JPH09150589A - Original plate of direct writing waterless lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain an improvement in a greasing property by making an ink- receptive heat-sensitive layer contain carbon black. SOLUTION: An ink-receptive heat-sensitive layer is made to contain carbon black, particularly carbon black of a furnace type, as a photothermal conversion substance for absorbing laser light efficiently and converting it into heat. The particle size of the carbon black is 15-29nm preferably, and the quantity of the photothermal conversion substance to be used is 2-10wt.% more preferably 5-60wt.%, to the whole composition of the ink-receptive heat-sensitive layer. It is preferable, besides, that the ink-receptive heat-sensitive layer is made to contain a hydroxyl-containing polymer in order to improve the adhesion to a silicone rubber layer, that is, the resistance to printing. According to this constitution, an improvement is made in a greasing property in comparison with usual direct writing waterless lithographic printing plate.

Description

Detailed Description of the Invention

[0001]

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

[0002]

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

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

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

[0005] Above all, the method using laser light is superior to other methods in resolution and plate making speed.
There are many types.

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

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

[0008]

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

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

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

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

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

The thermal destruction method (6) has the drawback of lower sensitivity than the above-mentioned method, but on the contrary, it has the advantage that it can be handled in a bright room, and the output of the semiconductor laser serving as a light source is sharp. Recently, its usefulness has been reconsidered due to recent progress and cost reduction.

For example, JP-A-6-55723, JP-A-6-199064, JP-A-7-164773, US
P5339737, USP5353705, EP0
573091 and EP0580393 describe direct drawing type waterless planographic printing plate precursors using a laser beam as a light source.

The laser-sensitive layer of the thermal destruction printing plate precursor uses carbon black as a laser light absorbing compound, and this absorbs the laser light to convert it into heat energy. That is, the laser-sensitive layer is a heat-sensitive layer, the heat destroys the laser-sensitive layer, and by removing this portion by development, the upper silicone rubber layer is peeled off to form an ink inking portion.

However, in this printing plate, when the temperature of the plate surface rises during printing, the ink adheres to the silicone rubber layer, which is a non-image area, and as a result, the printed matter is stained (ground stain). Had.

The cause is that the thickness of the silicone rubber layer is thin.

Therefore, in order to improve the background stain resistance, it is necessary to increase the film thickness of the silicone rubber layer. However, if the film thickness is increased, there arises a problem that the developability is deteriorated.

Further, since the cells in the image area are deep, there is a problem that too much ink is deposited and the ink consumption tends to increase.

Further, USP5379698 describes a direct drawing type waterless planographic printing plate precursor which forms a metal thin film as a heat sensitive layer in a similar manner.

In this case, the depth of the cells in the image area is shallower because the heat-sensitive layer is a thin film, but since the plate structure is the same as that of the carbon black type, the stain resistance during printing is
It had the same problem.

These problems are common to the waterless planographic printing plate of the upper layer of silicone rubber, and as a method for solving this problem, in the conventional waterless planographic printing plate, the silicone rubber layer is provided below the photosensitive layer. A so-called silicone rubber lower layer waterless planographic printing plate is described in Japanese Patent Publication No. 56-14976.

This is not a direct drawing type but an ordinary waterless planographic printing plate. However, laminating a photosensitive layer on a silicone rubber layer is preferable because the silicone layer easily repels many liquids. It is extremely difficult to apply.

Further, even if the coating can be applied satisfactorily, there is a problem that the surface layer is easily peeled off by printing due to poor adhesion to the silicone rubber layer, resulting in poor printing durability.

This was due to the difficulty of forming a chemical bond between the silicone rubber layer and the photosensitive layer.

In order to remedy the drawbacks of the prior art, the present invention provides a silicone rubber layer below the ink-receptive heat-sensitive layer, adds a hydroxyl group-containing compound to the ink-receptive heat-sensitive layer, or a silicone rubber layer, Alternatively, by adding a silane coupling agent to the ink-receptive heat-sensitive layer, the adhesion to the silicone rubber layer was improved, resulting in improved scumming resistance. The purpose is to provide.

[0027]

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

1. In a direct drawing type waterless lithographic printing plate precursor comprising a substrate, a silicone rubber layer provided on the substrate and an ink receiving heat sensitive layer provided on the silicone rubber layer, the ink receiving heat sensitive layer contains carbon black. A direct drawing type waterless planographic printing plate precursor characterized by that.

2. 1. The direct drawing type waterless planographic printing plate precursor as described in 1 above, wherein the carbon black is a furnace type carbon black.

3. 1. The direct drawing type waterless lithographic printing plate precursor as described in 1 above, wherein the ink-receptive heat-sensitive layer contains at least one of a hydroxyl group-containing polymer and a hydroxyl group-containing monomer.

4. 1. The direct drawing type waterless lithographic printing plate precursor as described in 1 above, wherein the ink-receptive heat-sensitive layer contains nitrocellulose.

5. 1. A waterless lithographic printing plate precursor for direct drawing, wherein the silicone rubber layer or the ink-receptive heat-sensitive layer in 1 above contains a silane coupling agent.

6. 1. The direct drawing type waterless lithographic printing plate precursor as described in 1 above, wherein the silicone rubber layer or the ink-receptive heat-sensitive layer contains at least one of acrylsilane, methacrylsilane, vinylsilane and allylsilane.

7. 1. The direct drawing type waterless lithographic printing plate precursor as described in 1 above, wherein the silicone rubber layer or the ink-receptive heat-sensitive layer contains at least one of epoxysilane, aminosilane and mercaptosilane.

8. The direct drawing type waterless planographic printing plate precursor as described in any one of 1 to 7 above is selectively exposed and developed.
Waterless planographic printing plate.

9. Direct drawing type waterless lithographic printing, characterized in that a substrate having a silicone rubber layer on one side and a film having an ink-receptive heat-sensitive layer on one side are laminated so that the silicone rubber layer surface and the ink-receptive heat-sensitive layer surface are in contact with each other. Plate original plate manufacturing method.

10. The ink-receptive heat-sensitive layer is removed by irradiating the direct drawing type waterless planographic printing plate precursor according to any one of 1 to 7 above with a laser beam to expose the lower silicone rubber to expose the ink repellent non-image area. A method for producing a direct drawing type waterless planographic printing plate, which comprises forming

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Here, 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 used in the present invention will be described.

The ink-receptive heat-sensitive layer used in the present invention efficiently absorbs laser light and converts it into heat, which is momentarily partially or entirely decomposed and is laminated on the silicone layer. Therefore, it is necessary to have good coatability and adhesiveness to silicone rubber.

First, in order to efficiently absorb the laser light and convert it into heat, it is preferable to contain a photothermal conversion substance.

The compound is not particularly limited as long as it is a substance capable of absorbing light and converting it into heat. For example, black pigments such as carbon black, carbon graphite, aniline black, cyanine black, and the like, Phthalocyanine, naphthalocyanine green pigment,
Iron powder, diamine-based metal complex, dithiol-based metal complex, phenolthiol-based metal complex, mercaptophenol-based metal complex, arylaluminum metal salts, water-containing inorganic compound, copper sulfate, chromium sulfide, silicate compound, titanium oxide, Addition of metal oxides such as vanadium oxide, manganese oxide, iron oxide, cobalt oxide and tungsten oxide, hydroxides and sulfates of these metals, and metal powders such as bismuth, tin, tellurium, iron, aluminum and magnesium. It is preferable to add an agent.

Among these, the photothermal conversion efficiency and
Carbon black is particularly preferable in terms of economy and handleability. Furthermore, even in carbon black,
Furnace type carbon black is particularly preferable due to its variety.

The carbon black having various particle sizes is commercially available.
A particle size of 5 nm to 29 nm is preferable. Particle size is 15
This is because if it is smaller than nm, the particles are likely to aggregate to reduce the dispersibility, and if it is larger than 29 nm, the coloring property is deteriorated and the laser light cannot be efficiently absorbed.

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

The amount of these light-heat converting substances used is preferably 2-70% by weight, more preferably 5-60% by weight, based on the total ink-receptive heat-sensitive layer composition. 2% by weight
If less than, the sensitivity of the printing plate is likely to decrease,
If the amount is more than 70% by weight, the printing durability of the printing plate tends to decrease.

Next, among the above-mentioned conditions, as compounds satisfying thermal decomposability, ammonium nitrate, potassium nitrate,
Nitro compounds such as sodium nitrate and nitrocellulose are preferably used.

Further, among these, nitrocellulose is a polymer, so that it has a high viscosity in a solution, and therefore, the coating property to silicone becomes good.

Further, nitrocellulose is JIS K 6
It has a hydroxyl group as defined by 703, and this hydroxyl group acts extremely effectively on the adhesiveness to the silicone layer. This is because nitrocellulose is a linear polymer, and since D-glucose, which is a repeating unit, has a maximum of 3 hydroxyl groups, a condensation reaction occurs at the interface with the silicone layer, especially in terms of adhesiveness. This is because it works effectively in.

The nitrogen content of nitrocellulose is defined by the degree of substitution of the nitro group, and the nitrogen content used in the present invention is preferably 6.8% to 13.5%, more preferably 10.3. % To 12.8%. When the nitrogen content is less than 6.8%, the sensitivity of the printing plate is reduced, and when it is more than 13.5%, the number of hydroxyl groups in one molecule is decreased, so that the silicone layer is Adhesiveness is reduced, and as a result, printing durability is reduced, which is not preferable.

Further, nitrocellulose having various molecular weights depending on the average degree of polymerization can be obtained, and all of them can be used. However, those used in the present invention preferably have an average degree of polymerization of 35 to 480. , And more preferably 45 to 290. Average degree of polymerization is 35
When it is less than 480, the viscosity of the ink-receptive heat-sensitive layer becomes low, and the coating property on the silicone layer is liable to be deteriorated. When it is more than 480, the viscosity becomes too high and the handling becomes inconvenient.

The amount of these thermally decomposable compounds used is preferably 10 to 80% by weight, more preferably 20 to 60% by weight, based on the total ink receiving heat-sensitive layer composition. If the amount used is less than 10% by weight, the sensitivity of the printing plate decreases,
If the amount is more than 80% by weight, the storage stability of the printing plate tends to decrease.

Further, the ink-receptive heat-sensitive layer preferably contains a hydroxyl group-containing polymer in order to improve the adhesiveness to the silicone rubber layer, that is, the printing durability.

As this hydroxyl group-containing polymer, a cellulose derivative other than the above-mentioned nitrocellulose, that is,
Carboxymethyl cellulose, cellulose acetate,
Other than cellulose propyl acetate, cellulose butyl acetate, cellulose triacetate, hydroxypropyl cellulose ether, ethyl cellulose ether, cellulose phosphate, etc., epoxy resin, phenol resin, acrylic resin, polyvinyl alcohol, polyvinyl butyral, polyvinyl alcohol-acetal copolymer , Polyvinyl acetal, polyvinyl alcohol-polyacetal copolymer, polyvinyl alcohol-polyvinyl butyral copolymer, and the like, among them,
Cellulose acetate, epoxy resin, phenol resin and the like are preferable, and cellulose acetate and epoxy resin are more preferable.

The amount of these hydroxyl group-containing polymers used is
It is preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight, based on the total ink receiving heat-sensitive layer composition. If the content is less than 10% by weight, the printing durability tends to decrease, and if it exceeds 60% by weight, the sensitivity tends to decrease.

A silane compound is preferably added to the ink-receptive heat-sensitive layer for the purpose of strengthening the adhesiveness to the underlying silicone rubber layer.

As such a silane-based compound, any known compound having a silyl group can be used in addition to a known silane coupling agent. In the present invention, acrylsilane and methacrylsilane ( Hereinafter, both are collectively referred to as (meth) acrylic silane),
Unsaturated group-containing silane coupling agents such as vinylsilane and allylsilane, and functional group-containing silane coupling agents such as epoxysilane, aminosilane, and mercaptosilane are preferably used.

Among these, the unsaturated group-containing silane coupling agent copolymerizes with other monomers when the heat-sensitive layer is subjected to light or heat curing, and exhibits an adhesive force at the interface with the silicone layer. In the invention, it effectively acts on the adhesion of the heat-sensitive layer.

Specific examples of the (meth) acrylsilane include N- (3- (meth) acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane,
Bis ((meth) acryloxypropyl) -1,1,3
3-tetramethyldisiloxane, 2- (meth) acryloxyethyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, (meth) acryloxypropylbis (trimethylsiloxy) methylsilane, 3
-(Meth) acryloxypropyldimethylchlorosilane, 3- (meth) acryloxypropylmethyldichlorosilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyldimethylethoxysilane, 3- (meth) Acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryl Roxypropyltrimethoxysilane, 3- (meth) acryloxypropylpentamethyldisiloxane, 3-
(Meth) acryloxypropyltris (methoxyethoxy) silane, 3- (meth) acryloxytris (trimethylsiloxy) silane, 2- (trimethylsiloxy) ethyl (meth) acrylate, trimethylsilyl (meth)
Examples thereof include acrylates, and preferably 3- (meth) acryloxypropyltrimethoxysilane, 3-
(Meth) acryloxypropyldimethylethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, 3- ( Examples thereof include (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane.

Further, vinylsilane and allylsilane exhibit an adhesive force by reacting with hydrogenpolysiloxane, especially when the lower silicone rubber layer is an addition type.

Specific examples of vinylsilanes include bis (dimethylamino) methylvinylsilane, 1-bromovinyltrimethylsilane, chloromethyldimethylvinylsilane, 3-chloropropyldimethylvinylsilane, 1-chlorovinyltrichlorosilane and N, N-dimethylamino. Vinyldiethoxysilane, diphenylvinylchlorosilane, diphenylvinylethoxysilane, 1,3-divinyl-1,3-dimethyl-1,3-dichlorodisiloxane, divinyldimethylsilane, 1,3-divinyl-1,
3-diphenyl-1,3-dimethyldisilazane, 1,3
-Divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyltetratetraethoxydisiloxane, 1,3-divinyltetramethyldisilazane, 1,3-divinyltetramethyldisiloxane, 1,
4-divinyl-1,1,4,4-tetramethyldisilylethylene, phenyldimethylvinylsilane, phenylmethylvinylchlorosilane, phenylmethylvinylsilane, phenylvinylchlorosilane, phenylvinyldimethoxysilane, 1,1,3,3-tetravinyl Dimethyldisiloxane, tetravinylsilane, 1,3,5,7-
Tetravinyltetramethylcyclotetrasiloxane, triphenylvinylsilane, trivinylmethylsilane,
1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, vinyldiethylmethylsilane,
Vinyldimethylchlorosilane, vinyldimethylethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, 1-vinylsilatrane, vinyltriacetoxysilane, vinyltrichlorosilane,
Vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltrimethylsilane, vinyltriphenoxysilane, vinyltris (tri-s-butoxysiloxanyl) silane, vinyltris (t-butylperoxy) silane, vinyltris ( 2-methoxyethoxy) silane and vinyltris (trimethylsiloxy) silane can be mentioned, but preferably,
They are vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrimethoxysilane, divinyldiethoxysilane and vinyltriacetoxysilane.

Specific examples of the allylsilane include allyldimethylchlorosilane, allyldimethylsilane, allylmethyldichlorosilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diallyldiethoxysilane, diallyldimethoxysilane and triallylethoxysilane. , Triallylmethoxysilane,
Phenylallyldiethoxysilane, phenylallyldimethoxysilane, phenyldiallylethoxysilane, phenyldiallylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethylsilane, diphenyldiallylsilane, phenylallyldichlorosilane, tetraallyloxysilane, O-trimethylsilyl Examples include allyl alcohol, but preferably allyltriethoxysilane, allyltrimethoxysilane,
These are diallyldiethoxysilane and diallyldimethoxysilane.

The epoxysilane is 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
As aminosilane, N-2- (aminoethyl) -3
-Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and as the mercaptosilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Examples include propyltriethoxysilane.

The amount of the silane compound added is
It is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, based on the total heat-sensitive layer composition.

Alternatively, the silane coupling agent may be dissolved in an appropriate solvent and applied as a dilute solution onto the silicone rubber layer to be used as an adhesive layer.

In this case, the film thickness of the silane coupling agent layer is sufficient if the film thickness is such that a monomolecular film of the silane coupling agent is formed. Specifically, it is preferably 1000 angstroms or less, It is preferably 500 angstroms or less. When the film thickness is thicker than 1000 angstrom, the adhesiveness with the silicone rubber layer is likely to be lowered, and the printing durability and solvent resistance of the printing plate are reduced.

For the purpose of improving the sensitivity of the heat-sensitive layer, urea and urea derivatives, zinc white, lead carbonate, lead stearate,
It is also effective to add a thermal decomposition aid such as glycolic acid. The addition amount of these thermal decomposition aids is preferably 0.02 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total photosensitive layer composition.

These heat-sensitive layers preferably have a crosslinked structure in order to improve solvent resistance to printing ink.

Examples of the polyfunctional crosslinking agent used for introducing the crosslinked structure include an isocyanate compound, an epoxy compound, a polymerizable monomer and the like. In the present invention, the polymerizable monomer is preferably used. Further, among the polymerizable monomers, a monomer containing a hydroxyl group is more preferably used. The reason for this is that, as in the case of the nitrocellulose described above, the hydroxyl group acts extremely favorably on the adhesion to the lower silicone rubber layer.

As such a hydroxyl group-containing photopolymerizable monomer, any one can be used as long as it has an alcoholic or phenolic hydroxyl group in the molecule, but particularly preferable ones are a diamine compound and glycidyl (meth). The following monomers are obtained by reacting an acrylate and a monoglycidyl compound.

As the aliphatic hydroxyl group-containing monomer,
N, N, N ', N'-tetra- (2-hydroxy-3
-(Meth) acryloyloxypropyl) monooxyethylenediamine, N, N, N ', N'-tetra- (2-
Hydroxy-3- (meth) acryloyloxypropyl) dioxyethylenediamine, N, N, N ', N'-
Tetra- (2-hydroxy-3- (meth) acryloyloxypropyl) decaoxyethylenediamine, N,
N, N ', N'-tetra- (2-hydroxy-3- (meth) acryloyloxypropyl) tritriacontaoxyethylenediamine, N, N, N', N'-tetra-
(2-hydroxy-3- (meth) acryloyloxypropyl) trioxyethylenediamine, N, N, N'-
Tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N'-mono (2-hydroxy-3-methoxypropyl) monooxyethylenediamine, N,
N, N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) dioxyethylenediamine, N, N'-di- (2 -Hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-methoxypropyl) monooxyethylenediamine, N, N'-di- (2-hydroxy-3- (meth ) Acryloyloxypropyl) -N, N'-di-
(2-Hydroxy-3-methoxypropyl) dioxyethylenediamine, N, N, N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N '
-Mono- (2-hydroxy-3-butoxypropyl) monooxyethylenediamine, N, N, N'-tri- (2
-Hydroxy-3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-butoxypropyl) dioxyethylenediamine, N, N'-di-
(2-Hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-butoxypropyl) monooxyethylenediamine, N, N '
-Di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3
-Butoxypropyl) dioxyethylenediamine, N,
N, N ', N'-tetra- (2-hydroxy-3- (meth) acryloyloxypropyl) monooxypropylenediamine, N, N, N', N'-tetra- (2-hydroxy-3- (meth ) Acryloyloxypropyl) decaoxypropylenediamine, N, N, N ', N'-tetra- (2-hydroxy-3- (meth) acryloyloxypropyl) tritriacontaoxypropylenediamine, N, N, N', N'-tetra- (2-hydroxy-3- (meth) acryloyloxypropyl) trioxypropylenediamine, N, N, N ', N'-tetra-
(2-hydroxy-3- (meth) acryloyloxypropyl) hexaoxypropylenediamine, N, N, N
′ -Tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N′-mono (2-hydroxy-3
-Methoxypropyl) monooxypropylenediamine,
N, N, N'-tri- (2-hydroxy-3- (meta)
Acryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) dioxypropylenediamine, N, N, N'-tri- (2-hydroxy-3)
-(Meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) decaoxypropylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N,
N'-di- (2-hydroxy-3-methoxypropyl)
Monooxypropylenediamine, N, N-di- (2-hydroxy-3- (meth) acryloyloxypropyl)
-N, N'-di- (2-hydroxy-3-methoxypropyl) dioxypropylenediamine, N, N, N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N'- Mono- (2-hydroxy-3-butoxypropyl) monooxypropylenediamine, N,
N, N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-butoxypropyl) dioxypropylenediamine, N, N'-di- ( 2-hydroxy-3- (meth)
Acryloyloxypropyl) -N, N'-di- (2-
Hydroxy-3-butoxypropyl) monooxypropylenediamine, N, N'-di- (2-hydroxy-3-
(Meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-butoxypropyl) dioxypropylenediamine, N, N, N'-tri- (2-hydroxy-3- (meth) acryloyl Oxypropyl) ―
N'-mono- (2-hydroxy-3-2 ethylhexyloxypropyl) trioxypropylenediamine, N,
Examples include N, N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-phenoxypropyl) trioxypropylenediamine.

As the aromatic hydroxyl group-containing polymerizable monomer, N, N, N'-tri- (2-hydroxy-
3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) m-xylylenediamine, N, N, N'-tri- (2-hydroxy-3- (meth)) Acryloyloxypropyl) -N
´-Mono- (2-hydroxy-3-methoxypropyl)
p-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl)-
N, N'-di- (2-hydroxy-3-methoxypropyl) m-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl)
-N, N'-di- (2-hydroxy-3-methoxypropyl) p-xylylenediamine, N-mono- (2-hydroxy-3- (meth) acryloyloxypropyl)-
N, N ', N'-tri- (2-hydroxy-3-methoxypropyl) m-xylylenediamine, N-mono- (2
-Hydroxy-3- (meth) acryloyloxypropyl) -N, N ', N'-tri- (2-hydroxy-3--
Methoxypropyl) p-xylylenediamine, N, N,
N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) m-xylylenediamine,
N, N, N'-tri- (2-hydroxy-3- (meta)
Acryloyloxypropyl) -N'-mono- (2-hydroxy-3-methoxypropyl) p-xylylenediamine, N-mono- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N ', N'-Tri-
(2-Hydroxy-3-methoxypropyl) m-xylylenediamine, N-mono- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N ', N'-
Tri- (2-hydroxy-3-methoxypropyl) p-
Xylylenediamine, N, N, N'-tri- (2-hydroxy-3- (meth) acryloyloxypropyl)-
N'-mono- (2-hydroxy-3-butoxypropyl) m-xylylenediamine, N, N, N'-tri-
(2-hydroxy-3- (meth) acryloyloxypropyl) -N'-mono- (2-hydroxy-3-butoxypropyl) p-xylylenediamine, N, N'-di-
(2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-butoxypropyl) m-xylylenediamine, N, N'-di- (2-hydroxy- 3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-butoxypropyl) p-xylylenediamine, N, N, N
′ -Tri- (2-hydroxy-3- (meth) acryloyloxypropyl) -N′-mono- (2-hydroxy-
3-2 ethylhexyloxypropyl) m-xylylenediamine, N, N, N'-tri- (2-hydroxy-3-
(Meth) acryloyloxypropyl) -N'-mono-
(2-hydroxy-3-2 ethylhexyloxypropyl) p-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl)
-N, N'-di- (2-hydroxy-3-2ethylhexyloxypropyl) m-xylylenediamine, N, N '
-Di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3
-2 ethylhexyloxypropyl) p-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth)
Acryloyloxypropyl) -N, N'-di- (2-
Hydroxy-3-phenoxypropyl) m-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di-
(2-hydroxy-3-phenoxypropyl) p-xylylenediamine and the like can be mentioned.

Among these, in particular, N, N'-di-
(2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-methoxypropyl) m-xylylenediamine, N, N'-di- (2-hydroxy- 3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-methoxypropyl) p-xylylenediamine, N, N'-
Di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-
Butoxypropyl) m-xylylenediamine, N, N '
-Di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3
-Butoxypropyl) p-xylylenediamine, N, N
′ -Di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N′-di- (2-hydroxy-
3-2 ethylhexyloxypropyl) m-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di-
(2-hydroxy-3-2 ethylhexyloxypropyl) p-xylylenediamine, N, N'-di- (2-hydroxy-3- (meth) acryloyloxypropyl)
-N, N'-di- (2-hydroxy-3-phenoxypropyl) m-xylylenediamine, N, N'-di- (2
-Hydroxy-3- (meth) acryloyloxypropyl) -N, N'-di- (2-hydroxy-3-phenoxypropyl) p-xylylenediamine is more preferably used.

In addition to the above-mentioned monomers, polyfunctional alcohols such as glycerin and trimethylolethane, to which ethylene oxide and propylene oxide are added and then (meth) acrylated, JP-B-48-417.
No. 08, JP-B-51-37193, urethane acrylates as described in JP-B-48-64
183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3
Polyester acrylates described in JP-A-0490, polyfunctional acrylates such as epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and methacrylates, and the like, having a hydroxyl group. Any material can be preferably used.

Furthermore, by introducing an organic silyl group into the molecular chain of the polyfunctional crosslinking agent described in Japanese Patent Application No. 4-2715222,
Those having improved adhesion to the lower silicone layer can also be preferably used.

By using the above-mentioned hydroxyl group-containing polymerizable monomer in combination with a known photopolymerization initiator, thermal polymerization initiator and sensitizer, crosslinking becomes possible.

The amount of the hydroxyl group-containing polymerizable monomer used is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, based on the total ink-receptive heat-sensitive layer composition.
When the amount is less than 1% by weight, the solvent resistance of the printing plate tends to decrease. When the amount is more than 50% by weight, the printing plate becomes hard and the printing durability tends to decrease.

Further, the heat-sensitive layer may appropriately contain additives such as antiseptics, antihalation dyes, defoamers, antistatic agents, dispersants, emulsifiers and surfactants.

Particularly, it is preferable to add a fluorine-containing surfactant in order to improve the coating property. The amount of these additives added is usually 10% by weight or less based on the total ink-receptive heat-sensitive layer composition.

The composition for forming the ink-receptive heat-sensitive layer is DMF, 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, methyl alcohol,
Ethyl alcohol, cyclopentanol, cyclohexanol, diacetone alcohol, benzyl alcohol,
It is prepared as a composition solution by dissolving it in a suitable organic solvent such as butyl butyrate or ethyl lactate. An ink-receptive heat-sensitive layer is formed by uniformly coating such a composition solution on a substrate and heating at a required temperature for a required time.

It is necessary to carry out the thermal curing of these at a temperature at which the thermally decomposable compound does not decompose, usually at 160 ° C. or lower. For this reason, it is preferable to use a catalyst in combination.

Alternatively, when a photopolymerizable monomer is used, it is necessary to carry out photocuring with a light source such as an ultrahigh pressure mercury lamp or a halogen lamp after coating and heating.

The thickness of these ink-receptive heat-sensitive layers was 0.
2 μm to 10 μm is preferable, more preferably 0.5
It is from 5 μm to 5 μm. When the film thickness is less than 0.2 μm, the sensitivity of the heat-sensitive layer is likely to be lowered, and the heat-sensitive layer is easily peeled off from the silicone layer during printing. On the other hand, when the thickness is more than 10 μm, the heat sensitive layer is not completely decomposed during exposure and the underlying silicone is not exposed, so the above range is particularly preferable.

The ink-receptive heat-sensitive layer can be coated on the silicone rubber layer, but can also be laminated by laminating a film formed on another film on the silicone rubber layer. is there.

In this case, since it is not necessary to take account of cissing, which is a problem when coating on the silicone rubber layer, it is possible to more easily form the ink-receptive heat-sensitive layer.

As a substrate for this printing plate, a dimensionally stable plate is used. Such dimensionally stable plate-like objects include those conventionally used as substrates for printing plates, and they can be suitably used. Such substrates include paper, plastic (eg, polyethylene,
Paper laminated with polypropylene, polystyrene, etc., such as aluminum (including aluminum alloys), metal plates such as zinc, copper, etc., such as cellulose, carboxymethyl cellulose, cellulose acetate, polyethylene terephthalate, polyethylene. , Polyester, polyamide, polyimide, polystyrene,
A film of a plastic such as polypropylene, polycarbonate, polyvinyl acetal, etc., a paper or a plastic film on which a metal such as the above is laminated or vapor-deposited are included. Of these substrates,
Aluminum plates are particularly preferred because they are extremely dimensionally stable and 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 precursor used in the present invention may be provided with a primer layer in order to strengthen the adhesion between the substrate and the silicone rubber layer. The primer layer of the direct drawing type waterless planographic printing plate precursor used in the invention is required to satisfy the following conditions. That is, the substrate is well adhered to the silicone rubber layer, is stable over time, and has good solvent resistance to the solvent of the developer. Japanese Patent Publication Sho 6
In addition to those containing an epoxy resin as disclosed in JP-A 1-54219, polyurethane resin, phenol resin, acrylic resin, alkyd resin, polyester resin, polyamide resin, melamine resin, urea resin, benzoguanamine resin, vinyl chloride-acetic acid. Use vinyl copolymer, vinyl chloride resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, polycarbonate resin, polyacrylonitrile-butadiene copolymer, polyether resin, polyether sulfone resin, milk casein, gelatin, etc. Can be done. These resins may be used alone or in combination of two or more.

A composition similar to the silicone rubber layer, which is cured by light or heat, may be used.

Of these, polyurethane resins, polyester resins, acrylic resins, epoxy resins, urea resins and the like are preferably used alone or in admixture of two or more.

As the anchor agent constituting the primer layer, a known adhesive such as a silane coupling agent can be used, and organic titanate is also effective.

Further, it is optional to add a surfactant for the purpose of improving the coatability.

Further, it is preferable to add an additive such as a dye or a pigment in the primer layer to improve the plate inspection property.
In this case, the dye or pigment has a different hue from that of the heat-sensitive layer,
Anything can be used, but green, blue, yellow dyes and pigments, or white pigments are preferred.

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

The primer layer has a thickness of 0.5 as a coating layer.
５０50 g / m ² , preferably 1-10 g
/ M ² . When the thickness is less than 0.5 g / m ² , the effect of blocking morphological defects and chemical adverse effects on the substrate surface is reduced,
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 silicone rubber layer, all conventional silicone rubber compositions for waterless lithographic printing plates can be used.

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

[0097]

Embedded image (Here, n is an integer of 2 or more. R has 1 to 10 carbon atoms.)
Alkyl, aryl, or cyanoalkyl group. Preferably, 40% or less of the whole R is vinyl, phenyl, vinyl halide, or halogenated phenyl, and 60% or more of R is a methyl group. Further, it has at least one or more hydroxyl group in the molecular chain at the chain end or in the form of a side chain. In the case of the silicone rubber layer applied to the printing plate of the present invention, a silicone rubber (R
TV, LTV type silicone rubber) can be used. As such a silicone rubber, one in which a part of R of the organopolysiloxane chain is replaced by H can be used, but usually, the end groups represented by the following formulas (II), (III) and (IV) are not used. Are crosslinked by the condensation of. In some cases, an excess of a crosslinking agent may be present.

[0098]

Embedded image

Embedded image

Embedded image (Where R is the same as R described above; R1, R2
Is a monovalent lower alkyl group, and Ac is an acetyl group. ) Silicone rubber which performs such condensation type crosslinking includes:
Metal carboxylates such as tin, zinc, lead, calcium, manganese, for example, dibutyltin laurate, tin (II) octoate, naphthenates, etc., or catalysts such as chloroplatinic acid are added.

Further, as the silicone rubber layer used in the present invention, which has been crosslinked by the addition reaction of the following formulas (V) and (VI), a polyvalent hydrogenorganopolysiloxane and two or more units in one molecule are used. A composition obtained by reaction with a polysiloxane having a bond of formula (VI), preferably a composition comprising the following components, which has been crosslinked and cured.

[0100]

Embedded image

[Chemical 6] (1) 100 parts by weight of organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to silicon atoms in one molecule (2) Organo having at least two groups of formula (V) in one molecule Hydrogen polysiloxane 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 at the terminal or in the middle of the molecular chain, and may be an organic compound other than the alkenyl group. As a basis,
It is a substituted or unsubstituted alkyl group or aryl group.
Component (1) preferably has a small amount of hydroxyl groups.
The component (2) reacts with the component (1) to form a silicone rubber layer, but plays a role of imparting adhesiveness 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 components (1) and (2) are methyl groups as a whole in terms of improving ink repellency. The molecular structure of component (1) and component (2) may be linear, cyclic or branched, and it is preferable that at least one of them has a molecular weight of more than 1000 from the viewpoint of rubber physical properties. )
It is preferred that the molecular weight of is over 1000. As the component (1), α, ω-divinylpolydimethylsiloxane, a methyl group having both end terminals (methylvinylsiloxane)
Examples of the component (2) include (dimethylsiloxane) copolymers and the like. Examples of the component (2) are polydimethylsiloxane having hydrogen groups at both terminals, α, ω-dimethylpolymethylhydrogensiloxane, and (methylhydrogensiloxane) having methyl groups at both terminals. Examples thereof include (dimethylsiloxane) copolymer and cyclic polymethylhydrogensiloxane. The addition catalyst of the component (3) is arbitrarily selected from known catalysts, and is particularly preferably a platinum compound, such as platinum alone, 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, It is also possible to add a crosslinking inhibitor such as propylene glycol monomethyl ether. These compositions have the characteristic that, when the three components are mixed, an addition reaction occurs and curing starts, but the curing rate increases rapidly as the reaction temperature increases. Therefore, for the purpose of prolonging the pot life of the composition until it becomes rubber, and shortening the curing time on the photosensitive layer, the curing conditions of the composition are temperature conditions in which the characteristics of the substrate and the photosensitive layer do not change, Further, it is preferable to keep the temperature at a high temperature until it is completely cured, from the viewpoint of stability of the adhesive force with the photosensitive layer.

At this time, it is preferable to add a silane coupling agent as an adhesive component.

As the silane coupling agent at this time,
All of the silane coupling agents added to the above-mentioned ink-receptive heat-sensitive layer can be preferably used.

The addition amount of these silane coupling agents is 0.01 to 1 based on the total silicone rubber layer composition.
0 wt% is preferable, and more preferably 0.05 to 5 wt%
It is.

In addition to these compositions, it is optional to add a known filler such as silica for the purpose of improving rubber strength.

As described above, the thickness of the silicone rubber layer has a great influence on the background smearing property of the printing plate, so that it is preferably as thick as possible.

In particular, in the present invention, since the silicone rubber layer is below the ink-receptive heat-sensitive layer, it is possible to increase the film thickness and improve the background stain resistance.

Specifically, the film thickness is 0.5 to 50 g.
/ M ² is preferable, and more preferably 0.5 to 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 when it is more than 50 g / m ² , it is disadvantageous from an economic viewpoint.

For the purpose of protecting the ink-receptive heat-sensitive layer on the surface of the direct drawing type waterless lithographic printing plate precursor constructed as described above, the surface of the heat-sensitive layer is thinned by a plane or uneven treatment. It is also possible to laminate the protective film or to form a polymer coating film which is soluble in the developing solvent described in JP-A-5-323588.

Further, as described above, it is also possible to laminate the film having the ink-receptive heat-sensitive layer formed thereon on the silicone rubber layer.

In particular, when a protective film is laminated, laser exposure is performed on the protective film, and then the protective film is peeled off to form a pattern on the printing plate. It is also possible to create.

Next, the method for producing the waterless planographic printing plate precursor according to the invention will be described. An ordinary coater such as a reverse roll coater, an air knife coater, and a Mayer bar coater or a spin coater such as a whaler was applied on the substrate, and the primer layer composition was applied if necessary and cured at 100 to 300 ° C. for several minutes. Then, a silicone rubber composition is applied and heat-treated at a temperature of 50 to 150 ° C. for several minutes to cure the rubber to form a rubber composition. Then, the ink-receptive heat-sensitive layer composition is applied, or a film on which the ink-receptive heat-sensitive layer is applied in advance is laminated.

When applying, drying is carried out at a temperature of 50 to 160 ° C. for several minutes and, if necessary, thermal curing or optical curing.

Then, a protective film is laminated or a protective layer is formed, if necessary.

The directly imageable waterless planographic printing plate precursor thus obtained is imagewise exposed with a laser beam after peeling off the protective film or on the protective film.

Laser light is usually used for the exposure, and the light source at this time has an oscillation wavelength of 300 nm to 1500.
such as Ar ion laser, Kr ion laser, He-Ne laser, He-Cd laser, ruby laser, glass laser, semiconductor laser, YAG laser, titanium sapphire laser, dye laser, nitrogen laser, metal vapor laser in the range of nm. Various lasers can be used. Among them, the semiconductor laser is preferable because it is miniaturized due to the recent technical progress and is economically advantageous over other laser light sources.

The direct drawing type waterless planographic printing plate exposed by the above method basically does not require development when exposed after peeling off the protective film, but when exposed from above the protective film. , Peeling development, or usual solvent development treatment.

The developing solution used in the present invention includes, for example, water, one obtained by adding the following polar solvent to water, and aliphatic hydrocarbons (hexane, heptane, "Isopar E,
G, H "(trade names of isoparaffinic hydrocarbons manufactured by ESSO), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), and halogenated hydrocarbons (trichlene, etc.). A mixture obtained by adding at least one of the following polar solvents to a mixed 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
-Hexanediol, etc.) Ethers (ethylene glycol monoethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2
-Ethylhexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dioxane, tetrahydrofuran, etc. Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) , Diacetone alcohol, etc. Esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.) Acid (2-ethylbutyric acid, Prong acid, caprylic acid, 2-ethylhexanoic acid, capric acid, oleic acid,
In addition, a known surfactant can be freely added to the above-mentioned developer composition. In addition, further alkaline agent,
For example, sodium carbonate, monoethanolamine, diethanolamine, diglycolamine, monoglycolamine, triethanolamine, sodium silicate, potassium silicate, potassium hydroxide, sodium borate and the like can be added.

At the time of developing, the developing solution can be developed by impregnating a non-woven fabric, absorbent cotton, cloth, sponge or the like with the developing solution and wiping the plate surface.

For development, Japanese Patent Laid-Open No. 63-163357.
It is possible to suitably develop by pretreatment of the plate surface with the above-mentioned developing solution using an automatic developing machine as described in 1) and then rubbing the plate surface with a rotating brush while showering with tap water or the like.

The development can also be performed by spraying hot water or steam onto the plate surface instead of the above developing solution.

[0122]

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

Examples 1 to 6 A 0.15 mm thick aluminum plate (Sumitomo Metal Industries, Ltd.) was coated with the following primer composition using a bar coater, and 2
Heat treatment was performed at 20 ° C. for 2 minutes to provide a primer layer of 5 g / m ² .

(A) 90 parts by weight of polyurethane resin (Samprene LQ-T1331, manufactured by Sanyo Kasei Co., Ltd.) (b) 15 parts by weight of block isocyanate (Takenate B830, manufactured by Takeda Pharmaceutical Co., Ltd.) c) Epoxy-phenol-urea resin (SJ9372, manufactured by Kansai Paint Co., Ltd.) 8 parts by weight (d) Tetraglycerol dimethacrylate 0.2 parts by weight (e) Dimethylformamide 725 parts by weight Then, for this primer layer After spin coating a silicone rubber composition having the following composition on the above, 115 ° C., dew point 30
It was cured by heat and humidity at 3.5 ° C. for 3.5 minutes to provide a 5 g / m ² silicone rubber layer.

(A) Polydimethylsiloxane (molecular weight of about 25,000, terminal hydroxyl group) 100 parts by weight (b) Vinyltri (methylethylketoxime) silane 8 parts by weight (c) "Isopa-E" (manufactured by Exxon Chemical Co., Ltd.) 1400 parts by weight Next, the following heat-sensitive layer composition was applied onto a polypropylene film “Trephan” (manufactured by Toray Industries, Inc.) having a thickness of 80 μm.
It was applied using a coater and dried in hot air at 120 ° C. for 1 minute to form a heat-sensitive layer having a film thickness of 2 μm.

(A) Nitrocellulose (viscosity 1/2 second, nitrogen content 11.0% “Berge rac NC” SNP Japan Co., Ltd.) 25 parts by weight (b) Furnace type carbon black (Average particle diameter 28 nm, # 33 manufactured by Mitsubishi Chemical Corporation) 15 parts by weight (c) Silane coupling agent (Table 1) (d) Hydroxyl group-containing polymerizable monomer (Table 1) (e) Polyvinyl butyral (# 2000- L Denki Kagaku Co., Ltd.) 20 parts by weight (f) Irgacure 651 (manufactured by Chiver Geigy Co., Ltd.) 7 parts by weight (g) Methyl ethyl ketone 700 parts by weight Laminating was performed using a calendar roller so that the coated surfaces of were in contact with each other to obtain a direct drawing type waterless planographic printing plate precursor.

Further, this laminated plate was exposed for 60 seconds by using a metal halide lamp (Idle Fin 2000 manufactured by Iwasaki Electric Co., Ltd.).

The protective film of this printing original plate was peeled off and mounted on a thermal image-setter TE-R1070 (manufactured by Dainippon Screen Co., Ltd.) for image exposure.

The obtained printing plate was mounted on an offset printing machine (Komori Sprint 4-color machine) without development,
Dainippon Chemical Co., Ltd. "Dry color" black ink,
Printing was carried out on high-quality paper using indigo, red, and yellow inks, and the temperature of the plate surface when stains were observed on the printed matter was evaluated as the background stain temperature.

Comparative Examples 1 and 2 In Examples 1 and 2, a primer layer, an ink-receptive heat-sensitive layer, and a silicone rubber layer were applied in this order on the substrate with the same composition (only the thickness of the silicone rubber layer was 2 g / m ^2). Was changed), and the rest were all evaluated in the same manner.

It can be seen from Table 1 that the printing plate of the present invention has improved background stain resistance as compared with the conventional one.

[0132]

[Table 1]

[0133]

EFFECT OF THE INVENTION The direct drawing type waterless planographic printing plate of the present invention has improved scumming property as compared with the conventional direct drawing type waterless planographic printing plate.

Claims (10)

[Claims] 1. A direct drawing type waterless lithographic printing plate precursor comprising a substrate, a silicone rubber layer provided on the substrate and an ink receiving heat sensitive layer provided on the silicone rubber layer, wherein the ink receiving heat sensitive layer is A direct drawing type waterless planographic printing plate precursor characterized by containing carbon black. 2. The carbon black according to claim 1,
Direct drawing type waterless planographic printing plate precursor characterized by being furnace type carbon black. 3. The ink-receptive heat-sensitive layer according to claim 1,
A direct-drawing waterless planographic printing plate precursor comprising at least one of a hydroxyl group-containing polymer and a hydroxyl group-containing monomer. 4. The ink-receptive heat-sensitive layer according to claim 1,
A direct drawing type waterless planographic printing plate precursor characterized by containing nitrocellulose. 5. A direct drawing type waterless planographic printing plate precursor according to claim 1, wherein the silicone rubber layer or the ink-receptive heat-sensitive layer contains a silane coupling agent. 6. A direct drawing type waterless device according to claim 1, wherein the silicone rubber layer or the ink-receptive heat-sensitive layer contains at least one of acrylic silane, methacrylic silane, vinyl silane and allyl silane. Original planographic printing plate. 7. A direct-drawing waterless planographic printing plate according to claim 1, wherein the silicone rubber layer or the ink-receptive heat-sensitive layer contains at least one of epoxysilane, aminosilane and mercaptosilane. Original version. 8. A waterless lithographic printing plate obtained by selectively exposing and developing the direct drawing type waterless lithographic printing plate precursor as claimed in any one of claims 1 to 7. 9. A substrate having a silicone rubber layer on one side,
A method for producing a direct drawing type waterless lithographic printing plate precursor, which comprises laminating a film having an ink-receptive heat-sensitive layer on one side so that the silicone rubber layer surface and the ink-receptive heat-sensitive layer surface are in contact with each other. 10. The direct drawing type waterless planographic printing plate precursor according to claim 1 is irradiated with a laser beam to remove the ink-receptive heat-sensitive layer and expose the underlying silicone rubber. A method for producing a direct drawing type waterless planographic printing plate, which comprises forming an ink repellent non-image portion.