JPH03182754A - Photosensitive planographic printing plate requiring no dampening water - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate that does not require dampening water, and in particular has a primer layer and has excellent adhesion between the primer layer and the support. The present invention relates to a photosensitive lithographic printing plate that does not require dampening water.

[Prior art] Conventionally, in lithographic printing, it was necessary to perform printing by making use of the lipophilicity of the image area and the hydrophilicity of the non-image area, and by maintaining a delicate balance between water and ink, which required considerable skill. Needed.

In other words, in the conventional printing method that requires dampening water, an image-like lipophilic portion is formed by passing an image film through a plate material coated with a lipophilic photosensitive layer on a hydrophilic support, and then developing it. A printing plate is prepared by providing a hydrophilic area which is a non-image area. During printing, water is first transferred to the non-image areas, and then ink is transferred. Ink does not adhere to non-print areas where water is present, but only to print areas. However, this method
It is difficult to control the delicate balance between dampening water and ink, which causes emulsification of the ink, and the ink mixes with the dampening water, causing poor ink S and dirt, which is a major cause of wasted paper. It had

Furthermore, the transfer of dampening water to the printing material causes a change in the dimensions of the printing material, which also has the disadvantage that the sharpness of the image is impaired, especially when printing in multiple colors.

For this reason, attempts have been made to develop a lithographic printing plate that does not require dampening water. A waterless lithographic plate having a structure is disclosed, and a plate-making method is also described in which the photosensitive layer is dissolved in a developer to remove the upper silicone rubber layer to form an image area. Also, Special Publication No. 54-26923 and No. 5
No. 6-23150 has a structure similar to the above in that a silicone rubber layer is provided on a photosensitive layer on a support, but the photosensitive layer does not dissolve in a developer and the photosensitive layer and silicone rubber layer are separated by image exposure. A method is disclosed in which the rubber layer' undergoes photo-adhesion or photo-peeling and selectively swells and removes only the silicone rubber layer.

Further, JP-A-60-229031 discloses a waterless lithographic plate having a structure in which a photosensitive layer and a silicone layer are provided on a primer layer on a support.

[Problems to be Solved by the Invention] Particularly in a photosensitive lithographic printing plate that does not require dampening water and has a primer layer, the adhesion of the primer layer to the support is determined by, for example, the difference in exposure solubility between the primer layer and the photosensitive layer. It is well known that it has a great influence on various performances such as image forming ability by enlargement, development latitude, and storage performance of image characteristics.

However, since aluminum, which is commonly used as a conventional support, is an inorganic substance, it has been difficult to dramatically improve the adhesive force with a primer layer made of an organic substance, including in the prior art described above.

Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has excellent adhesion between a primer layer and a support.

Another object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and is excellent in image forming ability, development latitude, and storage stability of image characteristics.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to form a primer layer, a photosensitive layer, and a silicone rubber layer on a support from the support side. The inventors have found that the present invention can be achieved by providing a dampening water-free photosensitive lithographic printing plate characterized in that the primer layer contains a silane coupling agent.

The present invention will be explained in more detail below.

In the present invention, the silane coupling agent contained in the primer layer is Non-1! Basic silane coupling agents are preferably used, and vinyl-based, acrylic-based, and epoxy-based silane coupling agents are particularly preferably used.

Such silane coupling agents include, for example, vinyltrichlorosilane, vinyltriethoxysilane, γ-chloropropylmethyldichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-amitubu Opyltriethoxy Silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-mel, captopropyltrimethoxysilane, γ-glyside Examples include xyprobyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and preferably vinyltriethoxysilane and γ-mercapto. Propyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-Glycidoxypropylmethyldimethoxysilane, T
-Methacryloxypropyltrimethoxysilane or γ-
Methacryloxypropylmethyldimethoxysilane is used, particularly preferably vinylethoxysilane or γ-methacryloxypropyltrimethoxysilane.

Moreover, two or more of the above silane coupling agents can also be used in combination.

In the present invention, the silane coupling agent is preferably contained in the brimer layer in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.

As the primer layer in the present invention, any of a variety of known primer layers can be applied, but a photocurable primer layer by photocrosslinking, photodimerization, photopolymerization, etc., especially a layer consisting of a diazo resin and a hydroxyl group-containing polymer, can be photocured. A brimer layer formed by the above method is preferably used.

As the diazo resin, for example, Photographic Science and Engineering (Photo
, Sci, Eno, ) Volume 17, Page 33 (19
73), U.S. Patent No. 2.063.631, U.S. Patent No. 2,
No. 679.498 and No. 3,050,502, respectively.
A diazo compound and an active carbonyl compound (for example, formaldehyde, acetaldehyde, or benzaldehyde, etc.), the manufacturing method of which is described in Book 1, JP-A-59-78340, etc., are mixed in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid. Diazo resin obtained by condensation with
A diazo resin obtained by condensing a diazo compound and a diphenyl ether derivative, the manufacturing method of which is described in Publication No. 4001, can be used.

The counter anion of the diazo resin used in the present invention is
It contains an anion that forms a stable salt with the diazo resin and makes the resin soluble in organic solvents.

These include organic carboxylic acids such as decanoic acid and benzoic acid;
Contains organic phosphoric acids and sulfonic acids such as phenyl phosphoric acid,
Typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-humanOxy4-methoxybenzophenone-5-sulfone acid, hydroquinone sulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5
-Aliphatic and aromatic sulfonic acids such as sulfoisophthalate, 2.2', 4.4'-tetrahydroxybenzophenone, 1,2.3-trihydroxybenzophenone, 2.2', 4-? - Hydroxyl group-containing aromatic compounds such as hydroxybenzophenone, hexafluorophosphoric acid,
Halogenated Lewis acids such as tetrafluoroboric acid, Cff
Examples include, but are not limited to, perhalogen acids such as 1O+ and IO4. The weight average molecular weight of the coupled product with β-naphthol measured by gel permeation chromatography (GPC) is 200 to 100.
00 (in terms of styrene) is preferable, and the range is 500 to 5
ooo II! More preferably.

In the present invention, the proportion of the diazo resin in the brimer layer is preferably 3 to 8011%, more preferably 5 to 60% by weight.

Moreover, as the hydroxyl group-containing polymer, an ester or amide of alcoholic hydroxyl group-containing poly(meth)acrylic acid is preferably used.

Examples of the monomer having an alcoholic hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-(4-hydroxyethylphenyl)methacrylamide, and hydroxy-methyldiacetone (meth)acrylamide.

The monomer copolymerizable with the above hydroxyl group-containing monomer includes (1) a monomer having an aromatic hydroxyl group, such as N-(4
-Hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, 〇-1l-1p
-Hydroxystyrene, 0-1p-hydroxyphenyl acrylate or -methacrylate, (2>α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, etc., (3>methyl acrylate, acrylic acid Ethyl, butyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic 1-
(4) Substituted alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (4) methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-
(W1-substituted) alkyl methacrylate such as dimethylaminoethyl methacrylate, (5>acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, Nhexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxy Edylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-
Acrylic acid or methacrylamide such as N-phenylacrylamide, (6) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (7) Vinyl Vinyl esters such as acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (8) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene; (9) Methyl styrene and ethyl vinyl ketone. , vinyl ketones such as propyl vinyl ketone, phenyl vinyl ketone, (10) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (11) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, Examples include methacrylonitrile and the like.

Water i in the above hydroxyl group-containing polymer! The amount of monomer containing 11 groups is not particularly limited, but is preferably 5% by weight or more.
95% by weight, particularly preferably 10% to 90% by weight.

The weight average molecular weight of the hydroxyl group-containing polymer of the present invention measured by GPC is preferably 5,000 to 1,000,000 (in terms of styrene). If the value is lower than 5000, it may be damaged by the coating solvent or developer of the photosensitive layer even after exposure.
If the value is larger than 1,000,000, it is difficult to select a coating solvent.

In addition, polyvinyl alcohol derivatives, epoxy resins,
Novolac resins, gelatin, cellulose, etc. can also be used.

The proportion of the hydroxyl group-containing polymer in the brimer layer is preferably 5 to 95% by weight.

In the present invention, in addition to the above components, the primer layer may include fillers such as titanium oxide, antihalation agents, colorants such as dyes and pigments, coating improvers, plasticizers, stabilizers, and oil sensitizers. It may also contain agents and the like in an amount not exceeding 10% by weight.

As the above dye, for example, Victoria Pure Blue-8
Day 0, Oil Blue #312, Patent Pure Blue, Crystal Violet, Leuco Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B1 Basic Tsuksin, Malachite Green, Leucomalachite Green, Cabinet-Cresol Purple, Cresol Red, Xylenol Blue, rhodamine B1 auramine, triphenylmethane type represented by 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenylacetanilide, etc.
Examples include diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes.

Examples of coating properties improvers include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka)), FC-430 (Sumitomo 3M), etc. (manufactured by), etc.

Examples of plasticizers for imparting flexibility and abrasion resistance to coating films include butylphthalyl, polyethylene glycol,
Examples include tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrafurfuryl oleate, oligomers of acrylic acid or methacrylic acid, etc. .

In addition, in order to improve the printing ink adhesion of images, various additives having hydrophobic groups are used, such as p-octylphenol/formalin novolac resin, p-[-butylphenol/formalin novolac resin, p-t-butylphenol/benzaldehyde resin. , a modified novolac resin such as a rosin-modified novolak resin, or an O-naphthoquinonediazide sulfonic acid ester (esterification rate of OH group: 20 to 70 mol %) of these modified novolak resins can be added.

The above-mentioned photocurable diazo resin or a composition containing the same is dissolved in an appropriate organic solvent together with other additives added as necessary, coated on a support, dried, and then exposed to light. The diazo resin is completely decomposed and cured to form a brimer layer.

The thickness of the brimer layer is 11g/dv' to 200g/d
It is preferably 1z, more preferably 3mg/
df ~ 100u/df.

Specifically, the photosensitive layer includes, for example, a photoinsolubilizable photosensitive layer containing an O-quinonediazide compound, an O-nitrobenzyl carbinol ester compound, etc., a photoinsolubilizable photosensitive layer containing a diazo compound, a compound having an addition-polymerizable vinyl group, etc. Examples include a photosensitive layer.

The above-mentioned 0-quinonediazide compounds are compounds having at least one 0-quinonediazide group, preferably 0-benzoquinonediazide group or 0-naphthoquinonediazide group, and include known compounds of various structures, such as those described in J. Kosar's book Light Sensitive Systems J (published by John Wiley & Sams, 1965)
Compounds described in detail on pages 339 to 353 are included.

For example, various hydroxyl compounds and benzoquinone-1
, 2-diazide sulfonic acid, naphthoquinone-1,2-diazide sulfonic acid, and the like. Examples of the hydroxyl compound used include condensation resins of phenols such as phenol, cresol and pyrogallol and carbonyl group-containing compounds such as formaldehyde, benzaldehyde and acetone, particularly resins obtained by condensation in the presence of an acidic catalyst.

As the photosensitive layer containing a diazo compound, a photosensitive layer containing the same diazo resin as contained in the related brimer layer is preferably used.

The proportion of the diazo resin in the photosensitive layer is preferably 3 to 60% by weight, more preferably 5 to 50% by weight.

Furthermore, the same hydroxyl group-containing polymer contained in the above-mentioned Brimer [1] can be used for the photosensitive layer. The proportion of such hydroxyl group-containing polymer in the photosensitive layer is preferably 5 to 95% by weight, more preferably 10 to 90% by weight.
Weight%.

In addition to the above-mentioned materials, dyes, pigments, exposure visible image agents, coating properties improvers, etc. may be added to the photosensitive layer as necessary to improve the development visible image properties, exposure visible image properties, and coating properties. It can improve your sexuality.

As the above-mentioned dye and coatability improver, the same ones as those contained in the above-mentioned brimer layer are used.

The above-mentioned dyes are generally present in the photosensitive layer in a range of 0.01. It can be contained in an amount of up to about 10% by weight, preferably about 0.05 to 8% by weight.

Further, examples of the exposure-visible image agent include triazine compounds and oxadiazole compounds.

In the present invention, the thickness of the photosensitive layer is 0.11 g, / df
~30ma/df is preferred, 0.5mg/df~1
0u/dw' is more preferred.

In the present invention, a silicone rubber layer is further provided on the photosensitive layer, and the silicone rubber used in the silicone rubber layer is preferably linear or crosslinked organopolysiloxane. The organopolysiloxane usually has molecular fingers ranging from 1 to 100,000,
At room temperature, it will be liquid or waxy or cake-like.
It is something that has been done by I. The organopolysiloxanes are classified into condensed type and addition type depending on the method of crosslinking.

The condensed type is one in which crosslinking is performed by a condensation reaction, and water, alcohol, ionic acid, etc. are released by the reaction. Particularly useful condensation type silicone rubbers include a mixture of a linear organopolysiloxane having hydroxyl groups at both ends or a part of the main chain and a silicone crosslinking agent, or one in which the hydroxyl groups are reacted with a silicone crosslinking agent. In either case, adding a condensation catalyst is advantageous in terms of crosslinking speed.

The organopolysiloxane has the following repeating units in its main chain.

1 -(-8i -(1- 2 In the formula, R1 and R2 are alkyl, aryl, alkenyl, or a combination thereof, each of which may have a substituent such as a cyano group, a halogen atom, or a hydroxyl group, and a methyl group, phenyl A vinyl group, a trifluorobyl group, and a trifluorobyl group are preferable, and a methyl group is particularly preferable.

As the silicone crosslinking agent, / -ococro3. So-called acetic acid-removed type, oxime-eliminated type, alcohol-eliminated type, deaminated type, which has a functional group represented by -0-N \8. or -〇〇 (in the formula, R and R' are alkyl groups), Examples include condensation type silicone crosslinking agents such as dehydrated type. Examples of such crosslinking agents include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane,
Diethyldiacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, methyltris(acetoneoxime)silane, methyltri(N-methyl, N
-acetylamino)silane, vinyltri(methylethylketoxime)silane, methyltri(methylethylketoxime)silane or oligomers thereof.

All of these crosslinking agents are organopolysiloxane 10
The amount is preferably in the range of 0.5 to 30 parts by weight relative to 0 parts by weight.

Examples of the condensation catalyst include organic carboxylic acids, titanate esters, naphthenic acids, and the like.

The addition type refers to one in which a (3i-H) group in a crosslinking agent is added to an unsaturated group in the main body, such as a vinyl group (Ic=C2), resulting in crosslinking.

Specifically, vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like are mixed with platinum-based catalysts (for example, platinum chloride, etc.).

The organopolysiloxane has a repeating unit similar to the orthopedic type described above in the main chain.

In the silicone rubber layer of the present invention, either or both of condensation type and addition type silicone rubbers can be used.

It is also possible to use condensed and addition type organopolysiloxanes having hydroxyl groups, unsaturated groups, etc. in one organopolysiloxane.

Among the commercially available silicone rubbers according to the present invention, preferred examples include KS705F and K manufactured by Shin-Etsu.
E-41, 42, 44, Toshiba Silicone (manufactured by) Y
E 5505. YF 3057, East Silicone (
SH-781, PRX-305, 5H-237W condensation type silicone rubber and Shin-Etsu IIKS-837, K
Additive silicone rubbers include E-103, KE-106, KE-1300, TSE-3032 and RTU-8 manufactured by Toshiba Silicone Co., Ltd., and SH-9555 manufactured by Toshiba Silicone Co., Ltd.

Furthermore, for the purpose of improving the strength of silicone rubber, inorganic fillers such as silica, titanium oxide, and aluminum oxide may be added, and silica is particularly preferably used.

From the viewpoint of dispersibility or dispersion stability, such fillers preferably have an average particle diameter of 500 nl or less.

In the present invention, the thickness of the silicone rubber layer is preferably as thin as possible from the point of view of image quality and developability.On the contrary, a certain degree of thickness is required from the point of view of printing durability, printing and staining, etc., so generally 3 mmdf ~501Mdf is preferred, and 5aMdf~
301! J/df is more preferred.

In the present invention, an adhesive layer made of, for example, epoxy resin may be provided between the photosensitive layer and the silicone rubber layer, and the adhesive layer may contain various reactive crosslinking agents, silane coupling agents, etc. The thickness of the adhesive layer is 0.
02■o/d111-11Mdf is preferred.

Furthermore, the photosensitive lithographic printing plate that does not require dampening water of the present invention may be provided with a protective layer on the silicone rubber layer, and a method for providing the protective layer is to use a polypropylene film or the like as described in Japanese Patent Publication No. 61-614. How to do it and JP-A-61-27
A method of coating a high molecular weight polymer described in No. 545 is known.

As the support used in the present invention, it is possible to use a support that is flexible enough to be set in a normal lithographic printing machine and that is insulating as long as it can withstand the load applied during printing. Not restricted. Examples include papers such as coated paper, metal plates such as aluminum plates, and plastic films such as polyethylene terephthalate.

Supports used in the present invention include aluminum plates,
Alternatively, aluminum foil and other composite materials are preferred, and aluminum plates are particularly preferred from the viewpoint of printing durability.

In particular, in the present invention, it is possible to use an aluminum plate or aluminum foil whose surface has been anodized or anionized with sodium silicate, sodium phosphate, phosphoric acid, etc., if necessary. Furthermore, anodization treatment and 7-ionization relief may be used together. Preferably, the anodization treatment is followed by a 7-ionization treatment, and more preferably the anodization treatment is followed by a sodium silicate treatment.

Further, the thickness of the support is preferably 0.1 to 0.3 m.

After imagewise exposing the photosensitive lithographic printing plate that does not require dampening water, prepared as described above, it is developed with a developer to dissolve the photosensitive layer and removed along with the silicone rubber layer above it, resulting in the brimer layer being exposed as an image area. Then, a lithographic printing plate that does not require dampening water is formed.

In this case, it is preferable to dye the image area with a cationic dye such as crystal violet, Victoria Blue BOH, and Astrazonelet during or after development.

The light source used for exposure may be any general-purpose light source including ultraviolet rays of fauna or higher and visible light, but carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes and the like are particularly preferred.

The developer used in the development process includes water, the following polar solvents, alkaline compounds such as amines, surfactants, and, if necessary, aliphatic hydrocarbons (hexane, heptane, etc.).
"Isopar E, H, G" (trade name of aliphatic hydrocarbons manufactured by Esso Chemical) or gasoline, kerosene, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.) or halogenated hydrocarbons (such as trichlene). Those added are suitable.

Polar solvent alcohols (methanol, ethanol, water, etc.) Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carpitol, ethyl carpitol xane, etc.) Ketones (acetone, methyl ethyl ketone, etc.) Esters (ethyl acetate, methyl cellosolve acetate) , cellosolve acetate, carpitol acetate, etc.) The developer is a developer containing water as a main component, such as that described in JP-A No. 61-275759, which contains 30% by weight of water. Above, preferably 501
A developer containing 1% to 98% by weight of an organic solvent and a surfactant can also be used, and a developer containing an alkaline agent can also be used.

The yA image can be formed by various known methods, such as rubbing with a developing pad containing a developer as described above, or pouring a developer onto the printing plate and then rubbing with a developing brush.

【Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example-1 Synthesis of diazo resin-1 p-diazodiphenylamine sulfur 1j3i14.5g (5
0 mmol) was dissolved in 40.99 concentrated sulfuric acid under water cooling. To this reaction solution, 1.35111 (45 mmol) of paraformaldehyde was slowly added so that the reaction temperature did not exceed 10°C.

This reaction mixture was added dropwise to 500 u of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100-pure water, and a cold concentrated aqueous solution containing 6.8 g of zinc chloride was added to this solution. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 d 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 collected by filtration, washed with water, and then dried to obtain diazo resin-1.

Production of Aluminum Plate A An aluminum plate with a thickness of 0.24 mg + was 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 under the conditions of 5 A/df.
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 at a temperature of 90°C (9 mouths, 8.5°) for 25 seconds, washed with water, and dried. Thus, an aluminum plate a was obtained.

A brimer layer composition having the composition shown below was applied to an aluminum plate a, and after drying at 85° C. for 3 minutes, the entire surface was exposed to light of 10,100 O/Cf using a 3 KW ultra-high pressure mercury lamp. It was further dried at 100° C. for 4 minutes to form a 0.8 μm thick brimer layer.

(Brimer layer composition) (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60 - 192
Part (3) γ-methacryloxypropyltrimethoxysilane 2 parts (4) Methyl cellosolve 900 parts Next, a photosensitive composition having the composition shown below was applied onto the above-mentioned brimer layer and dried at 100°C for 2 minutes to determine the thickness. A 0.3 μm photosensitive layer was formed.

(Photosensitive composition) (1) Diazo resin - 170 parts (2) 2-hydroxyethyl methacrylate, N-(4
-Hydroxyphenyl) methacrylamide molar ratio 30/70 copolymer resin-23
0 parts (3) Victoria Pure Blue - 80 mouths (manufactured by Hodogaya Kagaku ■ dye) 1 part (4) Methyl cellosolve 900 parts Next, the following silicone rubber composition was applied on the photosensitive layer to a dry weight of 1.8 Q/f. It was applied as follows and dried at 90°C for 10 minutes.

(Silicone rubber layer composition) Dimethylpolysiloxane having hydroxyl groups at both ends (molecules 152,000>100
1 part triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar E
(Esso Kagaku [)] 900 parts Next, a 5 μm thick single-sided matted polypropylene film was laminated on the silicone rubber layer to obtain a waterless planographic plate.

After a positive film was vacuum-adhered to the upper surface of the above plate material, it was exposed to light using a metal halide lamp as a light source.

Next, after performing standard development by immersing it in the developer-1 below for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer to remove the silicone rubber layer and photosensitive layer in the unexposed areas. A printing plate with well reproduced halftone dots was obtained.

Further, the image area of the above printing plate could be vividly dyed by applying a dyeing liquid having the composition shown below to a cloth, lightly rubbing the plate, and then washing with water.

(Developer-1) β-anilinoethanol 0.5 parts Propylene glycol 1.0 parts p-ter
t-Butylbenzoic acid 9 1.0 part Potassium hydroxide 1.0 part Polyoxyethylene lauryl ether 0.1 part Potassium sulfite
2.0 parts potassium metasilicate
3.0 parts water
91 parts (staining liquid) Solfit (manufactured by Kuraray Sobren Chemical ■ Solvent> 20 parts Residor T W-0120 (manufactured by Kao ■ Surfactant> 0.5 parts Benzyl alcohol 5.0 parts Victoria Pure Blue - BO mouth 1 .0 part water
10
0 parts Also, the above developer-1 was developed in the same manner at a temperature of 35°C to check the over-developability.
As a result of evaluating the under-developability by developing the printing plate in the same manner using a fatigued developer after 5f processing per printing plate, it was possible to obtain a printing plate in which halftone dots were well reproduced as in standard development.

Furthermore, even if the above-obtained dampening water-free photosensitive lithographic printing plate sample was subjected to forced deterioration storage at 55°C for 3 days or at 40°C and relative humidity y180% for 3 days, exposure and standard development were performed. I was able to get a copy.

Example 2 A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 1, except that the primer layer composition of Example 1 was changed as follows.

(Primer layer composition) (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60 - 192
Part (3) T-methacryloxypropyltrimethoxysilane 0.1 part (4) Methyl cellosolve 900 parts When development was carried out in the same manner as in Example 1, the silicone rubber layer in the unexposed area was It was possible to obtain a printing plate in which the halftone dots were removed and the halftone dots were well reproduced. Further, even when development was performed after storage for forced deterioration, a good printing plate could be obtained.

Example 3 A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 2, except that the primer layer composition of Example 2 was changed as follows.

(Primer layer composition) (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60 - 192
Part (3) γ-methacryloxypropyltrimethoxysilane 10 parts (4) Methyl cellosolve 900 parts When development was carried out in the same manner as in Example 1, the silicone rubber layer in the unexposed areas was removed under all development conditions. It was possible to obtain a printing plate in which halftone dots were well reproduced. Further, even when development was performed after storage for forced deterioration, a good printing plate could be obtained.

Comparative Example 1 A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 1, except that the primer layer composition of Example 1 was changed as follows.

<Primer layer composition> (1) Diazo resin [1-18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60-192
Part (3) Methyl cellosolve 900 parts When the obtained material was then developed with developer-1 used in Example 1, the primer layer peeled off from the support, and the material could not be used as a printing plate. was not obtained.

Example 4 A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 1, except that the primer layer composition of Example 1 was changed as follows.

(Primer layer composition) (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate, acrylonitrile, glycidyl methacrylate in a molar ratio of 20/40/40 -
392 parts (3) Vinyltriethoxysilane 2 parts (4
) Methyl cellosolve 900 parts The obtained material was subjected to standard development in the same manner as in Example 1, whereby the silicone rubber layer in the unexposed areas was removed and a printing plate with well reproduced halftone dots was obtained.

Further, even when over-development or under-development evaluation was performed as in Example 1, a printing plate with good image formation could be obtained.

Furthermore, even when development was performed after forced deterioration storage, a good printing plate was obtained.

Comparative Example 2 A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example 1, except that the brimer layer composition of Example 1 was changed as follows.

(Brimer layer composition) (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate, acrylonitrile, glycidyl methacrylate in a molar ratio of 20/40/40 -
392 parts (3) 900 parts of methyl cellosolve When the obtained material was subjected to standard development in the same manner as in Example-1,
The silicone rubber layer in the unexposed areas was removed, and a printing plate with well reproduced halftone dots was obtained.

However, when over-development and under-development evaluation was performed in the same manner as in Example 1, the primer layer peeled off, and no material usable as a printing plate was obtained.

Further, when development was performed after storage for forced deterioration as in Example 1, the primer layer peeled off from the support, and no material usable as a printing plate was obtained.

The results of Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1.

[Effects of the Invention] As explained in detail above, the present invention improves the adhesion between the brimer layer and the support, resulting in excellent image forming ability, development latitude, and storage stability of image characteristics. A photosensitive lithographic printing plate that does not require dampening water can be provided.

Claims (2)

[Claims] (1) A photosensitive lithographic printing plate that does not require dampening water and has a primer layer, a photosensitive layer, and a silicone rubber layer in this order from the support side on a support, characterized in that the primer layer contains a silane coupling agent. Photosensitive planographic printing plate that does not require dampening water. (2) In a photosensitive lithographic printing plate that does not require dampening water and has a primer layer, a photosensitive layer, and a silicone rubber layer in this order from the support side on a support, 0.1 to 10% by weight of a silane coupling agent is added to the primer layer. A photosensitive lithographic printing plate that does not require dampening water.