JPH10319579A - Direct writing waterless lithographic printing master plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the production of a harmful gas such as nitrogen oxides by the radiation of laser light by forming a thermosensitive layer containing a hydroxyl group-contg. compd. and a photothermal converting material and having a crosslinked structure. SOLUTION: This direct writing waterless lithographic printing master plate is produced by successively forming at least a thermosensitive layer and a silicone rubber layer on a substrate. The thermosensitive layer contains a hydroxyl group-contg. compd. and a photothermal converting material and has a crosslinked structure. This method features that if the thermosensitive layer does not contain an easily pyrolyzable compd. such as nitrocellulose, only the bonds which crosslink the silicone layer and the thermosensitive layer are broken by the radiation of laser beam, but the thermosensitive layer is not damaged or at least a part of the layer remains. Therefore, even when the thermosensitive layer contains a nitrogen-contg. compd. as a binder, the binder itself is not decomposed or combusted, thereby producing no nitrogen oxides as a harmful gas.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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.

[0003] In recent years, new types of various lithographic printing materials have been developed with the rapid progress of output systems such as prepress systems, imagesetters, and laser printers.

[0004] These lithographic printing plates can be classified according to plate-making methods, such as 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, an ink repelling layer or an ink coating with an ink jet. Examples include a method of forming a layer. Above all, the method using laser light is superior to other methods in terms of resolution and plate making speed, and there are many types.

[0005] Lithographic printing plates using this laser beam are further classified into two types: a photon mode type by photoreaction and a heat mode type by which photothermal conversion is performed to cause a thermal reaction.

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

However, the method (1) uses an argon ion laser mainly as a laser light source, so that the apparatus becomes large, and the printing plate uses a high-sensitivity photopolymer. There is a drawback that care must be taken and the storage stability tends to decrease.

The electrophotographic lithographic plate (2) has the advantage that it can be handled in a bright room, but the dark decay becomes large between 2 and 5 minutes after charging of the photosensitive layer, so that the exposure and development treatment 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 the sensitivity is high. There is also a problem that requires attention.

In the silver halide composite lithographic plate (4), a high-sensitivity silver halide emulsion layer is exposed on a photosensitive layer with an argon ion laser, developed, and then exposed and developed with ultraviolet rays using the exposed layer as a mask. . 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 of (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 the advantage that it can be handled in a bright room, and has recently become useful due to the rapid progress of the output of the semiconductor laser serving as a light source and the rapid progress of the output of the semiconductor laser serving as a light source. Sex is being reviewed.

For example, US Pat. No. 5,379,698 describes a direct-drawing waterless lithographic printing plate using a metal thin film as a heat-sensitive layer. However, the sensitivity of the printing plate is poor because the metal thin film itself transmits laser light. There was a problem. For this reason, in order to increase the absorptance of laser light, an antireflection layer must be provided, and the coating process is further increased,
The consequences are costly.

Further, Japanese Patent Application Laid-Open No. 6-199064, USP
No. 5,339,737, EP 0580393,
55723, EP0573091, USP5378
580, JP-A-7-164773, USP53
33705 and EPO0644647 also describe a direct-drawing waterless planographic printing plate precursor using laser light as a light source.

The heat-sensitive layer of the printing plate precursor of this thermal destruction method is
For example, carbon black is used as a laser light absorbing compound, nitrocellulose is used as a thermal decomposition compound, and a silicone layer is applied to the surface thereof. The carbon black in the heat-sensitive layer absorbs laser light and is converted into heat energy, and the heat destroys the heat-sensitive layer.
Finally, by removing this portion by development, the silicone rubber layer on which the ink is not deposited is simultaneously peeled off, and an image portion on which the ink is deposited is formed. However, at the time of heat-sensitive destruction, nitrocellulose is decomposed to generate harmful gases such as nitrogen oxides (NO _x ), and further, chemical species are decomposed to generate an unpleasant odor.

[0016]

To improve the shortcomings of the invention will to challenge Solved] The present invention is the prior art, by containing the easily decomposable compound in place of the nitrocellulose in the heat-sensitive layer, harmful gases such as NO _x by laser irradiation The object of the present invention is to provide a direct drawing type waterless lithographic printing plate precursor that does not emit a lithographic printing plate.

[0017]

To achieve the above object, the present invention comprises the following constitution.

(1) A direct-drawing waterless planographic printing plate precursor comprising at least a heat-sensitive layer and a silicone rubber layer sequentially laminated on a substrate, wherein the heat-sensitive layer contains a hydroxyl group-containing compound and a light-to-heat conversion material, and A direct-drawing waterless lithographic printing plate precursor having a crosslinked structure.

(2) The direct-drawing waterless planographic printing plate precursor as described in (1), wherein the hydroxyl group-containing compound is a substance other than nitrocellulose.

(3) The compound containing a hydroxyl group is a resole resin,
The direct drawing according to (1) or (2), comprising at least one of a novolak resin, a rosin-modified phenol resin, a phenol having a polymerizable or crosslinkable functional group and / or a polyphenol. Lithographic printing plate precursor without mold water.

(4) The direct-drawing waterless lithographic plate according to claim 1, wherein the hydroxyl group-containing compound is at least one compound selected from the following formulas (I) to (VII). Printing plate original.

[0022]

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Embedded image [Wherein L ¹ , L ² , L ³ , and L ⁴ are a hydrogen atom or a methyl group. R ¹ is a hydrogen atom, a methyl group, an ethyl group or a propyl group, R ² is a hydrogen atom, a methyl group or a cyclohexyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are a hydrogen atom or a methyl group. Group. X ¹ is a hydroxyl group, a hydrogen atom,
X represents a methyl group, a methoxy group or an ethoxy group.
X ¹ is a hydroxyl group, a hydrogen atom, a methyl group, a methoxy group or an ethoxy group, X ² is a hydroxyl group or a p-hydroxybenzyl group, X ³ is a hydroxyl group or a hydrogen atom, and X ⁴ is a methylol group or a methyl group. It is. Z is a methylene group or a carbonyl group. p is 0 or 1, q is 0, 1 or 2, r and s are 0 or 1
It is. (5) The direct-drawing waterless planographic printing plate precursor as described in (1), wherein the hydroxyl group-containing compound is a reaction product of an epoxy compound.

(6) The direct-drawing waterless planographic printing plate precursor as described in any one of (1) to (5), wherein the light-to-heat conversion material is carbon black.

(7) The glass transition temperature T _g of the binder resin in the heat-sensitive layer is 0 ° C. or less (1).
A direct drawing type waterless planographic printing plate precursor according to any one of (1) to (6).

(8) The direct-drawing waterless planographic printing plate precursor as described in any one of (1) to (7), wherein the heat-sensitive layer contains a polyurethane resin as a binder.

(9) The content of the hydroxyl group-containing compound in the heat-sensitive layer and the compound containing a reactive functional group that generates a hydroxyl group by a crosslinking reaction is 5 to the total heat-sensitive layer composition.
The direct drawing type waterless lithographic printing plate precursor as described in any one of (1) to (8), wherein the lithographic printing plate precursor is described in (1) to (8).

(10) The direct drawing type waterless lithographic printing plate precursor as described in any one of (1) to (9), wherein the lower layer of the heat-sensitive layer is colored blue, green or purple.

(11) Waterless lithographic printing obtained by exposing the direct-drawing waterless lithographic printing plate precursor according to any one of (1) to (10) and developing with water or a liquid containing water as a main component. Edition.

(12) A waterless planographic printing plate characterized in that the exposed heat-sensitive layer or primer layer is dyed by using a dye solution on the developed waterless planographic printing plate as described in (11).

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the direct drawing type means that 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.

Next, the direct drawing type waterless planographic printing plate of the present invention will be described.

It is important that the heat-sensitive layer used in the present invention efficiently absorbs the laser beam and is easily decomposed by the heat, or the adhesive strength with the upper silicone rubber layer is reduced. For this purpose, it is necessary to include a light-to-heat conversion substance and a thermally decomposable compound in the heat-sensitive layer.

First, examples of the thermally decomposable compounds include nitro compounds such as ammonium nitrate, potassium nitrate, sodium nitrate and nitrocellulose, and nitrogen-containing compounds such as azo compounds, diazo compounds and hydrazine derivatives. There was a problem that occurs.

In the present invention, a hydroxyl-containing compound is used instead of these nitrogen-containing compounds. Hydroxyl groups in the thermosensitive layer are
An alkoxy group, an alkenoxy group in the silicone rubber layer,
Acetoxy group, oxime group, amide group, silanol group,
Condensed with hydrogen siloxane or the like, and the heat-sensitive layer and the silicone rubber layer are cross-linked by C—O—Si bonds. It is known that the bond dissociation energy of this CO etheric bond is relatively low, and the bond can be easily dissociated by thermal energy. In this case, if the heat-sensitive layer does not contain a thermally decomposable compound such as nitrocellulose, the bond that crosslinks the silicone layer and the heat-sensitive layer is only broken at the time of laser irradiation, and the heat-sensitive layer is not destroyed. , At least in part. Therefore, even if a nitrogen-containing substance is contained in the heat-sensitive layer as a binder, the binder itself does not break or burn, so that nitrogen oxides, which are harmful gases, are not generated.

In the present invention, a bond which decomposes by heat is formed between the silicone rubber layer and the heat-sensitive layer instead of containing a compound which decomposes by heat.
In order to achieve such a bond, a hydroxyl group-containing compound is contained in the thermosensitive layer.

The hydroxyl group-containing compound contained in the heat-sensitive layer must be solid or capable of maintaining its shape by crosslinking. Further, instead of the hydroxyl group-containing compound, a compound containing a reactive functional group that generates a hydroxyl group by a crosslinking reaction may be used.

Specific examples of the hydroxyl-containing compound and the compound having a reactive functional group that generates a hydroxyl group by a crosslinking reaction are shown below, but the present invention is not limited to these.

(1) Epoxy compounds Bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ether epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, etc., and the epoxy functional group may be three or more. preferable. These compounds may contain a hydroxyl group, but do not need to contain a hydroxyl group since the epoxy ring is cleaved by a crosslinking reaction to form a hydroxyl group.

(2) Phenolic resins Resol resin, novolak resin, rosin-modified phenol resin, epoxy-modified phenol resin, lignin-modified phenol resin, aniline-modified phenol resin, melamine-modified phenol resin, etc. (3) Polymerizable or crosslinkable Phenols and polyphenols having a functional group such as allyl biphenol or allyl bisphenol represented by the general formula (I) and bisphenol carboxylic acid or bisphenol carboxylic acid ester represented by the general formula (II) (4) hydroxyl group in one molecule 4,4 ′, 4 ″ -methylidine trisphenol represented by the general formula (III), bis (4-hydroxyphenylmethyl) benzenediol represented by the general formula (IV), Shown in general formula (V) A pyrogallol compound, a methylol biphenol represented by the general formula (VI), or a methylol bisphenol; a 4,4 ′, 4 ″, 4 ′ ″-ethylidinetetrakisphenol represented by the general formula (VII); ', 4'',4'''-
(1,4-phenylenedimethylidyne) tetrakisphenol and the like, and 4,4 ′, 4 ″ -methylidinetriscyclohexanol and the like (5) Others terminal hydroxyl group xylene resin, cellulose and the like Among these compounds, (2) Phenol resins having a polymerizable (or crosslinkable) functional group of (3) and polyphenols are preferably used because of their high sensitivity.

These hydroxyl group-containing compounds and compounds having a reactive functional group capable of forming a hydroxyl group by a crosslinking reaction can be used alone or as a mixture of two or more kinds. It is preferably 5 to 60% by weight, more preferably 20 to 60% by weight based on the heat-sensitive layer composition.
５０50% by weight. When the content is less than 5% by weight, the sensitivity of the printing plate is reduced, and when the content is more than 60% by weight,
The solvent resistance of the printing plate tends to decrease.

In order to impart form retention, solvent resistance, and printing durability as a printing plate, it is necessary to form a network structure by crosslinking, particularly when the above components are in liquid form.

As a cross-linking method, there are a thermal cross-linking type in which a cross-linking reaction proceeds by heating and a photo-cross-linking type by light irradiation, and it is appropriately selected for each compound. The photo-crosslinking type requires that the object sufficiently transmit light, but has the characteristic that curing can be performed in a shorter time and at a lower temperature than the thermal crosslinking type.

For example, the epoxy compounds represented by the above classification (1) include butylated urea resin, butylated melamine resin, butylated benzoguanamine resin, butylated urea melamine cocondensation resin, aminoalkyd resin, isobutylated melamine resin, Methylated meminin resin, hexamethoxymethylolmelamine, methylated benzoguanamine resin,
Butylated benzoguanamine resin, amine compounds such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, metaxylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, and polyamides Amide compounds such as a system curing agent and dicyandiamide, hydroxyl-containing compounds such as phenolic resins and polyhydric alcohols, phthalic acid, hexahydrophthalic acid,
Thermal cross-linking can be performed by a combination with a carboxylic acid compound such as tetrahydrophthalic acid, dodecynylsuccinic acid, pyromellitic acid, chlorenic acid, maleic acid, and fumaric acid, or an anhydride or polyvalent thiol. Since a hydroxyl group is generated by the crosslinking reaction, it is not always necessary to include a hydroxyl group in the epoxy resin.

In these cases, a quaternary ammonium salt, KOH or SnC is used as a catalyst for accelerating the reaction.
It is preferable to use a known catalyst such as l ₄ , Zn (BF ₄ ) ₂ and an imidazole compound.

Among the above cross-linking agents, a combination of a polyfunctional epoxy compound and an amine compound is more preferable from the viewpoints of curing speed and handleability.

Further, a polyfunctional crosslinking agent having an organic silyl group or an amine group-containing monomer can be preferably used.

The compounds of the above-mentioned category (2) can be thermally cross-linked by themselves or with a catalyst, or can be cross-linked with a polyfunctional epoxy resin or a polyfunctional isocyanate compound. However, since the hydroxyl group becomes a cross-linking functional group, it is necessary to pay attention to the mixing ratio so that the hydroxyl group remains even after cross-linking.

When a double bond is present in a hydroxyl group-containing compound as in (3) of the above classification, a method of dissociating the double bond with a radical and polymerizing is generally used.

In the case of crosslinking by heat, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, tert-butyl hydroperoxide Peroxide, peracetic acid te
peroxides such as rt-butyl and tert-butyl perbenzoate, 2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobisisobutylamide, Azo compounds such as 2'-azobisisobutyronitrile and benzenesulfonyl azide,
4-bis (pentamethylene) -2-tetrazene and the like,
Used as a radical generator.

In the case of crosslinking by light, acetophenone compounds such as diethoxyacetophenone, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, benzoin, benzoin ethyl ether,
Benzoin based compounds such as benzoin isopropyl ether and benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-
Benzophenone compounds such as 4′-methyldiphenyl sulfide, 2-isopropylthioxanthone,
Thioxanthone compounds such as 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone, triethanolamine, triisopropanolamine, ethyl 4-dimethylaminobenzoate, 4,4′-bisdiethylaminobenzophenone, and 4,4′-bis Amine compounds such as dimethylaminobenzophenone (Michler's ketone), benzyl, camphorquinone, 2-ethylanthraquinone, and 9,10-phenanthrenequinone are used as radical generators.

In the case of a compound having at least three hydroxyl groups in one molecule as in the above-mentioned classification (4), the hydroxyl group itself may be used as a crosslinkable group. In this case, thermal crosslinking can be performed by combining with a polyfunctional isocyanate compound or a polyfunctional epoxy resin. However, also in this case, since the hydroxyl group becomes a cross-linking functional group, it is necessary to pay attention to the mixing ratio so that the hydroxyl group remains even after cross-linking.

The content of these crosslinking agents and radical generators is determined by the number of functional groups and double bonds of the hydroxyl-containing compound, respectively.

The photothermal conversion material is not particularly limited as long as it can absorb light and convert it into heat. For example, black pigments such as carbon black, aniline black and cyanine black, phthalocyanine and naphthalocyanine Green pigment, carbon graphite, iron powder, diamine-based metal complex, dithiol-based metal complex, phenolthiol-based metal complex, mercaptophenol-based metal complex, arylaluminum metal salts, inorganic water-containing inorganic compounds, copper sulfate, chromium sulfide, Metal oxides such as silicate compounds, titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, and tungsten oxide; hydroxides and sulfates of these metals; and bismuth, tin, tellurium, iron, and aluminum It is preferable to add an additive such as a metal powder.

Of these, carbon black is preferred from the viewpoints of light-to-heat conversion, economy and handling.

In addition to the above substances, dyes absorbing infrared or near-infrared rays are also preferably used as photothermal conversion substances.

As these dyes, 400 nm to 1200
Any dye having a maximum absorption wavelength in the range of nm can be used. Preferred dyes include those for electronics,
Recording dyes cyanine, phthalocyanine, phthalocyanine metal complex, naphthalocyanine, naphthalocyanine metal complex, dithiol metal complex, naphthoquinone, anthraquinone, indophenol, indoaniline, pyrylium, thiopyrylium , Squarylium, croconium, diphenylmethane,
Triphenylmethane, triphenylmethanephthalide, triallylmethane, phenothiazine, phenoxazine, fluoran, thiofluorane, xanthene, indolylphthalide, spiropyran, azaphthalide, chromenopyrazole, Leuco auramine, rhodamine lactam, quinazoline, diazaxanthene, bislactone, fluorenone, monoazo, ketone imine, diazo, methine, oxazine, nigrosine, bisazo, bisazostilbene, bis Azooxadiazole, bisazofluorenone, bisazohydroxyperinone, azochrome complex, trisazotriphenylamine, thioindigo, perylene, nitroso, 1: 2 type metal complex, intermolecular CT System, quinoline Quinophthalone-based, fluid-based acid dyes, basic dyes, pigments, oil-soluble dyes, triphenylmethane-based leuco dyes, cationic dyes, azo-based disperse dyes, benzothiopyran-based spiropyrans, 3,9-dibromoanthanthrone, indanth Ron, phenolphthalein, sulfophthalein, ethyl violet,
Methyl orange, fluorescein, methyl viologen, methylene blue, dimrosbetaine and the like can be mentioned.

Of these, dyes for electronics and recording, having a maximum absorption wavelength of 700 nm to 900 n
m, cyanine-based dye, azurenium-based dye, squarylium-based dye, croconium-based dye, azo-based disperse dye, bisazostilbene-based dye, naphthoquinone-based dye, anthraquinone-based dye, perylene-based dye, phthalocyanine-based dye, na Phthalocyanine metal complex dyes,
Black dyes such as dithiol nickel complex dyes, indoaniline metal complex dyes, intermolecular CT dyes, benzothiopyran spiropyrans, and nigrosine dyes are preferably used.

Further, among these dyes, those having a large molar absorbance coefficient are preferably used. Specifically, ε = 1 × 10 ⁴ or more is preferable, and more preferably 1 × 1 4
Is 0 ⁵ or more. This is because if ε is smaller than 1 × 10 ⁴ , the effect of improving sensitivity is unlikely to be exhibited.

These light-to-heat converting substances alone have an effect of improving sensitivity, but the sensitivity can be further improved by using two or more kinds in combination.

The content of these light-to-heat converting substances is preferably from 2 to 70% by weight, more preferably from 5 to 60% by weight, based on the whole heat-sensitive layer composition. When the amount is less than 2% by weight, the effect of improving sensitivity is not seen, and when the amount is more than 70% by weight, the printing durability of the printing plate tends to decrease.

The heat-sensitive layer preferably contains a binder polymer for the purpose of improving printing durability and storage stability, and has a glass transition temperature T _g of 0 for the binder.
Those below ° C are effective.

As binders having a T _g of 0 ° C. or less, polydienes such as polybutadiene, polyisoprene and chloroprene, polyalkenes such as polymethylene, polyethylene and polypropylene, ethyl polyacrylate, polypropyl acrylate, polybutyl acrylate and polybutylene Polyacrylates such as sec-butyl acrylate,
Polymethacrylates such as polyhexyl methacrylate, polyoctyl methacrylate, polydecyl methacrylate, poly-N-octyl acrylamide, poly-N
-Polyacrylamides such as dodecylacrylamide, polyvinyl ethers such as polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl propyl ether, polyvinyl thioether, polyvinyl halides such as polyvinylidene chloride, polyvinylidene fluoride, poly-4-hexyl styrene, poly Polystyrenes such as -4-octylstyrene, poly-4-decylstyrene and poly-4-tetradecylstyrene; polyoxides such as polymethylene oxide, polyethylene oxide, polytrimethylene oxide, polypropylene oxide and polyacetaldehyde; polydecamethylene Terephthalate, polyhexamethylene isophthalate, polyadipoyloxydecamethylene, polyoxy-2-butynyleneoxysebacoyl, Polyesters such as di oxyethyleneoxy malonyl, polyoxy-2-butenyl, alkylenedioxy carbonylimino hexamethyleneimino carbonyl, polyoxytetramethylene oxycarbonyl imino hexamethyleneimino carbonyl, polyoxy -2,
Examples thereof include polyurethanes such as 2,3,3,4,4,5,5-octafluorohexamethyleneoxycarbonyliminohexamethyleneiminocarbonyl, cellulose, and cellulose trihexanoate. In addition, ethylene, butadiene, acrylic acid, acrylate,
A methacrylic acid ester, acrylamide, vinyl alcohol, vinyl ether, vinyl ester, vinyl halide, ethylene oxide, and a copolymer of two or more monomers selected from acetal are also included, but the present invention is not limited thereto.

The content of these binders is preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, based on the total heat-sensitive layer composition. If the content is less than 10%, the printing durability tends to decrease, and if it exceeds 60% by weight, the sensitivity tends to decrease.

Further, in the heat-sensitive layer, a preservative, an antihalation dye, an antifoaming agent, an antistatic agent, a dispersant, an emulsifier,
An additive such as a surfactant may be appropriately contained.

In particular, it is preferable to add a fluorine-based surfactant in order to improve coatability. The content of these additives is usually 10% by weight or less based on the total heat-sensitive layer composition.

When an addition type silicone rubber is used for the silicone rubber layer, a compound having an ethylenically unsaturated double bond can be added for the purpose of improving the adhesion between the heat-sensitive layer and the silicone rubber layer. Examples of the compound having an ethylenically unsaturated double bond include the following compounds, and among them, epoxy acrylates are particularly preferable. The amount of the compound having an ethylenically unsaturated double bond to be used is preferably 0.5 to 30% by weight based on the total composition of the heat-sensitive rupture layer.

(1) An esterified product of a polyfunctional hydroxyl group-containing compound and acrylic acid or methacrylic acid.

Examples of the polyfunctional hydroxyl group-containing compound include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, hydroquinone, dihydroxyanthraquinone, bisphenol A, bisphenol S, resole resin, pyrogallol acetone resin,
Examples include hydroxystyrene copolymer, glycerin, pentaerythritol, dipentaerythritol, trimethylolpropane, polyvinyl alcohol, cellulose, and derivatives thereof, and polymers and copolymers of hydroxyacrylate and hydroxymethacrylate. The target compound can be obtained by subjecting these polyfunctional hydroxyl group-containing compounds to an acrylic acid or methacrylic acid esterification reaction by a known method. At this time, it is necessary to carry out the reaction at a ratio containing two or more ethylenically unsaturated groups in one molecule of the hydroxyl group-containing compound.

(2) Epoxy acrylates obtained by reacting an epoxy compound with acrylic acid, methacrylic acid, glycidyl acrylate, or glycidyl methacrylate.

Specific examples of the epoxy compound include compounds obtained by reacting the hydroxyl-containing compound described in the section (1) with epihalohydrin.

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

The desired epoxy acrylates can be obtained by reacting these epoxy compounds with acrylic acid, methacrylic acid or glycidyl acrylate or glycidyl methacrylate in a known manner.

(3) A compound obtained by reacting an amine compound with glycidyl acrylate, glycidyl methacrylate or acrylic acid chloride or methacrylic acid chloride.

As the amine compound, octylamine,
Monovalent amine compounds such as laurylamine, dioxyethylenediamine, trioxyethylenediamine, tetraoxyethylenediamine, pentaoxyethylenediamine, hexaoxyethylenediamine, heptaoxyethylenediamine, octaoxyethylenediamine, nonaoxyethylenediamine, monooxypropylenediamine, dioxypropylene Diamine, trioxypropylenediamine, tetraoxypropylenediamine, pentaoxypropylenediamine, hexaoxypropylenediamine, heptaoxypropylenediamine, okitaoxypropylenediamine, nonaoxypropylenediamine, polymethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetetramine , Tetraethylpentamine, etc. Aliphatic polyamine compound and, m
-Xylylenediamine, p-xylylenediamine, m-
Phenylenediamine, diaminodiphenyl ether, benzidine, 4,4′-bis (o-toluidine), 4,
4'-thiodianiline, o-phenylenediamine, dianisidine, 4-chloro-o-phenylenediamine, 4-
And polyamine compounds such as methoxy-6-methyl-m-phenylenediamine. The target compound can be obtained by reacting these amine compounds with glycidyl acrylate, glycidyl methacrylate or acrylic acid chloride or methacrylic acid chloride by a known method.

(4) A compound obtained by reacting a compound having a carboxyl group with glycidyl acrylate and glycidyl methacrylate.

Examples of the carboxyl group-containing compound include malonic acid, succinic acid, malic acid, thiomalic acid, racemic acid,
Examples thereof include citric acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, dimer acid, trimellitic acid, and carboxy-modified unvulcanized rubber.

The compound having a carboxyl group can be reacted with glycidyl acrylate or glycidyl methacrylate by a known method to obtain a desired compound.

(5) Urethane acrylates Glycerin diacrylate isophorone diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer and the like can be mentioned.

The compounds having two or more ethylenically unsaturated double bonds in one molecule can be used alone or in combination of two or more.

Further, in some cases, in order to improve the adhesiveness to the additional silicone rubber layer as the upper layer, hydrophobic silica whose surface is treated with a silane coupling agent containing a (meth) acryloyl group or an allyl group is used. The powder may be added in an amount of 20% by weight or less based on the total heat-sensitive layer composition.

The composition for forming the heat-sensitive layer is as follows:
Dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone, dioxane, toluene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether , Acetone, methanol, ethanol, cyclopentanol, cyclohexanol, diacetone alcohol, benzyl alcohol, butyl butyrate,
It is prepared as a composition solution by dissolving in a suitable organic solvent such as ethyl lactate. Such a composition solution is uniformly applied on a substrate and thermally cured at a required temperature for a required time to form a heat-sensitive layer.

The thickness of these heat-sensitive layers is preferably from 0.1 g / m ² to 10 g / m ² , more preferably 0.2 g / m ^2.
From 5 g / m ² . When the film thickness is less than 0.1 g / m ^{2, the} printing durability tends to decrease, and when the film thickness is more than 10 g / m ² , it is disadvantageous from an economic viewpoint.

A dimensionally stable plate is used as the substrate of the printing plate. Such dimensionally stable plate-like objects include those conventionally used as a substrate for a printing plate, and they can be suitably used. Such substrates include paper, plastics (eg, polyethylene, polypropylene, polystyrene, etc.), metal plates such as zinc, copper, etc., such as cellulose, carboxymethylcellulose, cellulose acetate, polyethylene,
Examples include a plastic film such as polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetate, and the like, and a paper or plastic film on which a metal is laminated or vapor-deposited as described above. Among these substrates, an aluminum plate is particularly preferable because it has excellent dimensional stability and is inexpensive. Further, a polyethylene terephthalate film used as a substrate for light printing is also preferably used.

The direct-drawing waterless planographic printing plate used in the present invention may use a primer layer in order to strengthen the adhesion between the substrate and the heat-sensitive layer. The primer layer of the direct drawing type waterless planographic printing plate precursor used in the present invention needs to satisfy the following conditions. That is, the substrate and the heat-sensitive layer are well adhered to each other, are stable over time, and have good resistance to the solvent of the developing solution. As those satisfying such conditions, in addition to those containing an epoxy resin as described in JP-B-61-54219, polyurethane resins, epoxy resins, phenol resins, acrylic resins, alkyd resins, polyester resins, polyamide resins, melanin Resin, urea resin, benzoguanamine resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, polyacrylonitrile-butadiene copolymer, resole resin, polyether resin, epoxy phenol urea resin, polyether sulfone resin, milk casein,
Gelatin or the like can be used. These resins can be used alone or in combination of two or more.

A composition similar to that of the heat-sensitive layer may be cured by light or heat.

Among these, it is preferable to use a polyurethane resin, a polyester resin, an acrylic resin, an epoxy resin, a urea resin, an epoxyphenol urea resin, a resole resin, or the like alone or as a mixture of two or more.

The content of these polymers is preferably from 20 to 98% by weight, more preferably from 40 to 95% by weight, based on the total primer layer composition.

It is preferable that a crosslinking agent is contained in the primer layer in order to impart solvent resistance.

As the crosslinking agent, a combination of the above resins, for example, an epoxy resin and an amino resin (a urea resin, a melamine resin, a benzoguanamine resin, etc.) can be used, but a combination of an isocyanate compound and a hydroxyl group-containing compound can be used. It is.

As such isocyanate compounds, for example, paraphenylene diisocyanate, 2,4-
Or 2,6-toluylene diisocyanate (TD
I), 4,4-diphenylmethane diisocyanate (M
DI), tolylene diisocyanate (TODI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate,
Meta-xylylene diisocyanate (MXDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanatomethylcaprolate), hydrogenated MDI (also known as 4,
4'-methylenebis (cyclohexylisocyanate)), hydrogenated TDI (also known as methylcyclohexane 2,
4 (2,6) -diisocyanate), hydrogenated XDI (also known as 1,3- (isocyanatomethyl) cyclohexane), isophorone diisocyanate (IPI), diphenyl ether diisocyanate, trimethylhexamethylene diisocyanate (TMDI), tetramethyl xylylene diisocyanate, polymethyl Methylenephenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8- Diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicyclo And the like heptane triisocyanate, high alcohol adduct polyisocyanates,
Alternatively, a polymer of a polyisocyanate is used.

Blocked isocyanates obtained by blocking the above isocyanate compounds with methyl ethyl ketoxime, phenol, ε-caprolactam and the like can also be used.

Examples of the compound having a hydroxyl group that can react with these isocyanate compounds include an epoxy resin, a phenol resin, a resole resin, a hydroxyl group-containing polyurethane, an acrylic resin, and a hydroxyl group-containing monomer or oligomer.

The content of these crosslinking agents is preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight, based on the total primer layer composition.

Further, it is optional to add an acid or an organotin compound as a catalyst for accelerating these reactions, or to add a surfactant for the purpose of improving coatability.

Further, in the exposed area of the printing plate, the heat sensitive layer may be partially peeled off to expose the hue of the primer layer. Preferably, it is improved. Dye in this case,
Any pigment can be used as long as it has a different hue from that of the heat-sensitive layer, but green, blue and purple dyes and pigments are preferred.

The composition for forming the above-mentioned primer layer is obtained as a composition solution by dissolving in a suitable organic solvent such as dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone, dioxane and the like. The primer layer is formed by uniformly applying such a composition solution on a substrate and heating it at a required temperature for a required time.

The thickness of the primer layer is 0.5
５０50 g / m ² , preferably 1-10 g
/ M ² . When the thickness is less than 0.5 g / m ² , there is an effect of blocking morphological defects and chemical adverse effects on the substrate surface,
If the thickness is more than 50 g / m ^2, it is disadvantageous from an economic viewpoint, so the above range is preferable.

As the uppermost silicone rubber layer, any conventional waterless planographic silicone composition can be used.

Such a silicone rubber layer is obtained by sparsely cross-linking a linear organopolysiloxane (preferably dimethylpolysiloxane). A typical silicone rubber layer is represented by the following formula (VIII). It has a repeating unit as shown below.

[0100]

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. It has at least one or more hydroxyl groups in the molecular chain in the form of a chain terminal or side chain. In the case of the silicone rubber layer applied to the printing plate of the present invention, a silicone rubber (R
TV, LTV silicone rubber).
As such a silicone rubber, those in which a part of R of the organopolysiloxane chain is substituted by H can be used, and usually, by condensation of terminal groups represented by (IX) and (X) and (XI), Crosslinked. In some cases, an excess of a crosslinking agent may be present.

[0101]

Embedded image

Embedded image

Embedded image (Here, R is the same as R described in the formula (VIII), R ₁ and R ₂ are monovalent lower alkyl groups, and Ac is an acetyl group.) Such condensation type crosslinking is performed. Silicone rubber includes metal carboxylate such as tin, zinc, lead, calcium, manganese, for example, dibutyltin laurate, tin (II)
A catalyst such as octoate, naphthenate, or chloroplatinic acid is added.

In addition to these compositions, known adhesion-imparting agents such as alkenyl trialkoxysilanes may be added, and the composition of the condensation-type silicone rubber layer may be a hydroxyl-containing organopolysiloxane, a hydrolyzable functional group. The addition of a silane (or siloxane) is optional, and a known filler such as silica is optionally added for the purpose of improving rubber strength.

Further, in the present invention, in addition to the above-mentioned condensation type silicone rubber, an addition type silicone rubber can be used.

As the addition type silicone rubber, those obtained by crosslinking and curing a hydrogen polysiloxane having an Si—H bond and a vinyl polysiloxane having a CH ＝ CH bond with a platinum-based catalyst as shown below are preferably used. Can be

(1) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to silicon atoms in one molecule. (2) An organopolysiloxane having at least two SiH groups in one molecule. Hydrogenpolysiloxane 0.1 to 1000 parts by weight (3) Addition catalyst 0.00001 to 10 parts by weight The alkenyl group of the component (1) may be located at the terminal of the molecular chain or in the middle, and may be an organic compound other than the alkenyl group. The group is a substituted or unsubstituted alkyl group or aryl group. Component (1) may have a trace amount of hydroxyl groups. Ingredient (2)
Reacts with the component (1) to form a silicone rubber layer, which plays a role in providing adhesion to the heat-sensitive layer. The hydrogen group of the component (2) may be at the terminal of the molecular chain or at the middle, and the organic group other than hydrogen is selected from those similar to the component (1). It is preferable that 60% or more of the organic groups of the component (1) and the component (2) are methyl groups as a whole in view of improvement of ink repellency. The molecular structure of the components (1) and (2) may be any of linear, cyclic and branched, and it is preferable that at least one of the molecular weights exceeds 1,000 from the viewpoint of rubber physical properties. Preferably has a molecular weight of more than 1,000. Examples of the component (1) include α, ω-divinylpolydimethylsiloxane, a (methylvinylsiloxane) (dimethylsiloxane) copolymer having a methyl group at both terminals, and the like. As the component (2), a hydrogen group having a hydrogen group at both terminals. Polydimethylsiloxane, α, ω-
Examples thereof include dimethyl polymethyl hydrogen siloxane, (methyl hydrogen siloxane) (dimethyl siloxane) copolymer having both terminal methyl groups, and cyclic polymethyl hydrogen siloxane. The addition catalyst of the component (3) is arbitrarily selected from known catalysts, and is particularly preferably a platinum-based compound, and examples thereof include simple platinum, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. In order to control the curing rate of these compositions, organopolysiloxanes containing vinyl groups such as tetracyclo (methylvinyl) siloxane, alcohols containing carbon-carbon triple bonds, acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol monomethyl ether It is also possible to add a crosslinking inhibitor such as. These compositions have the characteristic that an addition reaction occurs when the three components are mixed and curing starts, but the curing rate rapidly increases as the reaction temperature increases. Therefore, for the purpose of extending the pot life until rubberization of the composition, and shortening the curing time on the heat-sensitive layer, the curing conditions of the composition, the substrate, a temperature condition in a range that does not change the properties of the heat-sensitive layer, In addition, it is preferable to keep the temperature at a high temperature until it is completely cured, from the viewpoint of the stability of the adhesive force with the thermosensitive layer.

In addition to these compositions, it is also effective to add the above-mentioned known silane coupling agents for the purpose of improving the adhesion to the heat-sensitive layer.

In addition to the above, it is optional to add a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group-containing silane (or siloxane) as a composition of the condensation type silicone rubber layer, and to improve the rubber strength. It is optional to add a known filler such as silica for the purpose.

The thickness of these silicone rubber layers 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 g / m ² , it is disadvantageous from an economic point of view.

For the purpose of, for example, protecting the silicone rubber layer on the surface of the waterless planographic printing plate precursor configured as described above, a plain or irregularly-treated thin protective film is laminated on the surface of the silicone rubber layer. It is also possible to form a polymer coating film which can be dissolved in a developing solvent described in JP-A-5-323588.

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 is also possible to form.

A method for producing a waterless planographic printing plate according to the present invention will be described. Using a normal coater such as a reverse roll coater, an air knife coater, or a Meyer bar coater, or a spin coater such as a wheyer, apply the primer layer composition to the substrate as needed.
After thermosetting at 0 ° C. for several minutes, a heat-sensitive layer composition coating liquid is applied,
The composition is heat-cured or light-cured at 50 to 180 ° C. for several minutes, coated with a silicone rubber layer composition coating solution, and treated at a temperature of 50 to 200 ° C. for several minutes to cure the rubber. Thereafter, a protective film is laminated or a protective layer is formed as necessary.

The thus-obtained direct drawing type waterless planographic printing plate precursor is exposed on the image with a laser beam after the protective film is peeled off or from above the protective film.

For the exposure, a laser beam is usually used.
At this time, the light source has a transmission wavelength of 300 nm to 1500.
Ar ion laser, Kr ion laser, He-Ne laser, He-Cd laser, ruby laser, glass laser, semiconductor laser, YAG in the nm range
Laser, titanium sapphire laser, dye laser,
Various lasers such as 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 progress and is economically more advantageous than other laser light sources.

The direct drawing type waterless lithographic printing plate exposed by the above method is subjected to peeling development or ordinary solvent development if necessary.

Examples of the developer used in the present invention include water, those obtained by adding the following polar solvents to water, and aliphatic hydrocarbons (hexane, heptane, “Isoper E,
G, H "(brand name of isoparaffin hydrocarbons manufactured by ESSO), gasoline, kerosene, etc.), at least one kind of aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (trichlene, etc.) A solvent obtained by adding at least one of the following polar solvents to a solvent is preferably used.

Alcohols (methanol, ethanol,
Propanol, 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
Ethers (ethylene glycol monoethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol-2-ethylhexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl Ethers, dioxane, tetrahydrofuran, etc. Esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.) Carboxylic acid (2-ethyl Butyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, oleic acid,
(Lauric acid, etc.) It is also possible to freely add a known surfactant 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 developers, known basic dyes such as crystal violet, Victoria Pure Blue and Astrazone Red, acid dyes and oil-soluble dyes are added, and the image area is dyed simultaneously with the development. 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.

For the development, see JP-A-63-16335.
By using the automatic developing method described in No. 7, the plate can be suitably developed by treating the plate with the above developer and then rubbing the plate with a rotary brush while showering with tap water or the like.

Development is also possible by injecting hot water or steam into the plate instead of the above-mentioned developer.

[0121]

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

Example 1 A primer solution having the following composition was applied on a degreased aluminum plate having a thickness of 0.15 mm using a bar coater.
After drying at 00 ° C. for 2 minutes, a primer layer having a thickness of 4 g / m ² was applied.

(A) Polyurethane resin (Samprene LQ-T1331, manufactured by Sanyo Chemical Industries, Ltd.) 90 parts by weight (b) Blocked isocyanate (Takenate B830, manufactured by Takeda Pharmaceutical Co., Ltd.) 35 parts by weight (c) Epoxy 8 parts by weight of phenol / urea resin (SJ9372, manufactured by Kansai Paint Co., Ltd.) (d) 725 parts by weight of dimethylformamide Subsequently, the following heat-sensitive layer composition was applied thereon using a bar coater, and then applied at 150 ° C. for 1 minute. Dry, film thickness 1 g / m ²
Was provided. (A) 30 parts by weight of carbon black dispersed acrylic resin (15 parts by weight of carbon black) (b) 50 parts by weight of novolak resin (Sumilite Resin PR50731, manufactured by Sumitomo Durres Co., Ltd.) (c) Polyurethane resin (Samprene T1331, Sanyo 50 parts by weight (d) Dimethylformamide 500 parts by weight (e) Ethyl cellosolve 500 parts by weight Subsequently, a silicone rubber layer composition having the following composition was applied thereon using a bar coater. After drying at 200 ° C. for 2 minutes, a silicone rubber layer having a thickness of 2 g / m ² was provided.

(A) 90 parts by weight of vinyl group-containing polysiloxane (terminal hydroxyl group) (b) 8 parts by weight of hydrogen polysiloxane (c) 2 parts by weight of curing retarder (d) 0.2 part by weight of catalyst (e) DY39 -067 (adhesive component) 0.8 parts by weight (f) "Isopar E" (manufactured by Exxon Chemical Co., Ltd.) 1400 parts by weight On the laminate obtained as described above, an 8 μm-thick polyester film "Lumirror" was added. (Manufactured by Toray Industries, Inc.) was laminated using a calendar roller to obtain a direct-drawing waterless planographic printing plate precursor.

Thereafter, the "Lumirror" of the printing plate precursor was peeled off, and the semiconductor laser (O) mounted on the XY table was removed.
PC-A001-mmm-FC, output 0.75W, wavelength 780nm, OPTO POWER CORPORATE
ION), beam diameter 20 μm, exposure time 1
Pulse exposure was performed at 0 μs. At this time, the output of the laser was set to (a) 550 mW, (b) 500 mW, (c) 4
50 mW, (d) 400 mW, (e) 350 mW,
(F) The exposure was changed to 300 mW for 2 minutes each.

Subsequently, the exposed plate was rubbed 60 times with a cotton pad impregnated with water to develop the plate. Waterless lithographic ink (Waterless)
S, manufactured by The Intec Co., Ltd., red) was spread over the entire surface of the developed plate, and the ink adhesion was examined.

The plate surfaces of (a) to (f) were observed, the portion where the ink was deposited was judged to be the heat-sensitive portion, and the sensitivity of the plate was examined. The sensitivity of the plate mentioned here refers to the heat-sensitive portion having the lowest laser output and is represented by its energy value. Table 1 shows the results.

Examples 2 to 3 and Comparative Example 1 A plate material was prepared in the same manner as in Example 1 except that the amounts of the novolak resin and the polyurethane resin in the heat-sensitive layer were changed to Table 1, and the sensitivity was evaluated. . Table 1 shows the results.

Example 4 A plate material was prepared in the same manner as in Example 1 except that the novolak resin in the heat-sensitive layer was changed to a rosin-modified phenol resin (Tespol 1355, manufactured by Hitachi Chemical Co., Ltd.). evaluated. Table 2 shows the results.

Examples 5 to 6, Comparative Example 2 A plate material was prepared in the same manner as in Example 4 except that the amounts of the rosin-modified phenolic resin and polyurethane resin in the heat-sensitive layer were changed to those in Table 1. evaluated. Table 2 shows the results
Shown in

Comparative Example 3 A plate material was prepared in the same manner as in Example 1 except that the composition of the heat-sensitive layer coating solution was changed to the composition shown below, and the sensitivity was evaluated. Table 3 shows the results.

(A) carbon black 15 parts by weight (b) nitrocellulose 12 parts by weight (c) epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 37 parts by weight (d) melamine resin (Uban 2061, Mitsui (Manufactured by Toatsu Co., Ltd.) 36 parts by weight (e) 100 parts by weight of dimethylformamide (f) 800 parts by weight of methyl isobutyl ketone Comparative Example 4 In Example 1, except that the composition of the heat-sensitive layer coating liquid was changed to the composition shown below. All prepared plate materials in the same manner and evaluated the sensitivity. Table 3 shows the results.

(A) 30 parts by weight of carbon black dispersed acrylic resin (including 15 parts by weight of carbon black) (b) 35 parts by weight of epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) (c) Melamine resin (Uban 2061, manufactured by Mitsui Toatsu Co., Ltd.) 35 parts by weight (d) 100 parts by weight of dimethylformamide (e) 800 parts by weight of methyl isobutyl ketone The plate containing a hydroxyl group-containing compound (novolak resin, rosin-modified phenol resin) in the heat-sensitive layer is as follows. Detects laser light,
The silicone rubber layer of the laser irradiation part was peeled off, indicating that it has a function as a printing plate. Also unlike the plate containing nitrocellulose, it has never generates noxious gases such as NO _x.

[0134]

[Table 1]

[Table 2]

[Table 3]

[0135]

According to the present invention, by containing a hydroxyl group-containing compound other than nitrocellulose in the heat-sensitive layer, have never directly imageable waterless planographic printing plate produced of the NO _x during laser irradiation was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/023 511 G03F 7/023 511 7/035 7/035 7/40 521 7/40 521

Claims (12)

[Claims] 1. A direct-drawing waterless planographic printing plate precursor comprising at least a heat-sensitive layer and a silicone rubber layer sequentially laminated on a substrate, wherein the heat-sensitive layer contains a hydroxyl group-containing compound and a light-to-heat conversion material, and is crosslinked. A direct drawing type waterless lithographic printing plate precursor characterized by having a structure. 2. The direct drawing type waterless planographic printing plate precursor according to claim 1, wherein the hydroxyl group-containing compound is a substance other than nitrocellulose. 3. The method according to claim 1, wherein the hydroxyl group-containing compound contains at least one of a resol resin, a novolak resin, a rosin-modified phenol resin, a phenol and / or a polyphenol having a polymerizable or crosslinkable functional group. The direct-drawing waterless planographic printing plate precursor according to claim 1. 4. The compound having a hydroxyl group according to the following general formula (I):
The direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the lithographic printing plate precursor is a direct drawing type waterless lithographic printing plate precursor. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (Wherein L ¹ , L ² , L ³ and L ⁴ are hydrogen atoms or methyl groups. R ¹ is a hydrogen atom, methyl group, ethyl group or propyl group, and R ² is a hydrogen atom, methyl group or R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are a hydrogen atom or a methyl group, X ¹ is a hydroxyl group, a hydrogen atom,
A methyl group, a methoxy group or an ethoxy group, X ² is a hydroxyl group or a p-hydroxybenzyl group, X ³ is a hydroxyl group or a hydrogen atom, and X ⁴ is a methylol group or a methyl group. Z is a methylene group or a carbonyl group. p is 0 or 1, q is 0, 1 or 2, and r and s are 0 or 1. ) 5. The direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the hydroxyl group-containing compound is a reaction product of an epoxy compound. 6. A direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the photothermal conversion material is carbon black. 7. A claim glass transition temperature T _g of the binder resin in the thermosensitive layer is equal to or is 0 ℃ less 1-6
The direct drawing type waterless lithographic printing plate precursor described in. 8. The direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the heat-sensitive layer contains a polyurethane resin as a binder. 9. The content of the hydroxyl group-containing compound in the heat-sensitive layer and the compound having a reactive functional group that generates a hydroxyl group by a crosslinking reaction is 5 to 60% by weight based on the total heat-sensitive layer composition. The direct drawing type waterless planographic printing plate precursor according to any one of claims 1 to 8, wherein 10. A direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the lower layer of the heat-sensitive layer is colored blue, green or purple. 11. A waterless lithographic printing plate obtained by exposing the direct-drawing waterless lithographic printing plate precursor according to claim 1 to development with water or a liquid containing water as a main component. 12. A waterless lithographic printing plate characterized in that the exposed heat-sensitive layer or primer layer is dyed by using a dyeing solution on the developed waterless lithographic printing plate according to claim 11.