weight of a crosslinking agent (3) 5 to 30 parts by weight of a compound having a carboxyl group (4) 0.01 to 1 part by weight of a phosphorus-containing compound 5) Binder polymer 0 to 80 parts by weight (6) Colorant 0 to 10 parts by weight (7) Adhesive 0 to 10 parts by weight (8) Leveling agent 0 to 5 parts by weight More preferable composition is (1) epoxy compound 60 100 parts by weight (2) Crosslinking agent 10 to 40 parts by weight (3) Compound having a carboxyl group 5 to 20 parts by weight (4) Phosphorus-containing compound 0.05 to 0.5 part by weight (5) Binder polymer 0 to 80 Parts by weight (6) coloring agent 1 to 5 parts by weight (7) adhesive 0 to 10 parts by weight (8) leveling agent 0 to 5 parts by weight.

Next, the heat-sensitive layer in the present invention will be described.

In the present invention, it is important that the heat-sensitive layer is made of a metal thin film, efficiently absorbs the laser beam, and evaporates or melts instantaneously or partially by the heat.

In order to efficiently absorb laser light, the absorptance for the wavelength (around 800 nm) of a semiconductor laser used as a light source is important. The optical density of the heat-sensitive layer can be used as an index of the absorptivity for light near 800 nm, and it can be said that the higher the optical density, the more efficiently the laser light can be absorbed.

In the present invention, the optical density of the heat-sensitive layer is 0.5.
It is preferably from 6 to 2.3, and more preferably from 0.8 to 1.8.

When the optical density is lower than 0.6, the sensitivity of the printing plate tends to decrease because the laser light is not efficiently absorbed. When the optical density is higher than 2.3, the heat-sensitive layer is not used with a normal energy amount. The laser beam stops reaching the film of
As a result, extra energy is required to form an image, and the sensitivity tends to decrease.

Here, the optical density means the Ratten filter No. Using Macbeth densitometer RD-106
The numerical value when the measurement is performed at 514.

From the viewpoint of the sensitivity of the printing plate, the melting point of the metal is very important. That is, if the melting point is too high, the metal does not melt or change in evaporation or the like even when irradiated with laser light. In the present invention, the melting point of the metal constituting the heat-sensitive layer is preferably 2000 (K) or less.

Specific examples of such metals include barium, beryllium, bismuth, calcium, cerium, cobalt, copper, erbium, europium, iron, gadolinium, germanium, holmium, lanthanum, lutetium, magnesium, manganese, neodymium, nickel,
Lead, palladium, polonium, praseodymium, radium, antimony, scandium, silicon, samarium,
Tin, strontium, terbium, tellurium, thorium, titanium, thallium, thulium, yttrium, zinc, gallium, selenium and the like.

Among these, the melting point is more preferably 930 (K) or less from the viewpoint of the sensitivity of the printing plate. Specific examples of such a metal include tellurium, tin, antimony, gallium, magnesium, polonium, selenium, thallium, zinc, bismuth and the like. These metals are preferable when they are formed into a vapor-deposited film because a pattern can be easily formed by laser light.

However, conversely, even if the melting point is too low, the shape retention of the printing plate is apt to be deteriorated. Therefore, a particularly preferable range of the melting point is 500 (K) to 930 (K).

These metals are particularly preferable when they are made of two or three kinds of alloys, because the melting point can be easily adjusted and the sensitivity as a printing plate can be improved.

In the case of an alloy, various products can be produced depending on the combination of metals.
It can be used in an appropriate combination from metals of 0 (K) or less. Among them, two or three kinds of metals of tellurium, tin, antimony, gallium, bismuth and zinc are preferable from the viewpoint of ease of handling.

As a specific combination, the two alloys include tellurium / tin, tellurium / antimony, tellurium / gallium, tellurium / bismuth, tellurium / zinc, and tin / tin.
Antimony, tin / gallium, tin / bismuth, tin /
Zinc is preferred, more preferably tellurium / tin, tellurium / antimony, tellurium / zinc, tin / antimony, tin / zinc.

The three alloys include tellurium / tin / antimony, tellurium / tin / gallium, tellurium / tin / bismuth, tellurium / tin / zinc, tellurium / zinc / antimony, tellurium / zinc / gallium, and tellurium / zinc / bismuth. , Tin / zinc / antimony are preferred, more preferably tellurium / tin / antimony, tellurium / tin / zinc,
Tin / zinc / antimony.

At this time, the thickness of the thin film also greatly affects the sensitivity of the printing plate. That is, if the film thickness is too thick, the energy required for evaporating and melting the thin film becomes extra, and the sensitivity of the printing plate is reduced.

For this reason, the thickness is preferably 1000 Å or less, more preferably 200 Å or less.

As a method of forming such a metal thin film,
It is preferable to carry out by any of vacuum deposition and sputtering.

Vacuum evaporation is a method in which a metal is heated and evaporated in a vacuum vessel of 10 ⁻⁴ to 10 ⁻⁷ mmHg to form a thin film on the surface of a substrate.

The sputtering is performed at 10 ^-1 to 10 ^-3 mmH
In this method, a DC or AC voltage is applied to a pair of electrodes in a reduced-pressure container of g to generate glow discharge, and a thin film is formed on a substrate by using a sputtering phenomenon of a cathode.

Next, the silicone rubber layer will be described.
In the present invention, the silicone rubber layer may be composed of the same composition as the silicone rubber layer in the conventional waterless planographic printing plate precursor.

Examples of such a silicone rubber composition include those obtained by sparsely cross-linking a linear organopolysiloxane (preferably dimethylpolysiloxane). As a typical example, the following formula (3) )), Those having a repeating unit as shown in (1).

[0093]

Embedded image (Here, n is an integer of 2 or more. R has 1 to 10 carbon atoms.)
Alkyl, aryl, or cyanoalkyl group. Preferably, 40% or less of the whole R is vinyl, phenyl, vinyl halide, or halogenated phenyl, and 60% or more of R is a methyl group. Further, it has at least one or more hydroxyl group in the molecular chain at the chain end or in the form of a side chain. In the present invention, the silicone rubber layer is a silicone rubber which performs condensation type crosslinking (RTV, LTV type silicone rubber).
It is preferable to be formed by. In such a silicone rubber, a part of R of the organopolysiloxane chain is H.
Can be used, but it is usually crosslinked by condensation of terminal groups represented by the following formulas (4) and (5) or (6). An excess of a crosslinking agent may be present in this.

[0094]

Embedded image (Here, R is the same as R described in Formula (3).)

Embedded image (Where R is the same as R described in formula (3), and R1 and R2 are monovalent lower alkyl groups.)

Embedded image (Here, R is the same as R described in the formula (3), and Ac is an acetyl group.) Such a silicone rubber composition that performs condensation type crosslinking includes tin, zinc, lead, and calcium. Metal carboxylate, such as manganese, for example, dibutyltin laurate, tin (II)
A catalyst such as octoate, naphthenate, or chloroplatinic acid is added.

In addition to this, it is optional to add a hydrolyzable functional group-containing silane (or siloxane) which is a condensed silicone rubber composition. Is optional.

Further, in the present invention, an addition type silicone rubber composition may be used for the silicone rubber layer in addition to the condensation type silicone rubber composition described above.

Next, the addition type silicone rubber composition will be described. Examples of the addition type silicone rubber composition used in the present invention include a polyorganosiloxane having at least two vinyl groups in a molecule, a polyorganosiloxane having at least three SiH groups in a molecule, and a platinum compound. A silicone rubber layer is formed by diluting this with a suitable solvent, applying it on the heat-sensitive layer, drying by heating and curing.

At this time, examples of the organopolysiloxane having at least two vinyl groups in the molecule include those having a vinyl group at either the terminal or middle of the molecular chain, and those which are preferable as organic groups other than alkenyl groups. Is
It is a substituted or unsubstituted alkyl group or aryl group.
Further, it may contain a trace amount of hydroxyl group.

Specific examples of the polyorganosiloxane having two or more vinyl groups in the molecule include the following, but the present invention is not limited thereto.

Polydimethylsiloxane having vinyl groups at both terminals, (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals, (methylvinylsiloxane) (dimethylsiloxane) copolymer having vinyl groups at both terminals, A compound in which two or more molecules of a polydimethylsiloxane having a vinyl group have a dimethylene bridge between main chains, a (methyl 1-hexene siloxane) (dimethyl siloxane) copolymer having a methyl group at both ends, and a (methyl 1-hexene) having a vinyl group at both ends. Siloxane) (dimethylsiloxane) copolymer.

These vinyl group-containing polysiloxanes preferably have a molecular weight of 5,000 or more, more preferably 10,000 or more, from the viewpoint of rubber properties after curing. In addition, these vinyl group-containing polysiloxanes can be used alone, or a plurality of types can be used by mixing at an arbitrary ratio.

Examples of the polyorganosiloxane having at least three SiH groups in the molecule include those having a SiH group at either the molecular chain terminal or in the middle, and those preferable as organic groups other than the SiH group are substituted or substituted. Unsubstituted alkyl and aryl groups.

Specific examples of the polyorganosiloxane having at least three SiH groups in the molecule include the following, but the present invention is not limited thereto.

Polydimethylsiloxane having SiH groups at both terminals, polymethylhydrogensiloxane having methyl groups at both terminals, (methylhydrogensiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals, SiH groups at both terminals
(Methyl hydrogen siloxane) (dimethyl siloxane) copolymer, cyclic polymethyl hydrogen siloxane and the like.

Among these, those which can be preferably used in the present invention include at least three S
The value obtained by dividing the number of SiH groups in the polyorganosiloxane having an iH group by the molecular weight is preferably 0.001 mol / g or more, more preferably 0.002 mol / g or more. If the amount is less than 0.001 mol / g, the curing rate is undesirably reduced.

These SiH group-containing polyorganosiloxanes can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The organic groups of the polyorganosiloxane having a vinyl group and the polyorganosiloxane having a SiH group have a total of 60 groups in terms of improving the ink repellency.
% Or more is preferably a methyl group.

The ratio of the mixture of the vinyl group-containing polyorganosiloxane and the SiH group-containing polyorganosiloxane may be 1.5 to 1.5 when the number of vinyl groups in the silicone rubber composition is 1. A mixing ratio of 15 is preferable, and more preferably 1.5 to
12 is preferred.

When the number of SiH groups relative to the number of vinyl groups is 1.5
If less than, the curability of the silicone rubber layer decreases,
If it is more than 15, the silicone rubber becomes brittle and the wear resistance is undesirably reduced.

The platinum compound contained in the addition type silicone rubber composition is not particularly limited, but includes platinum alone, platinum chloride, chloroplatinic acid, olefin-coordinated platinum and the like. Among these, olefin-coordinated platinum is preferable.

In order to control the curing rate of the addition type silicone rubber composition, tetracyclo (methyl vinyl)
Vinyl group-containing organopolysiloxane such as siloxane, alcohol containing carbon-carbon triple bond, acetone,
It is preferable to add a reaction inhibitor such as methyl ethyl ketone, methanol, ethanol, and propylene glycol monomethyl ether.

The addition type silicone rubber composition preferably used in the present invention includes the following.

(1) 100 parts by weight of a polyorganosiloxane having at least two vinyl groups in a molecule (2) 0.1 to 10,000 parts by weight of a polyorganosiloxane having at least three SiH groups in a molecule (3) Platinum Compound 0.00001 to 10 parts by weight (4) Reaction inhibitor 0.1 to 10 parts by weight (5) Solvent 100 to 4000 parts by weight In addition to these compositions, a hydroxyl group-containing organopoly which is a condensation type silicone rubber composition It is optional to add siloxane or a hydrolyzable functional group-containing silane (or siloxane), and it is also optional to add a known filler such as silica for the purpose of improving rubber strength.

In the present invention, the condensation type and addition type silicone rubber compositions preferably contain a silane coupling agent in addition to the above composition.

Specific examples of the silane coupling agent include:
Known materials such as vinyl silane, (meth) acryloyl silane, epoxy silane, amino silane, mercapto silane and chloro silane can all be used, and among them, (meth)
Acryloyl silane, epoxy silane, amino silane,
Mercaptosilane is preferred.

Of these, epoxysilane is particularly preferred. Specific examples of epoxysilane include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

These silane coupling agents are preferably used at a ratio of 0.1 to 5% by weight, more preferably 0.5% by weight, based on the solid content of the silicone rubber layer composition.
３3% by weight.

The thickness of the silicone rubber layer is 0.5
To 50 g / m ² , more preferably 0.5 to 50 g / m ^2.
10 g / m ² . When the film thickness is less than 0.5 g / m ² , the ink repellency of the printing plate tends to decrease, and
If it is larger than m ² , it is disadvantageous from an economic point of view.

Further, for the purpose of protecting the silicone rubber layer, a thin protective film treated with a plane or uneven surface is laminated on the surface of the silicone rubber layer, or the surface of the silicone rubber layer is developed as described in JP-A-5-323588. It is also possible to form a coating of the polymer that dissolves in the solvent.

In particular, when a protective film is laminated, laser exposure is performed from above the protective film, and then the protective film is peeled off to form a pattern on the printing plate. It can also be created.

Preferred specific examples of the method for producing the direct-drawing waterless planographic printing plate precursor of the invention described above include the following method.

That is, a normal coater such as a reverse roll coater, an air knife coater, or a Mayer bar coater, or a rotary coating device such as a wheyer is used.
A heat insulating layer composition comprising an epoxy compound and a compound having a carboxyl group is applied on a substrate,
After curing for several minutes, a heat-sensitive layer is formed by vapor-depositing or sputtering a metal, followed by heating to cause a cross-linking reaction of the remaining functional groups in the heat-insulating layer, further applying a silicone rubber composition, and heating at 50 to 150 ° C. The rubber is cured by heating at a temperature for several minutes to form a silicone rubber layer. If necessary, a protective film is laminated on the silicone rubber layer, or a protective layer is formed to produce a desired direct-drawing waterless planographic printing plate precursor.

Further, the direct drawing type waterless planographic printing plate precursor thus obtained is imagewise exposed to laser light from a silicone rubber layer or a protective film, or after peeling off the protective film.

The light source of the laser beam used for the exposure includes an Ar ion laser, a Kr ion laser, a He—Ne laser, a He—Cd laser, a ruby laser, a glass laser, and an oscillation wavelength in the range of 300 nm to 1500 nm.
Various lasers such as a semiconductor laser, a YAG laser, a titanium sapphire laser, a dye laser, a nitrogen laser, and a metal vapor laser can be used. Among them, a semiconductor laser is preferable because it is downsized due to recent technological advances and is economically more advantageous than other laser light sources.

The direct-drawing type waterless planographic printing plate exposed by the above method is subjected to peeling development or solvent development as required.

In the solvent developing treatment, a developer preferably used is water, a solution obtained by adding the following polar solvent to water, an aliphatic hydrocarbon (hexane, heptane, isoparaffin hydrocarbon, gasoline, kerosene). ), Aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (tricrene, etc.) and at least one mixed solvent to which at least one of the following polar solvents is added. .

As the polar solvent, alcohols (methanol, ethanol, propanol, isopropanol,
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, hexylene glycol, 2-ethyl-1 , 3-hexanediol, etc.), ethers (ethylene glycol monoethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dioxane, Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.)
Diacetone alcohol, etc., esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), Carboxylic acids (2-ethylbutyric acid, caproic acid,
Caprylic acid, 2-ethylhexanoic acid, capric acid, oleic acid, lauric acid, etc.).

Further, a known surfactant may be added to the above developer composition. Further, an alkali agent such as sodium carbonate, monoethanolamine, diethanolamine, diglycolamine, monoglycolamine, triethanolamine, sodium silicate, potassium silicate, potassium hydroxide, sodium borate and the like can be added. .

To these developing solutions, known basic dyes such as crystal violet, Victor Pure Blue, Astrazone Red, etc., acid dyes and oil-soluble dyes are added to simultaneously develop and dye the image area. Can be.

In the development, the developer can be developed by impregnating a nonwoven fabric, absorbent cotton, cloth, sponge or the like with such a developer and wiping the plate surface.

Further, using an automatic developing machine as described in JP-A-63-163357, the plate surface is pre-treated with the above developing solution, and then the plate surface is rubbed with a rotating brush while showering with tap water or the like. Thereby, development can be suitably performed.

Development can also be performed by spraying hot water or steam onto the plate instead of the above-mentioned developer.

Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

[0134]

【Example】

Example 1 A heat insulating layer solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.24 mm, dried at 80 ° C. for 1 minute, and 4 g of a part of functional groups in the heat insulating layer composition crosslinked. / M
^Two heat insulating layers were provided.

(A) Denacol EX411 (epoxy compound manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) Reaction product of isophoronediamine and phenylglycidyl ether 20 parts by weight (c) Light ester HO-MP (carboxyl group-containing compound) 10 parts by weight (d) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 part by weight (e) Light ester PM (phosphorus-containing compound manufactured by Kyoeisha Chemical Co., Ltd.) 0.5 part by weight (f) 480 parts by weight of dimethylformamide Next, tellurium (melting point: 722 K) was formed on the heat-insulating layer by vacuum vapor deposition, and after providing the heat-sensitive layer, it was heated at 200 ° C. for 1 minute.

Next, a silicon having the following composition
Apply a rubber solution and dry at 120 ° C for 2 minutes.
g / m ² of a silicone rubber layer was provided.

(A) 100 parts by weight of α, ω-divinylpolydimethylsiloxane (degree of polymerization 770) (b) HMS-501 (methyl (methyl hydrogen siloxane) (dimethyl siloxane) copolymer at both ends Hwt% = about 0.7 Chisso Corporation 4 parts by weight (c) SZ6040 (epoxy group-containing silane compound manufactured by Toray Dow Corning Silicone Co., Ltd.) 5 parts by weight (d) Olefin coordinated platinum 0.02 parts by weight ( e) Reaction inhibitor 0.3 parts by weight (f) "Isopar E" (isoparaffin-based hydrocarbon manufactured by Exxon Chemical Co., Ltd.) 990 parts by weight An 8 μm-thick polyester film was added to the laminate obtained as described above. "Lumirror" (manufactured by Toray Industries, Inc.) was laminated using a calendar roller to obtain a direct-drawing waterless planographic printing plate precursor.

After that, the "Lumirror" of the printing plate precursor was peeled off, and the semiconductor laser (SL) mounted on the XY table was removed.
D-304XT, output 1 W, wavelength 809 nm, manufactured by Sony Corporation), beam diameter 20 μm, exposure time 1
Pulse exposure was performed at 0 μs. At this time, the laser output is L
The laser power on the printing plate was measured while being arbitrarily changed by a D pulse modulation driving device.

Subsequently, development was performed by rubbing with a cotton pad impregnated with a developer having the following composition.

(A) 80 parts by weight of water (b) 20 parts by weight of diethylene glycol mono-2-ethylhexyl ether The obtained printing plate was attached to an offset printing machine (Komori Sprint 4-color machine). Printing was performed on high quality paper using "Dryocolor" black, indigo, red, and yellow inks manufactured by Co., Ltd., and the number of sheets that could be printed without causing damage to the plate surface was evaluated as printing durability. Table 1 shows the results.

Example 2 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the heat insulating layer was changed to the following, and developed and printed in the same manner as in Example 1 to evaluate. did. Table 1 shows the results.

Insulation layer composition (a) Denacol EX411 (epoxy compound manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) Bis (3,4-diaminophenyl) sulfone 20 parts by weight (c) Light ester HO-MP ( Carboxyl group-containing compound (manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts by weight (d) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 part by weight (e) dimethylformamide 480 parts by weight Example 3 The composition of the heat insulating layer is changed to the following. Except for the above, a direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1, developed and printed in the same manner as in Example 1, and evaluated. Table 1 shows the results.

(A) Denacol EX411 (epoxy compound, manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) Uban 20SE60 (melamine resin, manufactured by Mitsui Toatsu Chemicals, Inc.) 20 parts by weight (c) Light ester HO-MP (carboxyl group-containing compound manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts by weight (d) Victoria pure blue BOH naphthalene sulfonic acid 0.1 part by weight (e) dimethylformamide 480 parts by weight Example 4 A direct-drawing waterless lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the lithographic printing plate was changed to that of Example 1, and developed and printed as in Example 1, and evaluated. Table 1 shows the results.

Insulation layer composition (a) Denacol EX411 (epoxy compound manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) 3,3′-dimethyl 4,4′-diaminodicyclohexylmethane 10 parts by weight (c) light ester HO-MP (carboxyl group-containing compound manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts by weight (d) Victoria pure blue BOH naphthalene sulfonic acid 0.1 part by weight (e) dimethylformamide 480 parts by weight Example 5 A direct-drawing waterless lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the lithographic printing plate was changed to that of Example 1, and developed and printed as in Example 1, and evaluated. Table 1 shows the results.

Insulation layer composition (a) Denacol EX411 (epoxy compound manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) 2-ethyl 4-methylimidazole 10 parts by weight (c) light ester HO-MP (containing carboxyl group) Compound Kyoeisha Chemical Co., Ltd.) 10 parts by weight (d) Victoria pure blue BOH naphthalene sulfonic acid 0.1 part by weight (e) Dimethylformamide 480 parts by weight Example 6 Except that the composition of the heat insulating layer was changed to the following, A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1, and developed and printed in the same manner as in Example 1 to evaluate. Table 1 shows the results.

Insulation layer composition (a) Epicoat 828 (epoxy compound manufactured by Yuka Shell Epoxy Co., Ltd.) 90 parts by weight (b) 2-ethyl 4-methylimidazole 10 parts by weight (c) light ester HO-MP (carboxyl group) Contained compound: Kyoeisha Chemical Co., Ltd.) 10 parts by weight (d) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 part by weight (e) Dimethylformamide 480 parts by weight Example 7 Except that the composition of the heat insulating layer was changed to the following A direct drawing type waterless planographic printing plate precursor was prepared in the same manner as in Example 1, and developed and printed in the same manner as in Example 1 to evaluate. Table 1 shows the results.

(A) Epicoat 828 (epoxy compound, manufactured by Yuka Shell Epoxy Co., Ltd.) 90 parts by weight (b) Reaction product of isophoronediamine and phenylglycidyl ether 20 parts by weight (c) Light ester HO-MP ( Carboxyl group-containing compound (manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts by weight (d) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 part by weight (e) Dimethylformamide 480 parts by weight Example 8 The silicone rubber layer composition was changed to the following. Except to do
A direct drawing type waterless planographic printing plate precursor was prepared in the same manner as in Example 7, and developed and printed in the same manner as in Example 7 to evaluate. Table 1 shows the results.

(A) 100 parts by weight of α, ω-divinylpolydimethylsiloxane (degree of polymerization 770) (b) HMS-501 (methyl (methyl hydrogen siloxane) (dimethylsiloxane) copolymer at both ends Hwt% = about 0.7 (manufactured by Chisso Corporation) 4 parts by weight (c) Olefin-coordinated platinum 0.02 parts by weight (d) Reaction inhibitor 0.3 parts by weight (e) "Isopar E" (isoparaffinic hydrocarbon Exxon Chemical ( 990 parts by weight Example 9 Except for changing the silicone rubber layer composition to the following,
A direct drawing type waterless planographic printing plate precursor was prepared in the same manner as in Example 7, and developed and printed in the same manner as in Example 7 to evaluate. Table 1 shows the results.

(A) 100 parts by weight of polydimethylsiloxane (molecular weight: about 25,000, terminal hydroxyl group) (b) 12 parts by weight of ethyltriacetoxysilane (c) 0.1 part by weight of dibutyltin diacetate (d) "Isopar- G ″ (isoparaffinic hydrocarbon manufactured by Exxon Chemical Co., Ltd.) 1200 parts by weight Example 10 Except that the composition of the silicone rubber layer was changed to the following,
A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 9, and developed and printed in the same manner as in Example 9 to evaluate. Table 1 shows the results.

(A) 100 parts by weight of polydimethylsiloxane (molecular weight: about 25,000, terminal hydroxyl group) (b) 12 parts by weight of ethyltriacetoxysilane (c) SZ6040 (epoxy group-containing silane compound Dow Corning Toray Toray Co., Ltd. 5 parts by weight (d) 0.1 parts by weight of dibutyltin diacetate (e) 1200 parts by weight of "Isopar-G" (isoparaffin-based hydrocarbon manufactured by Exxon Chemical Co., Ltd.) Example 11 Insulation layer composition A direct-drawing waterless lithographic printing plate precursor was prepared in the same manner as in Example 10, except that the composition was changed to the same as in Example 5, and developed and printed in the same manner as in Example 10 to evaluate. Table 1 shows the results.

Example 12 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the metal of the heat-sensitive layer was changed to antimony (melting point: 904K). Printed and evaluated. Table 1 shows the results.

Example 13 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the metal of the heat-sensitive layer was changed to an alloy of tellurium and tin (melting point: 920 K). Similarly, development and printing were performed and evaluated. Table 1 shows the results.

Example 14 The metal of the heat-sensitive layer was an alloy of tin, zinc and antimony (melting point 1
A direct drawing type waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the temperature was changed to 300K), and developed and printed in the same manner as in Example 1 to evaluate. Table 1 shows the results.

Example 15 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the metal of the heat-sensitive layer was changed to titanium (melting point: 1933 K). Printed and evaluated.
Table 1 shows the results.

Example 16 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the heat insulating layer was changed to the following, and developed and printed in the same manner as in Example 1 to evaluate. did. Table 1 shows the results.

(A) Denacol EX411 (epoxy compound manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) Reaction product of isophoronediamine and phenylglycidyl ether 20 parts by weight (c) Soarex R-BH (carboxyl group-containing compound) 10 parts by weight (d) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 part by weight (e) Light ester PM (phosphorus-containing compound manufactured by Kyoeisha Chemical Co., Ltd.) 0.5 part by weight ( e) Dimethylformamide 480 parts by weight Comparative Example 1 As a substrate, a polyester film (ICI Film)
s white 329 film), a heat-insulating layer was not provided, and no heating was performed after the formation of the heat-sensitive layer. A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 10, and developed in the same manner as in Example 10. -Printed and evaluated. Table 1 shows the results.

Comparative Example 2 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Comparative Example 1 except that the silicone rubber layer was changed to that of Example 9, and the development and development were performed in the same manner as in Comparative Example 1. Printed and evaluated. Table 1 shows the results.

Comparative Example 3 A direct drawing type waterless planographic printing plate precursor was prepared in the same manner as in Comparative Example 1 except that the silicone rubber layer was changed to that of Example 8, and the development and development were performed in the same manner as in Comparative Example 1. Printed and evaluated. Table 1 shows the results.

Comparative Example 4 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Comparative Example 1, except that the metal of the heat-sensitive layer was changed to titanium and the silicone rubber layer was changed to that of Example 9. Developed and printed in the same manner as in Comparative Example 1, and evaluated. Table 1 shows the results.

Comparative Example 5 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the heating temperature after the application of the heat insulating layer composition was changed to 200 ° C., and heating was not performed after the formation of the heat sensitive layer. Then, development and printing were performed in the same manner as in Example 1 and evaluated. Table 1 shows the results.

Comparative Example 6 A direct-drawing waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the heat insulating layer was changed to the following composition.
Developed and printed in the same manner as described above and evaluated. Table 1 shows the results.

(A) Denacol EX411 (epoxy compound, manufactured by Nagase Kasei Kogyo Co., Ltd.) 90 parts by weight (b) Reaction product of isophoronediamine and phenylglycidyl ether 20 parts by weight (c) Victoria Pure Blue BOH naphthalene sulfonic acid 0.1 Parts by weight (d) Light ester PM (phosphorus-containing compound manufactured by Kyoeisha Chemical Co., Ltd.) 0.5 parts by weight (e) dimethylformamide 480 parts by weight

[Table 1] As shown in Table 1, Examples satisfying the conditions of the present invention have excellent printing durability, whereas Comparative Examples did not provide sufficient printing durability.

[0163]

The method for producing a direct-drawing waterless planographic printing plate precursor according to the present invention is a method for producing a direct-drawing waterless planographic printing plate precursor in which a heat insulating layer, a heat-sensitive layer and a silicone rubber layer are sequentially laminated on a substrate. In, on the substrate, a heat insulating layer composition comprising an epoxy compound and a compound having a carboxyl group is applied, and in a state where the epoxy group of the heat insulating layer composition remains, to form a metal thin film that is a heat sensitive layer, the heat sensitive layer and The adhesiveness of the heat insulating layer is improved, and the printing durability is dramatically improved as compared with the conventional direct drawing type waterless lithographic printing plate.

Claims (9)

[Claims] In a method for producing a direct drawing type waterless planographic printing plate precursor comprising sequentially laminating a heat insulating layer, a heat-sensitive layer and a silicone rubber layer on a substrate, the substrate comprises a heat insulating layer comprising an epoxy compound and a compound having a carboxyl group. A method for producing a direct-drawing waterless lithographic printing plate precursor, comprising applying a composition and forming a metal thin film as a heat-sensitive layer in a state where the epoxy group of the heat-insulating layer composition remains. 2. The direct drawing water according to claim 1, wherein the epoxy compound in the heat insulating layer composition is cross-linked by at least one compound selected from the group consisting of an amine compound and an amine adduct compound. None Manufacturing method of lithographic printing plate precursor. 3. The method for producing a direct-drawing waterless lithographic printing plate precursor according to claim 1, wherein the heat-insulating layer composition contains a phosphorus-containing compound. 4. The method according to claim 1, wherein the silicone rubber layer contains a silane compound having an epoxy group.
A method for producing a direct-drawing waterless planographic printing plate precursor according to any one of the preceding claims. 5. The method for producing a direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the heat-sensitive layer is made of a metal having a melting point of 2000 (K) or less. 6. The heat-sensitive layer is made of one selected from tellurium, tin, antimony, gallium, bismuth, and zinc, or an alloy obtained by combining two or more of these. 5. The method for producing a direct-drawing waterless lithographic printing plate precursor according to any one of items 5 to 5. 7. The heat-sensitive layer according to claim 1, wherein the thickness of the heat-sensitive layer is 1000 Å or less.
Production method of direct drawing type waterless lithographic printing plate precursor as described in section. 8. The method for producing a direct-drawing waterless lithographic printing plate precursor according to claim 1, wherein the optical density of the heat-sensitive layer is 0.6 to 2.3. 9. The method for producing a direct-drawing waterless planographic printing plate precursor according to claim 1, wherein a heat treatment is performed after the heat-insulating layer composition is applied and after the heat-sensitive layer is formed.