JPH0411259A - Dampening-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To improve the adhesive property between an aluminum substrate and a coating layer to be provided thereon by providing a photosensitive layer and a silicone rubber layer in this order on the film of the aluminum substrate having a specific anodized film. CONSTITUTION:The aluminum substrate has the anodized film having pores of 200 to 2000Angstrom diameter. The photosensitive layer and the silicone rubber layer or a primer layer, the photosensitive layer and the silicone rubber layer are provided in this order on the film of this aluminum substrate. The secure adhesion is obtd. between the aluminum substrate and the coating layer provided thereon in this way and the printing plate withstands the strong rubbing with an org. solvent system or aq. developer.

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 to the adhesion between an aluminum substrate and a coating layer provided thereon in a wet state during development processing. This invention relates to a photosensitive lithographic printing plate that does not require dampening water and has been improved.

[Conventional technology]

For photosensitive lithographic printing plates that do not require dampening water and have a silicone rubber layer as a non-image area, for example, Japanese Patent Publication No. 44-23042
No., Special Publication No. 46-16044, Special Publication No. 54-2692
No. 3, JP 61-54222, JP 63-265
Various methods have already been proposed in No. 247 and the like.

Aluminum plates are widely used as supports for these photosensitive lithographic printing plates that do not require dampening water.

The reason is as follows. That is, the support of photosensitive lithographic printing plates that use dampening water, which currently makes up the majority of lithographic printing plates, is an aluminum plate.
Most of the lithographic printing presses currently in operation on the market have a structure suitable for mounting an aluminum plate. Therefore, by using aluminum as a support even in a lithographic printing plate that does not require dampening water, it becomes possible to use the plate mounting device of a printing press without special modification. In addition, workers who handle plates at the plate-making site of lithographic printing plates are familiar with handling printing plates made of aluminum supports, so the strength of aluminum,
For example, maintaining the advantages of an aluminum support, such as resistance to formation of nicks, resistance to deformation due to pressure, etc., dimensional stability before and after development processing, and relatively light weight for a metal support. I strongly desire. The above circumstances are the reasons why aluminum is used as a support even in lithographic printing plates that do not require dampening water.

On the other hand, particularly in planographic printing plates that do not require dampening water, sufficient adhesion between the aluminum substrate and the coating layer provided on the surface thereof is desired. That is, in a planographic printing plate that does not require dampening water, the non-image area is formed using the ink repellency of the silicone rubber layer of the coating layer, and the image area is formed using the ink receptivity of the photosensitive layer or primer layer. For example, during development, if part of the coating layer peels off from the support and the surface of the support is exposed, normal printed matter cannot be obtained. As a method to improve the adhesion between the coating layer to be installed and the aluminum substrate,
It has been proposed that the coating layer contain various compounds that have the effect of improving adhesion. For example, JP-A-63-305360 discloses that adhesion can be improved by incorporating a silane coupling agent into a brimer layer made of hardened gelatin provided adjacent to a support. .

However, the effect of improving adhesion by using a silane coupling agent is only achieved with a specific combination of the coupling agent and the coating layer, and the material design perspective is subject to significant restrictions. . Furthermore, in particular, water-based developers such as those described in JP-A No. 61-275759 and JP-A No. 63-3314
When a silicone layer is treated with a pretreatment liquid that swells as described in No. 0, and then developed while being rubbed with a brush in water or a treatment liquid whose main component is water, the effect is as follows. This is not satisfactory, and a problem arises in that the coating layer peels off from the aluminum surface at the periphery of the plate depending on conditions such as the temperature of the developer and the rubbing pressure of the brush.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has improved adhesion between an aluminum substrate and a coating layer provided thereon.

[Means to solve the problem]

As a result of various studies, the present inventors found that diameters of 200 Å to 2
A photosensitive layer, a silicone rubber layer or a primer layer, a photosensitive layer and a silicone rubber layer are provided in this order on an aluminum substrate having an anodized film having 0,000 pores, and no dampening water is required. The inventors have discovered that the above object can be achieved in a photosensitive lithographic printing plate, and have completed the present invention.

The present invention will be explained in detail below.

<Aluminum substrate> As the aluminum substrate equipped with an anodized film having pores of 200 Å to 2,000 in diameter, which is used in the present invention, the phosphate electrolytic aluminum substrate described in Japanese Patent Publication No. 46-26521, Aluminum substrates etched using phosphoric acid or polyphosphoric acid after sulfuric acid electrolysis described in JP-A-49-8428, JP-A-49-12903 and JP-A-50-138903; Aluminum substrates etched using an alkaline solution after sulfuric acid electrolysis as described in Japanese Patent Publication No. 50-138903 and Japanese Patent Application Laid-Open No. 1984-93101,
There is a tertiary sodium phosphate electrolytic aluminum substrate described in Japanese Patent No. 424.

Other examples include aluminum substrates anodized with a sulfuric acid/phosphoric acid mixture and aluminum substrates anodized with an aqueous sodium hydroxide solution. The amount of these anodic oxide films is 0.2 g/m to 2 g/n (preferably 0.5
g/m to 1.5 g/m.

In addition, in the commonly used anodic oxide film using sulfuric acid, the diameter of the pores is 50 Å to 150 Å, but with such an anodic oxide film support, the adhesion with the coating layer is insufficient, and during development and , the problem arises that the coating layer separates during printing.

However, as in the present invention, by setting the diameter of the pores in the anodic oxide film of the aluminum substrate to 200 Å to 2,000 Å, preferably 300 Å to 1000 Å, the substrate and the coating layer are firmly adhered to each other, and the above-mentioned problems can be solved. resolved.

Furthermore, the aluminum substrate used in the present invention may be subjected to a hydrophilic treatment if desired. Hydrophilic treatments include undercoating of water-soluble cellulose derivatives as described in JP-A-48-83902, JP-A-4963501, JP-A-49-96803, and JP-A-49-102403;
Silicate treatment described in Tokoku No. 475125 and No. 48-9007, Tokoku No. 561251
Examples include hot water treatment described in Publication No. 8. Other suitable hydrophilic treatments include polyvinylsulfonic acid, polymers and copolymers having sulfonic acid groups in their side chains, and undercoating of polyacrylic acid.

Furthermore, by surface treating the substrate with various silane coupling agents, the adhesion with the coating layer can be further improved. As a treatment method, it is common to use a silane coupling agent in an aqueous solution of 0.1 to 3% by weight, but even higher concentrations are acceptable, and the type of silane coupling agent and treatment time are acceptable. In some cases, sufficient improvement in adhesion is observed even at lower concentrations. The appropriate amount of the silane coupling agent to be applied is 5 .mu./m1 to 100 .mu./m' in terms of dry weight. Further, a brimer layer or the like may be further provided on the surface of these substrates for the purpose of preventing halation and for other purposes.

In addition to improving the adhesion between the substrate and the photopolymerizable photosensitive layer, the brimer layer can also prevent halation, improve printing properties,
Various methods can be used to improve the staining of images as the case may be.

For example, various photosensitive polymers as disclosed in JP-A No. 60-22903 are cured by exposure to light before laminating a photopolymerizable photosensitive layer, and JP-A No. 62-5
0760, a heat-cured epoxy resin, a hardened gelatin disclosed in JP-A-63-133151, other hardened zein, and polyurethane. ,polyamide,
Styrene/butadiene rubber, carboxy-modified styrene/
Butadiene rubber, acrylonitrile/butadiene rubber,
Examples include carboxy-modified acrylonitrile/butadiene rubber, polyisoprene, and acrylate rubber. Furthermore, these materials may be used in any arbitrary mixture, and depending on the purpose, dyes, pH indicators, print-out agents, photopolymerization initiators, adhesion aids (e.g., polymerizable monomers, diazo resins, Additives such as silane coupling agents, titanate coupling agents, aluminum coupling agents, isocyanate compounds, carboxylic acid-containing resins), white pigments, and silica powder may also be included.

In general, the coating amount of the brimer layer is 0.5 to 20 g in dry weight.
/It is durable.

Photosensitive layer> The photosensitive resin layer used in the present invention generally has a difference in solubility in a developer due to exposure, or a change in adhesiveness at the interface with the upper silicone rubber layer. You can use whatever you have. Image formation may be negative type or positive type.

Compounds or compositions constituting such a photosensitive layer include the following.

(^) Photopolymerizable photosensitive composition: (1) Monomer or oligomer having an olefinically unsaturated double bond group, (2) used as necessary,
It consists of a photopolymerizable photosensitive material consisting of a polymer compound having film-forming ability and (3) a photopolymerization initiator.

In the photosensitive resin layer containing the above components (11 to (3)), a polymer compound in which components (11 and (2)) are bonded, that is, a side chain that is photopolymerizable or photocrosslinkable and has an olefinic unsaturated A photosensitive resin layer containing a polymer compound having a double bond group and a film-forming ability is also suitable for use in the present invention. A photosensitive resin layer to which the monomer or olicomer of (1) is added is more suitable.

Compositions for photosensitive resins such as those described above are disclosed in, for example, Japanese Patent Application No. 1999.
Polyurethane resins or polyamide resins such as those described in Japanese Patent No. 301,568 are preferably used. Furthermore, those described in JP-A-1-214839 are also suitable.

(B) Photodimerization type photosensitive composition: In the main chain or side chain of the polymer (R: alkyl group having 1 to 10 carbon atoms) (R, and R2 each represent an alkyl group, and R and R2 are may be taken together to form a 5-membered ring or 6-membered ring), or (R: an alkyl group having 1 to 10 carbon atoms).

For example, polymers whose main component is a photosensitive polymer such as polyamides, polycarbonates, etc. as photosensitive groups in the main chain or side chain of the polymer, such as U.S. Patent No. 3,03
No. 0,208, No. 3,707,373 and No. 3.
Compounds such as those described in the specifications of No. 453,237); Main components are photosensitive polyesters derived from (2-propenylidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols. (e.g., U.S. Pat. No. 2,956°878 and U.S. Pat. No. 3,1
73,787); cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose, and the like (e.g., U.S. Pat. 2.690,966,
2,752,372, 2,732,301, etc.),
Furthermore, the polymers described in JP-A-58-25302 and JP-A-59-17550 are also included.

(C) A composition consisting of a photocurable diazo resin or azide resin, a photosensitizing side if necessary, and some filler additives: As the photocurable diazo resin, paradiazo diphenylamine, paradiazu monoethyl Examples include zinc chloride double salts of condensates of formaldehyde and diazo amines such as aniline and paradiazobenzylethylaniline.

This photosensitive resin layer is essentially different from the photosensitive resin layer mentioned in (A) in that it does not contain a compound having a photopolymerizable unsaturated double bond group.

Examples of the photocurable azide resin include azidophthalate ester of polyvinyl alcohol, azidobenzoate ester, ester of styrene-maleic anhydride copolymer, and aromatic azido alcohol such as β-(4-azidophenol)ethanol. can be given.

(D) Composition comprising an 0-quinonediazide compound: A particularly preferred 0-quinonediazide compound is an 0-naphthoquinonediazide compound, for example, U.S. Pat.
No. 18, No. 2.767, No. 092, No. 2, 772.
No. 972, No. 2.859.112, No. 2.907
．． No. 665, No. 3.046.110, No. 3.04
No. 6.111, No. 3, No. 046.115, No. 3.0
No. 46.118, No. 3.046,119, No. 3.
No. 046.120, No. 3.046.121, No. 3
, No. 046.122, No. 3.046.123, No. 3.061.430, No. 3.102.809, No. 3.106.465, No. 3, 635.709 ,
The specifications of Patent No. 3,647,443 are described in numerous publications, and these can be suitably used. Among these, O-naphthoquinonediazide sulfonic acid esters of aromatic hydroxy compounds or O-
-Naphthoquinonediazidecarboxylic acid esters and O-naphthoquinonediazide sulfonic acid amides or Q-naphthoquinonediazidecarboxylic acid amides of aromatic amine compounds are preferred.

Silicone Rubber Layer> The silicone rubber layer preferably used in the present invention is a linear or partially crosslinked polyolga/siloxane and has the following repeating units.

+5i-0+- Here, R represents an alkyl group, an aryl group, an alkenyl group, or a combination of these monovalent groups, and these include a halogen atom, an amine group, a hydroxy group, an alkoxy group, an aryloxy group, a (meth) It may have a functional group such as an acryloxy group or a thiol group. In addition, the silicone rubber may contain fine powders of inorganic substances such as silica, calcium carbonate, and titanium oxide, adhesion aids such as the silane coupling agents, titanate coupling agents, and aluminum coupling agents, and light. A polymerization initiator may also be added.

High molecular weight polymer whose main skeleton is the above-mentioned polysiloxane (
Polysiloxane, which has a molecular weight of several thousand to several hundred thousand and has a functional group at the end, is used as a raw material for silicone rubber.
This is crosslinked and cured in the following manner to obtain a silicone rubber layer. Specifically, a silane crosslinking agent represented by the following general formula is mixed into the polysiloxane having a hydroxyl group at both ends or only at one end, and if necessary, an organometallic compound such as an organotin compound is added. A catalyst such as an inorganic acid or an amine is added, and the polysiloxane and the silane crosslinking agent are heated or condensed and cured at room temperature.

RIISIX4-Fl Here, n is an integer of 1 to 3, R is the same substituent as R shown above, and X represents a substituent such as 10H1-OR"R'. Here, R2 , R3 have the same meaning as R described above, and R2 and R3 may be the same or different. Also, this represents an acetyl group.

Other organopolysiloxanes with hydroxyl groups at the ends,
The hydrogen polysiloxane crosslinking agent and, if necessary, the above-mentioned silane crosslinking agent are condensed and cured.

In addition, an addition-type silicone rubber layer crosslinked by an addition reaction between a SIH group and a -CH=CH- group is also useful.

The addition-type silicone rubber layer has the advantage that it is relatively unaffected by humidity during curing, can be crosslinked at high speed, and can easily obtain certain physical properties. In the case of a condensation type silicone rubber layer, if carboxylic acid is present in the photosensitive resin layer, curing failure may occur depending on the crosslinking agent used, whereas with an addition type silicone rubber layer, curing is sufficient even in the presence of carboxylic acid. happens. Since carboxylic acid is present in the photosensitive resin layer as described above, it is possible to easily design a photosensitive printing plate that can be developed with a developer mainly containing water or alkaline water. The addition-type silicone rubber layer used here is obtained by a reaction between a polyvalent hydrogen organopolysiloxane and a polysilosane compound having two or more -CH=CH- bonds in one molecule.
Desirably the following components: (1) 100 parts by weight of an organopolysiloxane having at least two alkenyl groups (preferably vinyl groups) directly bonded to silicon atoms in one molecule (2) At least a S i H in one molecule Organohydrodiene polysiloxane with 2 bonds 0.1-1
000 parts by weight (3) Addition catalyst A composition consisting of 0.00001 to 10 parts by weight is cured and crosslinked. Ingredients (1
The alkenyl group in ) may be located either at the end or in the middle of the molecular chain, and organic groups other than the alkenyl group include substituted or unsubstituted alkyl groups and aryl groups. Ingredients (1
) may optionally have a trace amount of hydroxyl group. Ingredient (2)
reacts with component +11 to form a silicone rubber layer, but also plays the role of imparting adhesiveness to the photosensitive resin layer.

The hydrogen group in component (2) may be located either at the end or in the middle of the molecular chain, and organic groups other than hydrogen are selected from those similar to component (11). From the viewpoint of improving ink repulsion, it is preferable that 60% or more of the groups are methyl groups.Component (1) and component (
The molecular structure of component (2) may be linear, cyclic, or branched, and it is preferred that the molecular weight of at least one of them exceeds 1,000 from the viewpoint of rubber physical properties.
The molecular weight of preferably exceeds 1,000.

Examples of component (11) include α,ω-divinylpolydimethylsiloxane, (methylvinylsiloxane)(dimethylsiloxane) copolymer having methyl groups at both ends, and component (2) such as polydivinylpolydimethylsiloxane having methyl groups at both ends. Examples include dimethylsiloxane, α,ω-dimethylpolymethylhydrodienesiloxane, (dimethylsiloxane) copolymer having methyl groups at both ends, and cyclic polymethylhydrodienesiloxane.

The addition catalyst of component (3) is arbitrarily selected from known ones, but platinum-based compounds are particularly preferred, and examples include simple platinum, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. For the purpose of controlling the curing rate of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo(methylvinyl)siloxane, carbon-carbon triple bond-containing alcohols, acetone, methyl ethyl ketone,
It is also possible to add crosslinking inhibitors such as methanol, ethanol, propylene glycol monomethyl ether.

In these compositions, an addition reaction occurs and curing begins when the three components are mixed, but the curing rate is characterized by rapidly increasing as the reaction temperature increases. Therefore, in order to lengthen the pot life of the composition until it turns into a rubber and shorten the curing time on the photosensitive resin layer, the curing conditions for the composition are set within a range that does not change the characteristics of the substrate and the photosensitive resin layer. From the viewpoint of stability of adhesive force with the photosensitive resin layer, it is preferable to maintain the temperature condition at a high temperature until completely cured.

In addition to these compositions, known adhesion promoters such as alkenyltrialkoxysilanes may be added, or organopolysiloxanes containing hydroxyl groups, silanes containing hydrolyzable functional groups (or It is also optional to add siloxane), and it is also optional to add a known filler such as silica for the purpose of improving the rubber strength.

The silicone rubber layer in the present invention serves as a printing ink repellent layer, and if the thickness is small, the ink repellency decreases,
If there are problems such as easy scratches and the thickness is large,
The thickness should be 0.5 μm because the developability will deteriorate.
m to 5 μm is suitable.

In the photosensitive lithographic printing plate that does not require dampening water as described herein, it is optional to further coat various silicone rubber layers on the silicone rubber layer, and the adhesion between the photosensitive resin layer and the silicone rubber layer is also optional. It is also optional to provide an adhesive layer between the photosensitive resin layer and the silicone rubber layer for the purpose of increasing the strength or preventing poisoning of the catalyst in the silicone rubber composition. For surface protection of silicone rubber layer,
On the silicone rubber layer, a transparent film such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, etc. may be laminated or a polymer coating may be applied.

<Development> The photosensitive lithographic printing plate that does not require dampening water according to the present invention is exposed to light through the original image, and is then treated with a developer that can dissolve or swell part or all of the photosensitive resin layer in the image area, or a developer that can swell the silicone rubber layer. Developed with a moist developer. In this case, there are cases in which the photosensitive resin layer in the image area and the silicone rubber layer thereon are removed, and cases in which only the silicone rubber layer in the image area is removed, and this can be controlled by the strength of the developer.

As the developer used in the present invention, those known as developers for photosensitive lithographic printing plates that do not require dampening water can be used. For example, aliphatic hydrocarbons (hexane, heptane,
“Isopar E, H, G” (trade name of aliphatic hydrocarbons manufactured by Esso Chemical ■, gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), or halogenated hydrocarbons (triclene, etc.) The following polar solvents can be added to the solvent, or the polar solvent itself can be used.

Alcohols (methanol, ethanol, propatool, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, 2-ethoxyethanol, carpitol monoethyl ether, carpitol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene glycol, polypropylene glycol, triethylene glycol, tetraethylene glycol) Ketones (acetone, methyl ethyl ketone) Esters (ethyl acetate, methyl lactate, lactic acid) ethyl, butyl lactate,
propylene glycol monomethyl ether acetate,
carpitol acetate, dimethyl phthalate, diethyl phthalate) Others (triethyl phosphate, tricresyl phosphate) In addition, as a developer suitable for the present invention, water may be added to the above organic solvent-based developer, or the above organic solvent may be surface activated. Solubilized in water using an alkali agent, such as carbonic acid), monoethanolamine, jetanolamine, triethanolamine, sodium silicate, potassium silicate, sodium hydroxide. , potassium hydroxide, boric acid), or in some cases, tap water or alkaline water can be used as the developer.

Furthermore, dyes such as crystal violet and astrazone red can be added to the developer to dye the image area simultaneously with development.

Development: Well-known methods can be used, for example, by rubbing the print with a developing pad containing a developer as described above, or by pouring the developer onto the printing plate and then rubbing it with a developing brush in water. As a result, the silicone rubber layer and photosensitive resin layer in the image area are removed, exposing the surface of the primer layer, which becomes the ink receiving area, or only the silicone rubber layer in the image area is removed and the photosensitive layer is exposed. The exposed portion becomes an ink receiving area (Effects of the Invention) According to the present invention, strong adhesion can be obtained between the aluminum substrate and the coating layer provided thereon, and organic solvent-based or aqueous developers can be used. It has the advantage of being able to withstand strong rubbing. Especially since it has excellent water resistance,
It has safety advantages compared to organic solvent-based developers, and is also advantageous in terms of the design of automatic processing machines.Since it can be rubbed strongly in an aqueous developer, it is possible to reproduce fine highlights and fine lines. This is an advantage.

〔Example〕

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 Commercially available polyester polyol (OD-X-105: condensate with a molecular weight of 2,000 consisting of adipic acid/ethylene glycol/butanediol: Dainippon Ink & Chemicals (
Co., Ltd.) 40.06 parts by weight, l.

6.50 parts by weight of 4-butanediol, 23.34 parts by weight of inphorone diisocyanate, and 4 parts by weight of dimethylacetamide.
Dissolved in 6.6 parts by weight, reacted at 90°C for 6 hours,
% solution of polyurethane resin liquid (1) was obtained.

Synthesis Example 2 Commercially available polyester polyol (OD-X-105: manufactured by Dainippon Ink and Chemicals Co., Ltd.) 40.06 parts by weight, 1
, 3.25 parts by weight of 4-butanediol and 23.34 parts by weight of isophorone diisocyanate were dissolved in 45.57 parts by weight of dimethylacetamide and reacted at 90°C for 6 hours. After that, isophoronediamine 1 was added as a chain extender.
．． 71 parts by weight was added and reacted at 90°C for 2 hours, resulting in a concentration of 60%
A polyurethane resin solution (n) was obtained.

(Substrate 1) An aluminum plate with a thickness of 0.30 mm was degreased by immersing it in 10% sodium hydroxide at 70°C for 60 seconds, then rinsed with running water, and soaked in 20% HNO3. Japanese wash and water wash. 5) 20% 83P, in aqueous solution, current density 2A/
The pore diameter of the anodic oxide film is 1000 A) to be anodized for 5 minutes so that the amount of the anodic oxide film is 1.2 g/m' in dm2. The substrate thus obtained is referred to as (substrate 1).

(Substrate 2> In the preparation of (Substrate 1), 20% instead of 83PO4 anodic oxidation)
2, anodic oxidation was performed for 2 minutes so that the thickness became 2.7 g/m'. Then, 25°C with 1% NaOH aqueous solution.
Open etching was performed for 20 seconds. The amount of the anodic oxide film after etching was 1.5 g/m' (the pore diameter of the anodic oxide film was 800 mm). The substrate thus obtained is referred to as (substrate 2).

(Substrate 3) In the preparation of (Substrate 1), 1 (3P port, instead of anodic oxidation, a current density of 5A/drn in a 1% Na[]H aqueous solution) was used.
In No. 2, anodic oxidation was performed for 1 minute so that the amount of the anodic oxide film was 1.2 g/m' (the pore diameter of the anodic oxide film was 800 mm). The substrate obtained in this way (substrate 3)
shall be.

(Substrate 4) (Substrate 1) was further immersed in a 2.5% aqueous solution of sodium silicate at 70° C. for 1 minute, washed with water, and dried. The substrate thus obtained is referred to as (substrate 4).

(Comparative Substrate 1) In the preparation of (Substrate 1), 20% H2 sulfur was used instead of 83PO and anodic oxidation. Anodizing was carried out in an aqueous solution for 2 minutes at a current density of 2 A/dm2 so that the amount of the anodic oxide film was 2.7 g/m'' (the pore diameter of the anodic oxide film was 1
50A>. The board obtained in this way (comparison board 1)
shall be.

(Comparative Substrate 2) In the production of (Substrate 1), anodization treatment was not performed. The substrate thus obtained is referred to as (comparative substrate 2).

<Preparation and evaluation of a photosensitive lithographic printing plate that does not require dampening water> (Example 1) A brimer solution having the following composition was applied onto (Substrate 1) and dried at 100°C for 2 minutes to give a dry weight of 4 g/m
'A primer layer was obtained.

Polyurethane resin liquid of Synthesis Example 1 10 parts by weight (1)
(60% N,N-dimethylformamide solution) 20.12 parts by weight of TlO 30 parts by weight of methyl ethyl ketone 30 parts by weight of propylene glycol monomethyl 21 rl+1 ether fluorine surfactant 0.01 part by weight On this primer layer, the following photopolymerizable photosensitive material was applied. Apply the photosensitive liquid to a dry weight of 3 g/m'',
℃ for 1 minute.

Polyurethane resin liquid of Synthesis Example 2 2.5 parts by weight (H)
(60% N,N-dimethylformamide solution) 4 mole adduct of xylene diamide 2 ethyl methacrylate Polyethylene glycol 0.4 parts by weight (molecular weight 400) Diacrylate Ethyl Michler's ketone 0.2 parts by weight Dimethylthioxanthone 0.1 part by weight Victoria Near Blue 0. 005 parts by weight BOH naphthalene sulfonate fluorine surfactant 0.01 parts by weight Methyl ethyl ketone 10 parts by weight Propylene glycol mono 1o heavy Is methyl ether Next, on the above photosensitive layer, the following silicone rubber composition liquid was applied by dry weight. So 2. 0 g/. m' and dried at 140°C for 2 minutes to obtain a silicone rubber layer.

α,ω-Divinylpolydimethyl 9 siloxane (degree of polymerization approximately 700) CH. C11. C) 13CH3CH3-
3i-0 + SiO +-1T-fSiO ←TSi
-CH.

CH3C1 (3 8 parts by weight CH3 1 part by weight Polydimethylsiloxane 0.5 parts by weight (degree of polymerization approximately 8,000) Olefin-chloroplatinic acid catalyst solution 0.2 parts by weight Inhibitor 0.15 parts by weight Isopar G 140 parts by weight (Esso Chemistry■
(manufactured by petroleum solvent) A 9 μm thick single-sided matted two-reel stretched polypropylene film was laminated on the surface of the silicone rubber layer obtained as described above so that the unmatted surface was in contact with the silicone rubber layer, A PS version without water was obtained.

A 200 lines/inch dot positive film was layered on this PS plate, and after image exposure using a commercially available vacuum printing frame, the laminated film was peeled off and
It was immersed in a solution at ℃ for 1 minute.

Thereafter, it was rubbed with a developing pad in water to obtain a lithographic printing plate (A> that does not require dampening water). The results are shown in Table 1.

(Example 2) Example 1. A lithographic printing plate (B) requiring no dampening water was obtained in exactly the same manner using (Substrate 2) instead of (Substrate 1). The results are shown in Table 1.

(Example 3) Example 1. A lithographic printing plate (C) without dampening water was obtained in exactly the same manner using (Substrate 3) instead of (Substrate 1). The results are shown in Table 1.

(Example 4) Example 1. A lithographic printing plate (D) requiring no dampening water was obtained in exactly the same manner using (Substrate 4) instead of (Substrate 1). The results are shown in Table 1.

(Example 5) On (substrate 1), a photosensitive liquid made of a photopolymerizable photosensitive material was applied to a dry weight of 3 g/m',
It was dried at 100°C for 1 minute.

Polyurethane resin liquid of Synthesis Example 2 2.5 parts by weight (n)
(60% N,N-dimethylformamide solution) 4 mole adduct of xylene diamide 2 ethyl methacrylate Polyethylene glycol 0.4 parts by weight (molecular weight 400) Diacrylate Ethyl Michler's ketone 0.2 parts by weight Dimethylthioxanthone 0.1 part by weight Victoria Near Blue 0. 005 weight 1 part BO) 1 naphthalene sulfonate fluorine surfactant 0.01 weight part Methyl ethyl ketone 10 weight parts Propylene glycol mono 10 weight 1 part Methyl ether Next, the following silicone rubber composition was applied on the above photosensitive layer. Apply the liquid to a dry weight of 2.0 g/m',
It was dried for 2 minutes at ℃ to obtain a silicone rubber layer.

α ω-Divinylpolydimethyl 9 parts by weight Siloxane (degree of polymerization approximately 700) CH3CH3CH3Cl13 CH3-3i-0+SiO') = Clove SiO - 5l
-CH3C113CH,HCH3 1 part by weight Polydimethylsiloxane 0.5 parts by weight (degree of polymerization approximately 8.000> Olefin-chloroplatinic acid catalyst solution 0.2 parts by weight Inhibitor 0.15 parts by weight Isopar 0140 parts by weight (Esso Chemical ■ (manufactured by petroleum solvent) A biaxially oriented polypropylene film having a thickness of 9 μm on one side and matted on one side was laminated on the surface of the silicone rubber layer obtained as above so that the unmatted surface was in contact with the silicone rubber layer, A PS version without water was obtained.

A 200 lines/inch dot positive film was layered on this PS plate, and after image exposure using a commercially available vacuum printing frame, the laminated film was peeled off and
It was immersed in a solution at ℃ for 1 minute.

Thereafter, the plate was rubbed with a developing pad in water to obtain a lithographic printing plate (E) that did not require dampening water. The results are shown in Table 1.

(Comparative example 1) In Example 1, instead of (substrate 1) (comparative substrate 1)
A lithographic printing plate (F) that does not require dampening water was obtained in exactly the same manner. The results are shown in Table 1.

(Comparative example 2) In Example 2, instead of (substrate 1) (comparative substrate 2)
A lithographic printing plate (G) that does not require dampening water was obtained in exactly the same manner. The results are shown in Table 1.

(Comparative example 3) In Example 5, instead of (substrate 1) (comparative substrate 2)
A lithographic printing plate (H) which did not require dampening water was obtained in exactly the same manner. The results are shown in Table 1.

Table 1) Evaluation Results From the above results, it is clear that the present invention is effective in improving adhesion.

Claims (2)

[Claims] (1) A photosensitive lithographic printing plate that does not require dampening water and is characterized in that a photosensitive layer and a silicone rubber layer are provided in this order on an aluminum substrate having an anodized film having pores with a diameter of 200 Å to 2000 Å. . (2) Photosensitivity without dampening water, characterized in that a primer layer, a photosensitive layer, and a silicone rubber layer are provided in this order on an aluminum substrate having an anodized film having pores with a diameter of 200 Å to 2000 Å. Lithographic printing plate.