JPH1159005A - Direct printing type waterless lithographic printing plate original form plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the generation of poisonous gas, such as NOx or the like, due to the irradiation of laser beam by a method wherein easily decomposable compound to be a substitute for nitrocellulose is contained in a heat sensitive layer. SOLUTION: A compound, having aryl connection or benzyl group (hereinafter shown by aryl group/benzyl group) and hydroxide group, is employed as pyrolitically decomposable compound. A π-radical, such as aryl radical or benzyl radical, is stabilized thermally whereby a compound, containing the generating sources of these radicals or (aryl group/benzyl group) is known that the connection is easily dissociated by heat. When the compound, containing (aryl connection/benzyl group), is shown typically by C=C-C-L, the C-L connection in the heat sensitive layer is cut by the irradiation of laser beam and the heat sensitive layer is ruptured or at least weakened. In this case, L shows hydrogen atom, alkane group, aryl group or the like arbitrarily, however, a functional group, such as alkoxy group or the like, is selected and when the C-L is ether connection, sensitivity is improved.

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, since the metal thin film itself transmits laser light, the sensitivity of the printing plate is reduced. There was a problem that was bad. Therefore, in order to increase the absorptivity of laser light,
An anti-reflection layer must be provided, which further increases the coating process, resulting in cost.

Further, Japanese Patent Laid-Open No. 6-199064, U.S. Pat.
SP5339737, EP0580393, JP-A-6-55723, EP0573091
JP, US Pat. No. 5,378,580, JP-A-7-16
No. 4773, US Pat. No. 5,333,705, EPO
No. 0644647 also discloses a direct drawing type waterless planographic printing plate precursor using a laser beam 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.

That is, in 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, the heat-sensitive layer comprises (I) (a) an allyl group or a benzyl group and ( A direct drawing type waterless planographic printing plate precursor comprising b) a compound having a hydroxyl group and (II) a photothermal conversion substance and having a crosslinked structure.

[0019]

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 compound 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, these nitrogen-containing compounds are not used as the thermally decomposable compound, but a compound having (a) an allyl bond or a benzyl group (hereinafter referred to as an allyl group / benzyl group) and (b) a hydroxyl group is used.

Π radicals such as an allyl radical and a benzyl radical are thermally stable, and a compound containing (aryl / benzyl) as a source of the radical is easily broken by heat. It has been known. (Allyl bond / benzyl group) -containing compound is schematically represented by C =
When expressed as CCL, the C in the heat-sensitive layer by laser irradiation
-L bonds are broken and the thermosensitive layer is destroyed or at least weakened. Here, L is arbitrary such as a hydrogen atom, an alkane group, and an aryl group. In particular, when a functional group such as an alkoxy group is selected and C-L is an ether bond, the sensitivity is further improved. This is because the other radical generated by the bond breaking is also thermally stable, and the bond dissociation energy of the C—O bond in the ether is low.

This is because.

When the compound having (allyl / benzyl) further has a hydroxyl group, the hydroxyl group and the alkoxy group, alkenoxy group, acetoxy group, oxime group, amide group, silanol group, hydrogensiloxane, etc. Is condensed, and the heat-sensitive layer and the silicone rubber layer are cross-linked by a C—O—Si bond. The C—O bond formed at this time is also easily cleaved, and the adhesive force between the silicone rubber layer and the heat-sensitive layer is weakened by laser irradiation. Therefore, the double effect can be obtained by containing a hydroxyl group.

Here, if a nitrogen-containing compound such as nitrocellulose is not contained in the heat-sensitive layer, a plate which is free of nitrogen oxides and is environmentally friendly is obtained.

The compound (allyl group / benzyl group) and the hydroxyl group-containing compound to be contained in the heat-sensitive layer must be solid or capable of maintaining the shape by crosslinking. Instead of a compound having a hydroxyl group as it is, a compound having a reactive functional group that generates a hydroxyl group by a crosslinking reaction may be used.

Specific examples of the compound having an (allyl / benzyl group) and a hydroxyl group are shown below, but the present invention is not limited thereto. The allyl group is treated as including a substituted allyl group such as a cinnamyl group, and the benzyl group is treated as including a substituted benzyl group such as a benzhydryl group or a trityl group.

(1) Alcohols Bifunctional or higher-functional alkenyl alcohols and alcohols having a carboxyl group such as benzyl alcohol, benzylic acid and tropic acid are exemplified.

(2) Allylphenols Allylphenol, allylbiphenol, allylbisphenol, allylbisphenol A type epoxy compounds and the like can be mentioned. Those having at least two functional groups of an allyl group and a hydroxyl group in one molecule are preferred.

(3) Glycidyl ethers (allyl / benzyl) glycidyl ether, ethylene glycol (allyl / benzyl) glycidyl ether, propylene glycol (allyl / benzyl) glycidyl ether, polyethylene glycol (allyl / benzyl)
Glycidyl ether, polypropylene glycol (allyl / benzyl) glycidyl ether and the like.

(4) Linear polymer having a hydroxyl group and (allyloxy group / benzyloxy group) in the side chain The linear polymer having a hydroxyl group and a halogen group in the side chain reacts with sodium (allyl alkoxide / benzyl alkoxide) to form an ether. Thus, the desired compound can be obtained. Examples of the linear polymer include a copolymer of vinyl alcohol and vinyl halide,
If necessary, maleic acid, fumaric acid, oleic acid, cinnamic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, elaidic acid and their esterified products,
A copolymer to which a monomer having an ethylenic double bond such as acrylamide, methacrylamide, or vinyl acetate may be used.

(5) Linear Polymer Having Hydroxyl Group and (Allyloxycarbonyl Group / Benzyloxycarbonyl Group) in Side Chain Ester of linear polymer having hydroxyl group and carboxyl group in side chain and (allyl alcohol / benzyl alcohol) It can be obtained by Examples of the linear polymer include a copolymer of vinyl alcohol and (acrylic acid / methacrylic acid), and if necessary, maleic acid, fumaric acid, oleic acid, cinnamic acid, crotonic acid,
Isocrotonic acid, elaidic acid and their esterified products, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, vinyl acetate, vinyl halide, using a copolymer containing a monomer having an ethylenic double bond such as styrene May be.

Of these, (allyl / benzyl) ethers and esters are preferable, and (3) in the above classification is preferred.
And (4) correspond to this. These thermally decomposable compounds may be used alone or in combination of two or more.

The content of the (allyl / benzyl group) and the compound having a hydroxyl group is preferably from 25 to 80% by weight, more preferably from 35 to 80% by weight, based on the whole thermosensitive layer composition.
60% by weight. When the content is less than 25% by weight, the sensitivity of the printing plate is reduced. When the content is more than 80% by weight,
The solvent resistance of the printing plate tends to decrease.

When an addition type silicone is used for the silicone rubber layer, not only the condensation reaction with the hydroxyl group but also the addition reaction with the double bond in the allyl group is consumed, so that the allyl group is consumed. Decrease. Therefore, it is necessary to pay attention to the amount of the additional component of the silicone rubber.

[0038] 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, especially when the above components are liquid.

As the crosslinking method, there are a thermal crosslinking type in which a crosslinking reaction proceeds by heating and a photo-crosslinking 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.

Compounds containing an epoxy group include polyhydric phenols such as resorcinol, pyrogallol, biphenol and bisphenol, polyhydric alcohols such as ethylene glycol, propylene glycol, erythritol and pentaerythritol, phthalic acid, hexahydrophthalic acid,
Thermal cross-linking can be performed in combination with a polycarboxylic acid such as tetrahydrophthalic acid, dodecynylsuccinic acid, pyrometic acid, chlorenic acid, maleic acid, fumaric acid, anhydrides thereof, or cellulose. Crosslinking with an amine compound is also possible, but is not preferred because it contains a nitrogen atom. In these cases, it is preferable to use a known catalyst such as KOH, SnCl ₄ , Zn (BF ₄ ) _{2 or} an imidazole compound as a catalyst for accelerating the reaction.

The compound having a carboxyl group can be crosslinked by a combination with an epoxy compound. The epoxy compound used at this time is preferably one having two or more functions.

A compound having no crosslinkable functional group such as an epoxy group or a carboxyl group can proceed a crosslinking reaction by using a part of an allyl group or a hydroxyl group as a crosslinking site. That is, a hydroxyl group can be thermally crosslinked by a combination with a polyfunctional isocyanate compound or a polyfunctional epoxy compound, and an allyl group can be polymerized by cleaving its ethylenic double bond with a radical. In this case, however, the compound must have at least two functional groups each containing an allyl group and a hydroxyl group.

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-butylhydrogen Peroxide, peracetic acid t
peroxides such as tert-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 and 1-hydroxycyclohexyl-phenylketone, and benzoin compounds such as benzoin, benzoinethyl ether, benzoinisopropyl ether and benzoinisobutylether are used. Compounds, benzophenone, benzophenone-based compounds such as methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylsulfide, 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 this case, however, it is necessary to adjust the compounding ratio of the crosslinking agent and the crosslinking conditions so that allyl groups and hydroxyl groups remain even after crosslinking.

Since the compounds of the above classes (4) and (5) already have a sufficient molecular weight, they need not necessarily be crosslinked, but can also be crosslinked by the above method.

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 compounds containing water of crystallization, 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.

The average particle size of the primary particles of carbon black is preferably from 15 nm to 29 nm, more preferably from 17 nm to 26 nm. When the average particle size of the primary particles is smaller than 15 nm, the heat-sensitive layer itself becomes transparent and cannot efficiently absorb laser light, and
When it is larger than 9 nm, the particles are not dispersed at a high density, so that the blackness of the heat-sensitive layer does not increase, and similarly, the laser light cannot be efficiently absorbed. This eventually causes a problem that the sensitivity of the printing plate is reduced.

Methods for measuring the primary particle size of carbon black include a sedimentation method, a microscopic method, a transmission method, an adsorption method, and an X-ray method. Among these, a method using an electron microscope and an X-ray method are preferable. As the X-ray method, an X-ray generator manufactured by Rigaku Corporation can be used.

A parameter that affects the sensitivity of the printing plate and the viscosity of the heat-sensitive layer coating solution is the oil absorption of carbon black. The oil absorption indicates the structure of carbon black, that is, the degree of particle aggregation. The larger the oil absorption, the larger the particle diameter. The smaller the oil absorption, the smaller the particle aggregation.

The oil absorption of carbon black is 50 ml / 1.
It is preferably from 00 g / 100 ml / 100 g, more preferably from 60 ml / 100 g / 90 ml / 100 g.
If the oil absorption is less than 50 ml / 100 g, the dispersion of carbon black is reduced and the sensitivity of the printing plate is apt to be reduced. If the oil absorption is more than 100 ml / 100 g, the concentration of the heat-sensitive layer coating solution is increased or the thixotropic property is reduced. It becomes tinged and difficult to handle.

The oil absorption referred to here is ASTM D241
It is defined in 4-70. The amount of DBP added at the time when a mixture of carbon black and DBP is on a paste is kneaded with a spatula while dropping DBP (dibutyl phthalate) into 100 g of carbon black on the powder. (Ml)
It is represented by the value of

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

As these dyes, 400 nm to 1200
Although all dyes having a maximum absorption wavelength in the range of nm can be used, preferred dyes are cyanine, phthalocyanine, phthalocyanine metal complex, naphthalocyanine, naphthalocyanine metal complex, dithiol metal complex, and naphthoquinone. , Anthraquinone, indophenol, indoaniline, pyrylium and thiopyrylium, squarylium, croconium, diphenylmethane, triphenylmethane, triphenylmethanephthalide, triallylmethane, phenothiazine, phenoxazine , Fluoran, thiofluoran, xanthene, indolylphthalide, spiropyran, azaphthalide, chromenopyrazole, leuco auramine, rhodamine lactam, quinazoline, diazaxane , Bislactone, fluorenone, monoazo, ketone imine, diazo, methine, oxazine, nigrosine, bisazo, bisazostilbene, bisazooxadiazole, bisazofluorenone, bisazohydroxy Perinone type,
Azochrome complex salt type, trisazotriphenylamine type,
Thioindigo type, perylene type, nitroso type, 1: 2 type metal complex salt type, intermolecular type CT type, quinoline type, quinophthalone type, fluoxide type acidic dye, basic dye, pigment, oil-soluble dye, triphenylmethane type Leuco dye, cationic dye, azo-based disperse dye, benzothiopyran-based spiropyran, 3,9-dibromoanthanthrone, indanthrone, phenolphthalein, sulfophthalein, ethyl violet, methyl orange, fluorescein, methyl viologen, methylene blue, Jim Roth Betaine and the like.

Among them, 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 total 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.

When the thermally decomposable compound has a highly crosslinked structure and has flexibility, it has sufficient printing durability as a printing plate. for the purpose of improving the storage stability, be contained binder polymer in the heat-sensitive layer is preferably, effective glass transition temperature T _g of the binder include the 0 ℃ below.

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. In addition, since these binders may burn when the heat-sensitive layer is destroyed, those containing no nitrogen atom are preferable.

The content of these binders is preferably at most 60% by weight, more preferably at most 40% by weight, based on the total heat-sensitive layer composition. These binders do not necessarily need to be added because the thermally decomposable substance may play their role in some cases. However, if the content is more than 60% by weight, the sensitivity of the plate 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 additional silicone rubber is used for the silicone rubber layer, silica powder or a (meth) acryloyl group or an allyl group may be used to improve the adhesion to the upper additional silicone rubber layer. The hydrophobic silica powder treated with the contained silane coupling agent 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 the heat-sensitive layer 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 , the heat-sensitive layer is not completely decomposed, so the above range is particularly preferable.

As the substrate of the printing plate, a dimensionally stable plate is used. 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 type 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.

Examples of such an isocyanate compound include paraphenylene diisocyanate and 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-mentioned 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, since the primer layer is exposed in the exposed area of the printing plate to form an image area, it is preferable to add an additive such as a dye or a pigment to the primer layer to improve the plate inspection property. In this case, any dyes and pigments can be used as long as they have a different hue from that of the heat-sensitive layer, but green, blue and purple dyes and pigments are preferable.

The composition for forming the above primer layer is obtained as a composition solution by dissolving in a suitable organic solvent such as dimethylformamide, methyl ethyl ketone, methyl isobutyl ketone and dioxane. 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 composition for forming the above 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 (I). It has a repeating unit as shown below.

[0086]

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 (II) and (III) and (IV), Crosslinked. In some cases, an excess of a crosslinking agent may be present.

[0087]

Embedded image

Embedded image

Embedded image (Where R is the same as R described in formula (I),
R ₁ and R ₂ are monovalent lower alkyl groups, and Ac is an acetyl group. Examples of the silicone rubber which performs such condensation type crosslinking include metal carboxylate salts such as tin, zinc, lead, calcium, and manganese, for example, dibutyltin laurate, tin (II)
A catalyst such as octoate, naphthenate, or chloroplatinic acid is added.

In addition to these compositions, a known adhesion-imparting agent such as alkenyl trialkoxysilane may be added, or a hydroxyl group-containing organopolysiloxane, which is a composition of a condensation type silicone rubber layer, or 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, it is also possible to use an addition type silicone rubber in addition to the above-mentioned condensation type silicone rubber.

As the addition type silicone rubber, one 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 is 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) At least two Si—H groups in one molecule. Organohydrogen polysiloxane having 1 to 1000 parts by weight (3) Addition catalyst 0.01 to 10 parts by weight.

The alkenyl group of the component (1) is
The organic group other than the alkenyl group may be a substituted or unsubstituted alkyl group or aryl group. Component (1) may have a trace amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer, and plays a role in imparting 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.

The hydrogen siloxane of the component (2) not only cures the silicone rubber by crosslinking with the vinyl group of the component (1), but also reacts with the vinyl or hydroxyl groups in the heat-sensitive layer to form a silicone rubber layer. Adhere to the heat sensitive layer. For this reason, it is necessary that the Si—H of the component (2) is excessively contained with respect to 1 equivalent of the C ＝ C bond of the component (1), and specifically, 1.2 to 3 equivalents are contained. Is preferred.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane, and a (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals. As the component (2), both terminals are used. Examples thereof include polydimethylsiloxane having a hydrogen group, α, ω-dimethylpolymethylhydrogensiloxane, (methylhydrogensiloxane) (dimethylsiloxane) copolymer having both terminal methyl groups, and cyclic polymethylhydrogensiloxane. 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 and a hydrolyzable functional group-containing silane (or siloxane), which are compositions 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 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 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.

The 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 a protective film by peeling off the protective film or by laser light from above the protective film.

A laser beam is usually used for exposure.
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 as required.

Examples of the developer used in the present invention include water, water obtained by adding the following polar solvent 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).

A known surfactant can be freely added to the above-mentioned 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.

At the time of 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 an automatic developing method described in Japanese Patent Application Laid-Open No. 7-107, the plate can be suitably developed by treating the plate with the above-mentioned developer and then rubbing the plate with a rotating brush while showering with tap water or the like.

Development can also be carried out by injecting hot water or steam into the plate instead of the above-mentioned developer.

[0111]

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, Takeda Pharmaceutical Co., Ltd.) )) 35 parts by weight (c) 8 parts by weight of epoxy phenol urea resin (SJ9372, manufactured by Kansai Paint Co., Ltd.).

<Solvent Component> (d) Dimethylformamide.

Subsequently, the following heat-sensitive layer composition was applied thereon using a bar coater and dried at 150 ° C. for 1 minute to provide a heat-sensitive layer having a thickness of 1 g / m ² . After that, the whole plate is 2.
Ultraviolet light of 1000 mJ / cm ² was irradiated using an 8 kW ultra-high pressure mercury lamp.

Composition of heat-sensitive layer (solid content: 11% by weight) (a) 30 parts by weight of carbon black-dispersed acrylic resin (15 parts by weight of carbon black) (b) Acrylic acid adduct of bisphenol A diepoxy (V # 540, Osaka, Japan) Organic Chemical Industry Co., Ltd.) 50 parts by weight (c) Copolymerized polyester resin (Vylon 300, manufactured by Toyobo Co., Ltd., Tg-7 ° C.) 15 parts by weight (d) Benzophenone 4 parts by weight (e) 4, 4 ′ -Bisdimethylaminobenzophenone 1 part by weight <Solvent component> (f) Dimethylformamide 50 parts by weight (g) Ethyl cellosolve 50 parts by weight.

Subsequently, a silicone rubber layer composition having the following composition was applied thereon using a bar coater, and cured by heat and moisture at a dew point of 30 ° C. and 125 ° C. for 3.5 minutes to form a film having a thickness of 2 g.
/ M ² of a silicone rubber layer.

(A) Polydimethylsiloxane (molecular weight: about 25,000, terminal hydroxyl group) 92 parts by weight (b) Vinyl tri (methylethylketoxime) silane 6 parts by weight <Solvent component> c) "Isopar E" (manufactured by Exxon Chemical Co., Ltd.).

A 10 μm-thick polypropylene film “Trefane” (manufactured by Toray Industries, Inc.) was laminated on the laminate obtained as described above using a calendar roller, and a direct-drawing waterless planographic printing plate precursor was laminated. I got

Using a metal halide lamp (Idolfin 200, manufactured by Iwasaki Electric Co., Ltd.) for the printing plate, UV
Meter (Oak Works, Light Measure Type UV
At -402 A), the entire surface was exposed at an illuminance of 11 mW / cm ² for 6 seconds.

Thereafter, "Trefane" of this printing plate precursor was used.
Was peeled off, and pulse exposure was performed using a semiconductor laser (wavelength 780 nm) mounted on an XY table with a beam diameter of 20 μm and an exposure time of 10 μs. At this time, the output of the laser was (a) 500 mW, (b) 450 mW,
(C) 400 mW, (d) 350 mW, (e) 300 m
The exposure was changed to W 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 (e) were observed, and the portion where the ink was deposited was judged to be a 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. A plate containing an acrylic acid adduct of bisphenol A diepoxy (V # 540), which is a “(a) compound containing an allyl group or a benzyl group and (b) a hydroxyl group”, in a heat-sensitive layer, detects laser light. The silicone rubber layer in the laser-irradiated portion was peeled off, indicating that it had a function as a printing plate.

Examples 2 to 3 and Comparative Example 1 The same procedures as in Example 1 were carried out except that the amounts of the acrylic acid adduct of bisphenol A epoxy and the copolymerized polyester resin in the heat-sensitive layer were changed as shown in Table 1. A plate material was prepared by the above method, 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 composition of the heat-sensitive layer coating solution was changed to the following composition, and the sensitivity was evaluated. Table 2 shows the results. A plate containing an esterified product of poly (vinyl alcohol) (acrylic acid) and allyl alcohol, which is "a compound containing (a) an allyl group or a benzyl group and (b) a hydroxyl group",
The laser beam was sensed, and the silicone rubber layer in the laser-irradiated portion was peeled off, indicating that it had a function as a printing plate.

Thermosensitive layer composition (solid content concentration: 11% by weight) (a) 30 parts by weight of carbon black-dispersed acrylic resin (15 parts by weight of carbon black) (b) Ester of poly (vinyl alcohol) (acrylic acid) and allyl alcohol 65 parts by weight (c) Copolymerized polyester resin (Vylon 300, manufactured by Toyobo Co., Ltd., Tg-7 ° C) 5 parts by weight <Solvent component> (d) 20 parts by weight of dimethylformamide (e) 30 parts by weight of ethyl cellosolve ( f) 50 parts by weight of tetrahydrofuran.

Examples 5 to 6, Comparative Example 2 In Example 4, all were changed except that the compounding amount of the esterified product of poly (vinyl alcohol) (acrylic acid) and allyl alcohol in the heat-sensitive layer was changed as shown in Table 2. A plate material was prepared in the same manner, and the sensitivity was evaluated. Table 2 shows the results.

Example 7 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 following composition.

(A) Near infrared absorbing agent (PA-1006, manufactured by Mitsui Toatsu Dye Co., Ltd.) 60 parts by weight (b) Acrylic acid adduct of bisphenol A diepoxy (V # 540, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 20 parts by weight (c) Copolymerized polyester resin (Byron 300, manufactured by Toyobo Co., Ltd., Tg-7 ° C.) 15 parts by weight (d) Benzophenone 4 parts by weight ( e) 4,4'-bisdimethylaminobenzophenone 1 part by weight <Solvent component> (f) 50 parts by weight of dimethylformamide (g) 50 parts by weight of ethyl cellosolve.

The thus-prepared printing plate precursor was exfoliated and the “trefan” was peeled off, and a semiconductor laser (wavelength: 780 nm) mounted on an XY table was used.
Pulse exposure was performed with an exposure time of 10 μs and a laser output of 500 mW. Subsequently, the exposed plate was rubbed 60 times with a cotton pad impregnated with the following dyeing solution,
Dyeing was performed simultaneously with development. Macbeth reflection densitometer (RD
514), the exposed portion (image portion) and the unexposed portion (non-image portion)
The optical densities were measured to be 1.50 and 0.56, respectively, and a printing plate having excellent contrast, that is, excellent plate inspection properties was obtained.

Composition of Staining Solution (a) Basic Dye (Crystal Violet, Hodogaya Chemical Industry Co., Ltd.) 1 part by weight (b) Basic Dye (Brilliant Basic Cyanine 6GH, Hodogaya Chemical Industry Co., Ltd.) 4 Parts by weight (c) 20 parts by weight of anionic activator (sodium 1-methyl-pentyl sulfate) (d) 100 parts by weight of butyl carbitol (e) Defoamer (KS-502, manufactured by Shin-Etsu Chemical Co., Ltd.) 02 parts by weight (f) 875 parts by weight of pure water.

Comparative Example 3 In Example 7, the exposed plate was rubbed 60 times with a cotton pad impregnated with water to perform development. Exposed area (image area) and unexposed area (non-image area) with Macbeth reflection densitometer
The optical densities of the obtained printing plates were 0.62 and 0.56, respectively. The resulting printing plates had poor contrast, that is, poor plate inspection properties.

Comparative Example 4 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.

Composition of heat-sensitive layer (solid content: 11% by weight) (a) 15 parts by weight of carbon black (b) 12 parts by weight of nitrocellulose (c) 37 weight parts of epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) Part (d) 36 parts by weight of melamine resin (Uban 2061, manufactured by Mitsui Toatsu Co., Ltd.) <Solvent component> (e) 20 parts by weight of dimethylformamide (f) 80 parts by weight of methyl isobutyl ketone.

Comparative Example 5 A plate material was prepared in the same manner as in Example 1 except that the composition of the heat-sensitive layer coating liquid was changed to the composition shown below, and the sensitivity was evaluated. Table 3 shows the results.

(Thermal layer composition (solids concentration 11% by weight)) (a) 30 parts by weight of carbon black dispersed acrylic resin (15 parts by weight of carbon black) (b) Epoxy resin (Epicoat 828, Yuka Shell Epoxy Co., Ltd.) 35 parts by weight (c) Melamine resin (Uban 2061, manufactured by Mitsui Toatsu Co., Ltd.) 35 parts by weight <Solvent component> (d) 20 parts by weight of dimethylformamide (e) 80 parts by weight of methyl isobutyl ketone.

Compounds having an (allyl group / benzyl group) and a hydroxyl group in the heat-sensitive layer (allyl glycidyl ether,
The plate containing the acrylic acid adduct of bisphenol A epoxy) senses the laser beam, and the silicone rubber layer in the laser-irradiated portion is peeled off, indicating that the plate has a function as a printing plate. Also unlike the plate containing nitrocellulose, it has never generates noxious gases such as NO _x.

[0138]

[Table 1]

[Table 2]

[Table 3]

[0139]

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.

Claims (10)

[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 comprises (I) (a) an allyl group or a benzyl group and ( (b) A direct-drawing waterless planographic printing plate precursor comprising a compound having a hydroxyl group, and (II) a photothermal conversion substance, and having a crosslinked structure. 2. A direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the compound having (a) an allyl group or a benzyl group and (b) a hydroxyl group is a reaction product of an epoxy compound. . 3. A direct drawing type waterless lithographic printing plate according to claim 1, wherein the compound having (a) an allyl group or a benzyl group and (b) a hydroxyl group further contains an ether bond. Original version. 4. The heat-sensitive layer according to claim 1, wherein the content of the compound having (a) an allyl group or a benzyl group and (b) a hydroxyl group is 25 to 80% by weight based on the total heat-sensitive layer composition. Item 4. A direct-drawing waterless planographic printing plate precursor according to any one of Items 1 to 3. 5. The direct drawing type waterless lithographic printing plate precursor according to claim 1, wherein the heat-sensitive layer does not contain nitrocellulose. 6. The method of claim glass transition temperature T _g of the binder resin in the thermosensitive layer is equal to or is 0 ℃ less 1-5
The direct drawing type waterless lithographic printing plate precursor according to any of the above. 7. 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. 8. A waterless planographic printing plate obtained by exposing the direct-drawing waterless planographic printing plate precursor according to claim 1 to development with water or a liquid containing water as a main component. 9. A waterless lithographic printing plate, characterized in that a dyeing solution is applied to the waterless lithographic printing plate according to claim 8, and a layer exposed by peeling off the silicone rubber layer is dyed. 10. A direct drawing type waterless lithographic printing plate precursor according to claim 1, which is exposed by exposing the silicone rubber layer simultaneously with development using a developing solution and / or a dyeing solution. Lithographic printing plate without water, dyed layer.