JPH03179446A - Production of damping waterless planographic printing plate material - Google Patents

Abstract

PURPOSE:To improve printing resistance as well as vacuum adhesion by forming a transparent film on a silicone rubber layer, sticking mist of a coating liq. contg. dissolved or dispersed resin to the film and forming a discontinuous mat layer with fixed solid particles on the film by drying or heat curing. CONSTITUTION:A photosensitive layer and a silicone rubber layer or a photosensitive silicone rubber layer is formed on a substrate and a transparent film on the silicone rubber layer. Mist of a coating liq. contg. dissolved or dispersed resin is stuck to the film and a discontinuous mat layer with fixed solid particles is formed on the film by drying or heat curing. Since the coating liq. is stuck as mist, swelling due to a solvent in the liq. can be prevented. Since the amt. of the solvent is reduced to the irreducible min., the adhesive property of the film to the silicone rubber layer is not adversely affected and the deterioration of printing resistance is not caused. Printing resistance as well as vacuum adhesion can be improved.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a lithographic printing plate material that does not require dampening water, and more specifically, a method for producing a lithographic printing plate material that does not require dampening water, and more specifically, a method that improves vacuum adhesion while maintaining printing durability. The present invention relates to a method for producing a lithographic printing plate material that does not require dampening water.

[Conventional technology]

To form an image on a lithographic printing plate material that does not require dampening water,
Normally, the original image is exposed to actinic light, but in order to faithfully reproduce the original image, it is necessary to bring the original image into complete contact with the upper surface of the printing plate. For this reason, a vacuum adhesion method has generally been used in which the printing plate and the original are placed one on top of the other between a rubber sheet and a pressure-bonding glass, and the space between the rubber sheet and the pressure-bonding glass is evacuated to bring them into close contact.

However, it is difficult to achieve sufficient vacuum adhesion, and various techniques have been proposed to improve this.

In JP-A No. 82-247888, a resin liquid is applied onto a film using a gravure roll.

After making a film with an uneven pattern corresponding to the engraving of the gravure roll, the film is laminated so that the smooth surface (the surface that does not tolerate unevenness) is in contact with the silicone rubber layer, thereby creating a matte layer on the cover film. Disclosed is a method for providing.

Furthermore, JP-A No. 55-55343 discloses a technique for coating an uneven transparent film on the uppermost silicone rubber layer, and as a method for providing unevenness, inorganic particles are coated on a substantially smooth protective film. A method of applying a solution is also described as being effective.

[Problem to be solved by the invention]

However, in all conventional methods, the cover film swells with the solvent of the resin being applied and peels off from the silicone layer.Also, even if the cover film does not swell, the solvent that penetrates may cause the silicone layer to harden or the silicone layer and photosensitive layer to separate. There is a problem that this adversely affects the adhesion between the silicone layer and the silicone layer peels off during development, resulting in poor printing durability.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a lithographic printing plate material that does not require dampening water and can improve vacuum adhesion and printing durability.

[Means to solve the problem]

The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, have arrived at the present invention.

That is, the method for producing a dampening water-free planographic printing plate material according to the present invention provides a dampening water-free planographic plate having a photosensitive layer, a silicone rubber layer or a photosensitive silicone rubber layer, and a light-transmitting film layer on a support. In the method for producing a printing plate material, a light-transparent film layer is formed on the silicone rubber layer, and then fine droplets of a coating liquid in which a resin is dissolved or dispersed are deposited on the light-transparent film layer. It is characterized in that it is dried or thermally cured to form a discontinuous matte layer on which solid particles are fixed on the light-transmitting film layer.

In a preferred embodiment of the present invention, fine droplets of the coating liquid are electrostatically sprayed and deposited on the light-transmitting film layer, and the solvent of the coating liquid is water or boiling point 1
It is an organic solvent with a temperature of less than 30°C.

[Effect]

In the method for producing a lithographic printing plate material that does not require dampening water according to the present invention, since the coating liquid forms droplets in the form of micromWl and adheres to the light-transmitting film layer, the amount of water in the droplets is The solvent evaporates easily and problems such as swelling caused by the solvent can be eliminated. In addition, since the amount of solvent can be reduced to the minimum required for adhesion onto the light-transmitting film layer (slight adhesion remains), the adhesion between the silicone rubber layer and the photosensitive layer can be improved. The discontinuous matte layer obtained by the production method of the present invention has no adverse effect on the adhesion between the light-transmitting film layer and the light-transmitting film layer, and therefore does not cause a decrease in printing durability. Therefore, the printing durability can be improved, which is a distant relative of the object of the present invention.

[Structure of the invention]

The present invention will be explained in detail below.

(Support) The support is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as metal plates such as aluminum, zinc, copper, and steel; Metal plates plated or vapor-deposited with zinc, copper, nickel, aluminum, iron, etc., paper, plastic films and glass plates, resin-coated paper, paper covered with metal foil such as aluminum, plastic films treated with wood-filtering, etc. can be mentioned. Among these, aluminum plates are preferred. When using aluminum plate,
Surface roughening treatments such as graining treatment and anodizing treatment may be performed.

The thickness of the support is preferably 50 to 400 JL, more preferably 100 to 300 IL.

(Primer layer) A primer layer may be provided on the support, and a resin, a silane coupling agent, a silicone primer, etc. can be used for the primer layer, and organic titanates and the like are preferably used.

Examples of resins include polyester resin, vinyl chloride, etc.
Vinyl acetate copolymer, acrylic resin, vinyl chloride resin,
Polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin.

Examples include polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

Among these, resins obtained by photocrosslinking or thermally crosslinking copolymer resins of (meth)acrylic esters having alcoholic OH groups, such as 2-hydroxyethyl methacrylate, are preferred.

The primer layer used in the present invention is preferably crosslinked in order to improve solvent resistance to the coating solvent of the photosensitive layer and the organic solvent of the developer.

As the component to be crosslinked, a polyvalent incyanate compound, a diazo resin, a polyvalent epoxy compound, a compound having two or more polymerizable ethylenically unsaturated double bonds, etc. are used.

Examples of the polyvalent isocyanate compound include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and Coronate E.

Examples include HL and EH (manufactured by Nippon Polyurethane Industries, Ltd., polyvalent incyanate compounds).

The diazo resins include 4-diazodiphenylamine, hexafluorophosphate-formaldehyde resin, 3-methoxy-diphenylamine-4-diazonium salt and 4.4'-
Examples include mesitylene sulfonate salt of a condensate of bis-methoxymethyl-diphenyl ether.

Examples of the polyvalent epoxy compound include bisphenol epoxy resin, bisphenol F diglycidyl ether, novolac glycidyl ether, hexahydrophthalic acid glycidyl ether, triglycidyl isocyanurate, and the like.

Examples of the compound having two or more polymerizable ethylenically unsaturated double bonds include trimethylolpropane triacrylate, tetramethylolmethane triacrylate, allyl acrylate, and 1,4-butanediol dimethacrylate. In addition, when using a compound having an ethylenically unsaturated double bond, a polymerization initiator or a photopolymerization initiator is used together.

Among the above crosslinking agents, diazo resins are preferred.

(Photosensitive layer) The photosensitive layer is coated on the support or a primer layer provided as necessary using a reverse roll coater, an air knife coater,
It is formed by applying and drying a photosensitive composition solution using an ordinary coater such as a Meyer bar coater or a spin coating device such as a Whaler. Note that heat curing is performed as necessary.

The structure of the photosensitive layer is not particularly limited, and various photosensitive substances can be used. Typical examples will be explained below.

First, quinonediazide-type positive photosensitive materials such as conventionally known 0-naphthoquinonediazide compounds are mentioned.

Suitable 0-naphthoquinone diazide compounds include naphthoquinone-(1,2)-diazide-(2)-sulfonic acid chloride and phenol or cresol-formaldehyde resins described in U.S. Pat. No. 3,048,120. There is an ester with. Other useful 0-naphthoquinone diazide compounds include 1, for example, U.S. Pat.
, 835.7013.
Ester of acetone resin and 0-naphthoquinonediazide sulfonic acid chloride, JP-A-55-78348, JP-A-55-78348, JP-A-55-78348;
Ester of polyhydroxyphenyl resin and O-naphthoquinonediazide sulfonic acid chloride described in No. B-1044 and No. 511i-1045, JP-A-1989-1989
A homopolymer of p-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in Japanese Patent Publication No. 113305 and ester-reacted with 0-naphthoquinonediazide sulfonic acid chloride. -17481, a reaction product of a polymer product of styrene monomer and a phenol derivative and 0-quinonediazide sulfonic acid, and an ester of polyhydroxybenzophenone and 0-naphthoquinonediazide sulfonic acid chloride.

A binder may be added to a photosensitive composition containing such a quinonediazide type photosensitive substance, if necessary.
For example, suitable examples include novolac resins soluble in aqueous alkaline solutions. Typical examples of such novolac resins include phenol-formaldehyde resin, cresol-formaldehyde resin, p-tert-butylphenol-formaldehyde resin, and phenol-modified xylene resin.

The amount of quinonediazide compound in the photosensitive composition is 10-5
It is 0% by weight, more preferably 20 to 40% by weight. In addition, the amount of the above-mentioned binder is 45 to 45% in the photosensitive composition.
It is 80i% by weight, preferably 50 to 70% by weight.

Further, as the photosensitive substance, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde is also used.

Particularly preferred are salts of condensates of P-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphates, tetrafluoroborates,
A diazo resin inorganic salt which is a reaction product of a perchlorate or a periodate and the above-mentioned condensate, and U.S. Pat.
Examples include diazo resin organic salts, which are reaction products of the above condensate and sulfonic acids, as described in No. 309. The diazo resin is preferably used together with a binder. Various polymeric compounds can be used as such a binder, but monomers having an aromatic hydroxyl group such as those described in JP-A-5-98FT13, such as N-(4-hydroxyphenyl), are preferable. ) acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m-1 or p-hydroxystyrene, o-
11, or a copolymer of p-hydroxyphenyl methacrylate, etc. and other monomers, U.S. Pat. No. 4,123,27
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit as described in No. 8, shellac,
Natural resins such as rosin, polyvinyl alcohol, polyamide resins described in U.S. Pat. No. 3,751,257, linear polyurethane resins described in U.S. Pat. No. 3,880,0137, phthalated resins of polyvinyl alcohol, Epoxy resins condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate are included.

Also, -CH=C as a photosensitive group in the main chain or side chain of the polymer.
Examples include those whose main component is a photosensitive polymer such as polyesters containing H-C-, polyamides 1, and polycarbonates. For example, JP-A-55-404
15, photosensitive polyesters obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol; cinnamylidene, as described in U.S. Pat. No. 2,956,878; -F a 7 acids etc. (7) (2
Photosensitive polyesters derived from -probeliden) malonic acid compounds and difunctional glycols, and the like.

Further examples include aromatic azide compounds in which the azide group is bonded directly or via a carbonyl or sulfonyl group to an aromatic ring. For example, polyazidostyrene as described in U.S. Pat. No. 3,098,311; Polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, the reaction product of 7didoarylsulfanyl chloride and an unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 1986-8613, and No. 210117,
4←No. 228, No. 44-22954 and No. 45-2
Examples include polymers having sulfonyl azide and carbonyl azide, as described in No. 4915.

Furthermore, a photopolymerizable composition comprising an addition polymerizable unsaturated compound may also be mentioned.

The thickness of the photosensitive layer is preferably 0.05 to 10 JLm, more preferably 0.1 to 2 JLm.

In the present invention, the photosensitive material may further contain filler 1 dyes, dyes, pigments, surfactants for improving coating properties and other conventional additives and auxiliaries.

Note that, if necessary, an adhesive layer may be provided on the photosensitive layer by coating and drying in a similar manner.

(Silicone rubber layer) A silicone rubber solution is coated on the photosensitive layer or an adhesive layer provided as necessary in the same manner as above, and usually 100%
Heat treatment at a temperature of ~120° C. for several minutes to fully cure and form a silicone rubber layer.

The silicone rubber used in the silicone rubber layer is mainly composed of a linear organic polysiloxane having the following repeating units, a molecular weight of several thousand to several hundred thousand, and an OH group in the main chain or at the end of the main chain. Preferably.

(-Si -0+n where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a vinyl group, an aryl group, one silanol group (0)), and Preferably, 60% or more of the methyl groups are methyl groups.

The silanol group (OH group) may be located either in the main chain or at the end of the main chain, but is preferably located at the end.

The silicone rubber useful in the present invention is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent as listed below.

(1) R-5i+OR") (2) R-Si+0Ac) (3) R-9i+0?CR"2)z Here, R has the same meaning as R explained earlier, and R' is a methyl group or an ethyl group. and AC is an acetyl group.

These silicone rubbers are also available as commercial products, such as YE-3085 manufactured by Toshiba Silicone Corporation.

Other useful silicone rubbers can be produced by reacting the base polymers listed above with silicone oils having the following repeating units, or by reacting silicone base polymers in which about 3% of R is vinyl groups. addition reaction,
Alternatively, it can also be obtained by a reaction between the silicone oils.

(In the formula, R has the same meaning as R above, Peng is an integer of 2 or more, and n is O or an integer of 1 or more.) In order to obtain silicone rubber by such a crosslinking reaction, the above-mentioned In addition to the ingredients, tin and zinc.

Organic carboxylates of metals such as cobalt, lead, calcium, manganese, etc., such as dibutyltin laurate, tin (
n) Catalysts such as octoate, cobalt naphthenate, etc. or chloroplatinic acid are added.

In addition, in order to improve the strength of silicone rubber and obtain silicone rubber that can withstand the frictional forces generated during printing operations,
Fillers can also be mixed. Silicone rubber pre-mixed with filler is commercially available as silicone rubber stock or silicone rubber dispersion, and as in the present invention, it can be coated with
If it is preferred to obtain a silicone rubber film, RT
Disversions of V or LTV silicone rubber are preferably used. An example of this is Syl (:Hf 23.5RX-257゜5) manufactured by Toray Silicone Co., Ltd.
There are silicone rubber dispersions for paper coach inks such as H237.

In the present invention, it is preferable to use condensation and crosslinking type silicone rubber.

In the present invention, in addition to the above-mentioned components, a small amount of photosensitizer can be included in the silicone rubber layer.

Preferably, the silicone rubber layer further contains a silane coupling agent to improve adhesion to the photosensitive layer.

Examples of silane coupling agents include the following.

(a) H2NCH2CH2HHCCIhCH2C1h
SiCOCH3)s(b) CToC)ICH20(C
)12)3si(OCH:+)x\/ (c) HS(CH2hSi(QC)I3)x(d)
GHz-CHSi(OCOCH3)z(f) GHz-
CHSi(OCR2CHxh(g))12NGHzG
82?1H(CH2hSi(OCH3)z(OH3)(
h) The thickness of the chlorosilane silicone rubber layer is preferably 0.1 to 10 gm, more preferably 0.5 to 2 gm.

Note that in the case of forming a photosensitive silicone rubber layer, a photosensitive layer is not necessary, and as such a photosensitive silicone rubber, γ-methacryloxypropyltrimethoxysilane or monocinnamoyljetoxysilane is added to the terminal OH group of dimethylpolysiloxane. Examples include compounds obtained by dealcoholization condensation of polydiorganosiloxane, compounds obtained by adding a bisazide compound to polydiorganosiloxane, or compounds obtained by reacting acryloyl chloride or p-azidobenzoate.

(Light-transparent film layer) Next, a light-transparent film is laminated on the silicone rubber layer to form a light-transparent film layer.

A light transmitting film layer is a layer composed of a film having light transmittance, and here, light transmittance is defined as having a light transmittance of 50% or more for active light (wavelength 30G+1+ to 500!I■). It refers to something.

Preferred examples of the resin used in the light-transmitting film layer include polyolefins such as polypropylene, polyethylene, polymethylpentene, and ethylene-butene copolymers, polystyrene, and fluororesins. Using these resins means that the photosensitive layer contains a quinonediazide compound,
This is effective when using diazo resin. That is, these photosensitive layers generate N2 gas when exposed to light, but these resins exhibit good N2 gas permeability. Note that these resins have low mechanical strength and dimensional stability.

In the present invention, when a substance other than a quinone diazide compound or diazo resin is used as the photosensitive layer, the resin used for the light-transmitting film layer is not limited to the above, and includes, for example, polyethylene terephthalate, nylon, polyvinyl alcohol, polycarbonate, Polymethyl methacrylate, polyimide, polyacrylonitrile, etc. can be used.

The thickness of the light-transmitting film layer is preferably 0.5 to 20 #Lm, more preferably 3 m8 thick.

(Discontinuous matte layer) Fine droplets of a coating liquid in which a resin is dissolved or dispersed are deposited on the light-transparent film layer, and then dried or thermally cured to fix solid particles on the light-transparent film layer. Discontinuous mark 2
Form one layer.

The coating liquid is a solution or dispersion of an organic solvent in which a resin is dissolved or dispersed, an aqueous solution, a dispersion, an emulsion solution, or the like.

The solvent of the coating liquid used in the present invention is water or boiling point 130
Preferably, the organic solvent has a temperature of less than .degree.

However, it may contain 5 to 40% of a softener solvent with a boiling point of 130° C. or higher.

Organic solvents with a boiling point of less than 130°C include methyl cellosolve, acetone, methanol, ethanol, propatool, butanol, ethyl acetate, methyl ethyl ketone, toluene, xylene, methyl butyl ketone, methyl isobutyl ketone, butyl acetate, propyl acetate, dioxane, propylene. There are glycol monomethyl ether, tetrahydrofuran, etc., and 1 m or 2 or more types can be selected and used from these.

Examples of organic solvents with a boiling point of 130° C. or higher include ethylene glycol, diethylene glycol 7-methyl ether, methyl lactate, dipropylene glycol, and cyclohexanone.

What resin is used in the coating solution?

■ For example, polyethylene, polymethyl methacrylate, polystyrene, phenolic resin, ionomer resin,
^BS [fat, ethylene-vinyl acetate copolymer, vinyl chloride resin, polyamide resin.

Fluororesin, polyester resin, epoxy resin (cured #
), Thermoplastic resins such as styrene-(meth)acrylic acid or methacrylic acid ester copolymer resins (2) Examples include resins obtained by adding a curing agent to epoxy resins, phenol resins, unsaturated polyester resins, etc.

The method for depositing the fine droplets of the coating liquid on the light-transmissive film layer is not particularly limited, but includes, for example, a method for depositing them electrostatically.

Examples of electrostatic attachment methods include the well-known electrostatic x7-spray method and the +ettt airless spray method.

Examples include a rotary atomization electrostatic coating method and an electrostatic coating method described in Japanese Patent Publication No. 55-28740.6 In the present invention, an electrostatic spraying method is preferred.

When using the method of the present invention, the organic solvent is evaporated as much as possible during the stage of spraying into droplets, that is, while the droplets are dispersed in the air, to reduce the solvent content of the droplet particles as much as possible. After that (to the extent that it has adhesiveness to the light-transmitting film), it is attached to the light-transmitting film. This is to eliminate the influence of the solvent by reducing the solvent content as much as possible at the time of adhesion.

If the resin is to be evaporated to the extent that it loses its adhesion to the light-transmitting film, use a resin with a melting point of 80 to 150°C (for example, styrene: methyl methacrylate: nibutyl acrylate copolymer, etc.) and heat-melt it. It is preferable to adopt a method of wearing the cloth.

The particles constituting the discontinuous matte layer formed by the above method can substantially transmit the exposing actinic rays,
The solid particles can also contain an ultraviolet absorber, a yellow dye, a yellow pigment, etc. in order to prevent the harmful effects of light scattered by the particles.

The coverage ratio of the particles of the light-transmitting film layer is 0.5 to 30
%, more preferably 1 to 5%. In this way, since the discontinuous mer2 layer does not cover the entire light-transmitting film layer, the light-transmitting film has good gas permeability.

The shape and size of the particles are not particularly limited when they are powder before fixation, but the height of the particles fixed on the light-transmitting film layer is 1 to 50 pm, more preferably 3 to 1 pm.
5 ILm, size (width) 5 to 200 IL11, more preferably IO to 1 (1 (l g m) hemispherical, semi-ellipsoidal, 1 cylindrical or preferred.

In the present invention, by pressing the surface of the particles,
The height of the convex portion can be made uniform.

Examples of the suppressing means include passing one plate material between heating rolls.

The dampening water-free lithographic printing plate material obtained by the above production method has a photosensitive layer, a silicone rubber layer and a light-transparent film layer on the four supports, and solid particles are formed on the light-transparent film layer. This is a discontinuous mat layer to which is adhered.

Further, the photosensitive layer and the silicone rubber layer may be a single photosensitive silicone rubber layer.

Next, a method for manufacturing a printing plate that does not require dampening water using the plate material that does not require dampening water of the present invention will be explained.

A positive film, which is the manuscript, is vacuum-adhered to the surface of the plate and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used.

At this time, the vacuum adhesion is improved due to the presence of discontinuous particles.

After exposure, the light-transmissive film is peeled off and developed with a developer to remove only the silicone rubber layer and photosensitive layer or silicone rubber layer in the unexposed areas.

A printing plate in which the recessed image portion is formed can be obtained as described above.

〔Effect of the invention〕

According to the present invention, it is possible to provide a method for producing a lithographic printing plate material that does not require dampening water and can improve vacuum adhesion and improve printing durability.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Synthesis I of diazo resin-1) p-diazodiphenylamine sulfate 14.5 g (50
40.9 mmol) under water cooling. of concentrated sulfuric acid.

1.35 g (45 mmol) of paraformaldehyde was slowly added to this reaction solution so that the reaction temperature did not exceed 10°C.

This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered. After washing and cooling with ethanol,
This precipitate was dissolved in 100 ml of pure water, and 8.
A cold concentrated aqueous solution of 8 g of zinc chloride was added. After filtering off the resulting precipitate, it was washed with ethanol, and this was washed with 1
It was dissolved in 50ml of pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered, washed with water, and then dried to obtain diazo resin-1.

(Manufacture of aluminum plate a) An aluminum plate with a thickness of 0.24 mm is immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then immersed in a 32% aqueous sulfuric acid solution at a temperature of 30°C and a condition of 5 A/dm''. 1
Anodized for 0 seconds, washed with water, immersed in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, further immersed in water (pH 8.5) at a temperature of 80°C for 25 seconds, washed with water, dried, An aluminum plate a was obtained.

(Preparation of plate material) A primer layer composition having the following composition was applied to an aluminum plate a, and after drying at 85° C. for 3 minutes, the entire surface was exposed to +000 mJ/cm'' using a 3 KW ultra-high pressure mercury lamp. It was dried at ℃ for 4 minutes to form a primer layer with a thickness of 0.8 in.

[Primer layer composition] Diazo resin - 18 parts by weight 2-hydroxyethyl methacrylate, methyl methacrylate, copolymer resin with a molar ratio of 34/ILLS - 192 parts by weight Methyl cellosolve 800 parts by weight Next, the following composition was applied on the primer layer: Apply a photosensitive composition of 10
It was dried at 0° C. for 2 minutes to form a photosensitive layer with a thickness of 0.3 pm.

[Photosensitive composition] Diazo resin - 150 parts by weight Molar ratio of 2-hydroxyethyl methacrylate to N-(4-hydroxyphenyl)methacrylamide 20780
Copolymer resin - 150 parts by weight Victoria Pure Blue BO, H (dye manufactured by Hodogaya Chemical ■) 1 part by weight Methyl cellosolve 800 parts by weight Next, the following silicone rubber composition was applied to the photosensitive layer at a dry weight of 1.8 g/m' It was applied and dried at 80°C for 4 minutes.

[Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends IQOfi parts (molecular weight 82,000) Triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar E (manufactured by Esso Chemical) SOO weight Next, a polypropylene film (Alphan EM201, manufactured by Honshu Paper Industries Co., Ltd.) having a thickness of 5 ILm and which had been corona-treated on one side was laminated on the silicone rubber layer so that the corona-treated side was the top surface.

The following coating solution was applied to the surface of the light-transmissive film layer obtained as above using an electrostatic air type spray.
It was heated and cured at 120°C for 3 minutes.

(Coating liquid) Epikote 1001 100 parts by weight Methyltetrahydrophthalic anhydride 36 parts by weight 2.4
．． 8-) Lis(dimethylaminomethyl)phenol 10 parts by weight Methyl cellosolve 1000i parts A moisturizer having a matte layer with particles having an average height of 87 Lm, a size of 15 to 150 μm, and a coverage of the light-transmitting film layer of 10%. A water-free lithographic printing plate material was obtained.

After vacuum-adhering the positive film to the top surface of the above plate material,
Exposure was performed using a metal halide lamp as a light source, and the light-transmitting film was peeled off.

Next, after immersing it in developer-1 or developer-2 below for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer to separate the unexposed portions of the silicone rubber layer and the photosensitive layer. A printing plate with good halftone dot reproduction was obtained.

This is a Heidelberg GTO with the dampening water supply system removed.
Installed on the printing machine, TOYOKING manufactured by Toyo Ink Co., Ltd.
When printed with tlLTRA-Ding KU Aquares G red ink, 2,000,000 prints without stains were obtained, and the reproducibility of highlighted areas was also good.

(Developer-1) β-anilinoethanol 0.5 parts by weight Propylene glycol t, o heavy H parts p −
Tert-butylbenzoic acid 1.0 parts by weight Potassium hydroxide 1.0 parts by weight Polyoxyethylene lauryl ether 0.2 parts by weight Potassium sulfite 2.0 parts by weight Potassium metasilicate 3.0 parts by weight Water
91 parts by weight (Developer-2) Benzyl alcohol 8 parts by weight Perex NBL (manufactured by Kao Atlas Co., Ltd. Anionic surfactant 3
5% aqueous solution) 5 parts by weight jetanolamine 2 parts by weight water
85 parts by weight Example 2 On the surface of the light-transmitting film layer obtained in Example 1, fine droplets of the following coating solution were applied and dried using an electrostatic coating device having a cup-shaped rotary atomizing head.

(Coating liquid) Methyl methacrylate: Ethyl acrylate: Acrylic acid-undercopolymer (Preparation weight ratio 68:20:12) 10 parts by weight Water 70 parts by weight Ethylene glycol 2oiH [average particle height 8
A lithographic printing plate material which does not require dampening water and has a matte layer having a size of 15 to 150 Kawaho and a light-transmitting film layer coverage of 10% was obtained.

Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 20,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.

Example 3 Fine droplets of the following coating solution were applied and dried on the surface of the light-transmissive film layer obtained in Example 1 using an electrostatic coating device having a cup-shaped rotating atomizing head.

(Coating liquid) Methyl methacrylate = 2-hydroxyethyl methacrylate: ethyl acrylate copolymer (charged weight ratio 80
:20:20) to parts by weight methyl cellosolve
70 parts by weight diethylene glycol 70 parts methyl ether 20 parts by weight Particles have an average height of 8 l and a size of 15 to 150 l,
A dampening water-free lithographic printing plate material having a matte layer with a light-transmitting film layer coverage of 10% was obtained.

Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 2,000,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.

Example 4 Fine droplets of the following coating solution were applied to the surface of the light-transmissive film layer obtained in Example 1 using an electrostatic coating device having a cup-shaped rotating atomizing head. After attachment, it was heated at 100° C. for 1 minute to fuse it.

(Coating liquid) Styrene: Methyl methacrylate: Nibutyl acrylate copolymer (charged weight ratio 30:30:30:10) 10
Parts by weight Methyl cellosolve 90 parts by weight 2
The average height of the particles is 8 parts by weight, the size is 20 to 170 dollars,
A dampening water-free lithographic printing plate material having a matte layer with a light-transmitting film layer coverage of 10% was obtained.

Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 20,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.

Example 5 The coating liquid used in Example 2 was applied to the surface of the light-transmissive film layer obtained in Example 1 using a two-fluid nozzle with a nozzle diameter of lam.
Lumina No. 4055T-5 (manufactured by Ikeuchi) Air pressure 3
The fine droplets were attached and dried by spraying at Kg/cm2.

A lithographic printing plate material which does not require dampening water and has a matte layer having a particle height of 8 mm on average, a size of 20 to 2001 L, and a coverage of the light-transmitting film layer of 10% was obtained.

Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 2,000,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.

Example 6 The following composition for a primer layer was applied to a smooth aluminum plate degreased in a conventional manner to a dry film thickness of 2 JL, and cured by heating at 120° C. for 5 minutes.

[Composition 1 for Primer Layer (Epicor) 1001 (Bisphenol A epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent: 450-500) too weight: 36 parts by weight of demethyltetrahydrophthalic anhydride 2.4.
8-) Lis(dimethylaminomethyl)phenol
IO weight city Methylseronlube acetate 600 parts by weight toluene SO
O! i part Methi Northern Methyl Ethyl Ketone 800 parts by weight On an aluminum plate coated with the above primer layer,
The following photosensitive composition containing a silane coupling agent and an organic tin compound was applied to a dry film thickness of 0.25 gm and dried.

[Photosensitive composition] 1=1 (molar ratio) of p-phenylene diacrylic acid ester and 1,4-dihydroxyethyloxycyclohexane Photosensitive unsaturated polyester obtained by polycondensation 10 parts by weight l-methyl-2
-benzoylmethylene-βnaphthothiazoline 0.6 parts by weight N-(β
(aminoethyl)aminomethylphenethyltrimethoxysilane 0.4 parts by weight dibutyltindioctanoate) 0.8. The lid part Sumitone Cyanine Blue VH514 (phthalocyanine blue pigment manufactured by Sumitomo Chemical Co., Ltd.) 2! i part methyl cellosolve acetate 600 parts by weight toluene
300 parts by weight Next, the following silicone rubber composition was applied on the photosensitive layer to a dry film thickness of 2.0 parts.
The silicone rubber cured layer was obtained by applying the coating to a thickness of m and drying.

[Silicone Rubber J#I Product 1 100 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight: approx. 100,000) 6.0 parts by weight of methylhydrodienepolysiloxane having trimethylsilyl groups at both ends (molecular weight: approx. 2500) -Methoxysilylpropyl-3,5-diallyl in cyanurate 3.3 parts dibutyltin dioctanoate 3
．． 3 parts by weight Einpar G (manufactured by Esso Chemical Co., Ltd.) 200
0 parts by weight Next, a 5 JLm thick polypropylene film (manufactured by Honshu Paper Industries, Furufan EN201) which had been corona treated on one side was laminated on the silicone rubber layer so that the corona treated side was the top side.

The following coating solution was applied to the surface of the light-transmissive film layer obtained as above using an electrostatic air type spray.
It was heated and cured at 120°C for 3 minutes.

(Coating W1) Epicoat 1001 100 parts by weight Methyltetrahydrophthalic anhydride 3B parts by weight 2.4
,11-tris(dimethylaminomethyl)phenol
10 parts by weight methyl cellosolve
A dampening water-free lithographic printing plate material having 1000 parts by weight particles having an average height of 8 ILm, a size of 15 to 150 JLII, and a matte layer with a coverage of the light-transmitting film layer of 10% was obtained.

A positive film was layered on this plate material, and the film was vacuum-adhered using Nuark's ET28V U
3 by FLIP-TOP PLATE MAKER
After 0 count exposure, the light-transmissive film was peeled off and developed with 80 parts by weight of Isopar H (manufactured by Esso Chemical Co., Ltd.), 7 parts by weight of diethylene glycol monobutyl ether, 3 parts by weight of diethylene glycol monoethyl ether, and 5 parts by weight of diethyl succinate. When it was immersed in the liquid for 1 minute and rubbed with a developing pad for 1 to 2 minutes, the photosensitive layer and silicone rubber layer in the unexposed areas were removed. In this way, a lithographic printing plate that did not require dampening water was obtained, which faithfully reproduced the image of the positive film over the entire surface of the printing plate.

Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 2,000,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.

Comparative Example 1 An uneven resin layer was subjected to gravure phase inspection on the 5ILm thick polypropylene film used in Example 1 using the same method as in Example 1 of JP-A No. 82-247868. I got the film.

This polypropylene film was laminated on the surface of the silicone rubber layer of Example 1 so that the smooth surface was in contact with the silicone rubber layer to obtain a plate material.

This plate material was exposed in the same manner as in Example 1.

Nitrogen gas generated during exposure was trapped between the light-transmissive (cover) film and the silicone layer, causing bubbles.

When developed in the same manner as in Example 1, printing blur occurred and halftone dot reproducibility was poor.

Claims (1)

[Scope of Claims] 1. A method for producing a dampening water-free lithographic printing plate material having a photosensitive layer and a silicone rubber layer or a photosensitive silicone rubber layer and a light-transmitting film layer on a support, wherein the silicone rubber A light-transparent film layer is formed on the layer, and then fine droplets of a coating liquid in which a resin is dissolved or dispersed are deposited on the light-transparent film layer and then dried or thermally cured to form the light-transparent film layer. A method for producing a lithographic printing plate material that does not require dampening water, comprising forming a discontinuous matte layer on which solid particles are fixed. 2. The method for producing a lithographic printing plate material that does not require dampening water according to claim 1, characterized in that fine droplets of the coating liquid are electrostatically sprayed and deposited on the light-transmitting film layer. 3. The method for producing a lithographic printing plate material that does not require dampening water according to claim 1 or 2, wherein the solvent of the coating liquid is water or an organic solvent with a boiling point of less than 130°C.