JPH0485541A - Photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To improve the adhesive strength between a nonsilicone photosensitive layer and a base by providing an intermediate layer contg. a polymer having a specific repeating unit. CONSTITUTION:The intermediated layer contg. the polymer having the repeating unit expressed by general formula is provided between a base and the nonsilicone photosensitive layer of this planographic printing plate. In the formula, R<1> denotes H or CH<3>;R<2>,R<3> denote H, alkyl group or aryl group; n denotes 1 to 10 integer; m denotes 1,2 or 3. As the monomer consisting of (meth) acrylate having such silyl group in the residual ester group, tau-(meth)acryloxy propyl triethoxy silane, etc. are usable and the monomer copolymerizable with this monomer is exemplified by (methyl)methacrylate, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate provided with a non-silicone photosensitive layer, and in particular, the adhesive strength between the support and the photosensitive layer is improved, and the stiffness resistance and cleaner resistance are improved. This invention relates to a photosensitive lithographic printing plate with improved resistance to chemicals such as.

[Conventional technology]

A support for a lithographic printing plate is used with a photosensitive layer provided on one or both sides. This photosensitive layer is applied either directly by the user or by the manufacturer of the precoated printing plate. This photosensitive layer is exposed by conventional photomechanical methods, either directly from the original or through the film. after that,
It is developed with an organic solvent or an alkaline aqueous solution, and an ink-receptive image area and a hydrophilic non-image area are formed.

Therefore, the following requirements are required for the image and non-image areas of the lithographic printing plate.

That is, in the image area, (a) the photosensitive layer must firmly adhere to the support to obtain more printed matter, and (C) various chemicals used on the printing press, such as cleaners, etc. The adhesion between the photosensitive layer and the support must not be reduced even if the photosensitive layer is adhered to the support.

On the other hand, in the non-image area, (a) the photosensitive layer must be easily removed from the support by a development operation in order to obtain a hydrophilic non-image area, and (a) the photosensitive layer must be exposed in the non-image area. The supported support must have a high affinity for water.

As a method that should meet these requirements, polyvinylphosphonic acid, vinylphosphonic acid, acrylic acid and A method of undercoating a copolymer based on vinyl acetate on a support, Japanese Patent Publication No. 4
A method of undercoating a support with a diazonium compound described in Japanese Patent No. 5-16603 is known.

However, even with this method, contamination is difficult to occur because the photosensitive layer in the non-image area is easily removed during development (
Moreover, since the adhesive force between the support and the photosensitive layer is strong, a photosensitive lithographic printing plate having high stiffness resistance and high resistance to various chemicals has not been obtained.

[Problem B to be Solved by the Invention] The purpose of the present invention is to produce a high-performance printing plate that has excellent rigidity, resistance to various chemicals, developability, etc. required in the field, is highly hydrophilic, and is free from contamination. It is an object of the present invention to provide a photosensitive lithographic printing plate that is difficult to use. In particular, the adhesive strength between the support and the photosensitive layer is improved, the printing durability is high even under the high speed and harsh printing conditions of rotary offset printing presses, and the resistance to chemicals such as cleaners is greatly improved. The purpose is to provide lithographic printing plates.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by providing an intermediate layer containing a polymer having a specific repeating unit between the support and the non-silicone photosensitive layer. The present invention has been completed based on this discovery.

That is, the present invention provides a photosensitive lithographic printing plate comprising a non-silicone photosensitive layer on a support, in which a polymer having a repeating unit represented by the following general formula is provided between the support and the non-silicone photosensitive layer. The present invention provides a photosensitive lithographic printing plate characterized by being provided with an intermediate layer containing coalescence.

[In the formula, R': H or CHl R'', R3: H, alkyl group or aryl group n: 1-
Integer m of 10: 1.2 or 3. ] Hereinafter, the present invention will be explained in detail step by step.

A suitable support for the photosensitive lithographic printing plate of the invention is a dimensionally stable plate. Such dimensionally stable plate-like materials include those conventionally used as supports for printing plates, and they can be suitably used in the present invention. Such supports include paper, paper laminated with plastics (e.g., polyethylene, polypropylene, polystyrene, etc.), plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate. , cellulose triacetate, cellulose propionate,
Plastic films such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above are included. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive.

Particularly preferred as a support for use in the present invention is a roughened aluminum plate, which can be manufactured in a variety of ways. For example, wire brush graining, brush graining in which the surface is roughened with a nylon brush while pouring a slurry of abrasive particles, ball graining,
The surface is grained by chemical graining, electrolytic graining, or composite graining that combines these roughening methods. Next, as necessary, sulfuric acid, phosphoric acid, oxalic acid, borium M
It is preferable to perform anodization in chromic acid, sulfamic acid, or a mixed acid thereof using a direct current or alternating current power source to form a strong passive film on the aluminum surface. Such a passive film itself makes the aluminum surface hydrophilic, but if necessary, it can be further treated as described in U.S. Pat. No. 2,714,066 and U.S. Pat. No. 3,181,461. Silicate treatments (sodium silicate, potassium silicate), potassium fluorozirconate treatments as described in U.S. Pat. No. 2,946,638, U.S. Pat.
．． 201,247, polyacrylic acid treatment as described in German Patent No. LO9L433, German Patent No. 1, . 1
34,093 specification and British Patent No. 1.230,447
The polyvinylphosphonic acid treatment described in the specification of
The phosphonic acid treatment described in Japanese Patent Publication No. 44-6409, the phytic acid treatment described in U.S. Pat. The hydrophilic treatment may be performed by a composite treatment using a hydrophilic organic polymer compound and a divalent metal as described in each publication, or by undercoating with a water-soluble polymer having a sulfonic acid group. Other hydrophilic treatment methods include silicate electrodeposition as described in US Pat. No. 3,658,662.

The most preferred aluminum support used herein is an aluminum plate that has been roughened, provided with an anodized coating, and then subjected to silicate treatment.

An intermediate layer containing a polymer having repeating units represented by the following general formula is provided on the support treated as described above.

(R3)3-1,1 [In the formula, R': H or CH3 R", R": H, alkyl group or aryl group n: 1-
Integer m of 10: 1.2 or 3. ] The polymer having the repeating unit represented by the above general formula is an acrylic silicone resin, and this acrylic silicone resin contains a monomer consisting of a (meth)acrylic acid ester having a silyl group represented by the following general formula in the ester residue, It can be obtained by copolymerization or graft polymerization with other monomers by a known method.

p+ (R3) 3-11 (The meanings of R', R2, Rff, n, and m are the same as above.) As a monomer consisting of a (meth)acrylic acid ester having such a silyl group in the ester residue, , especially r-(meth)acryloxypropyltrimethoxysilane, γ-(
Meta)acryloxypropyltriethoxysilane is preferred, and in addition to this, β-(meth)acryloxyethyltrimethoxysilane, β-(meth)acryloxyethyltriethoxysilane, β-(meth)acryloxyethylmethyldimethoxysilane, β-(meth)acryloxyethylmethyljethoxysilane, β-(meth)acryloxypropyltrimethoxysilane, β-(meth)acryloxypropyltriethoxysilane, T(meth)acryloxyethyltrimethoxysilane, r- Examples include monomers such as (meth)acryloxyethyltriethoxysilane.

Examples of monomers copolymerizable with the above-mentioned (meth)acrylic acid ester monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, acrylamide, N-butylacrylamide, and styrene. , vinyl acetate, etc.

The proportion of the repeating unit based on a monomer other than (meth)acrylic acid having a silyl group as an ester residue in the copolymer is preferably about 10 to 98% by weight.

Graft polymerization can be carried out, for example, by the following method.

(1) A method of polymerizing other polymers using a polymer having a polymerization initiating group in the backbone polymer as an initiator.

As the polymerization initiating group in the backbone polymer, a halogen group, a ketone group, a peroxide group, a diazo group, etc. are selected.

(2) A method of polymerizing in the presence of a backbone polymer and using a chain transfer reaction to the polymer.

In graft polymerization by chain transfer, the larger the chain transfer constant of the backbone polymer, the better the grafting, so for example, -3H is added to the backbone polymer.

It is preferable to introduce it.

(3) A method using a polymerization reaction between a polymer having a functional group in its side chain and a polymer having a functional group at its end.

Combinations of functional groups include hydrogen donating groups (e.g. -
0H1-5H1-NPIZ, -COOH1CO3H,
A combination of -CONH2, -3O□N1 (z, >NOH, etc.) and a hydrogen accepting group (eg, -N=C=O1 CH=CHz, c=cti, c=N, etc.) is preferred.

Any method can be used to apply the intermediate layer containing the acrylic silicone resin, such as coating with a wheeler coating machine, roll coater coating machine, barcoder coating machine, etc., or dipping treatment. .

The above acrylic silicone resin was diluted with an organic solvent and O.
An acrylic silicone resin coating solution containing 02 to 4.0% by weight is prepared, and after coating, the coating solution is dried with hot air at 60 to 110°C for 30 to 240 seconds to form an intermediate layer made of an acrylic silicone resin.

The dry coating amount of acrylic silicone resin is 0.1mg/m
The range is preferably from 2 to 1000 mg/m'', and particularly preferably from 0.5 to 500 gng/m''.

If the dry coating amount is less than 0.1 mg/m'', the stiffness resistance and resistance to chemicals such as cleaners will not be improved, and on the other hand, if it is more than 1000 mg/m2, it will become easily stained.

A non-silicone photosensitive layer is provided on the intermediate layer provided on the lithographic printing plate support thus obtained. Specific examples of the non-silicone photosensitive layer used in the present invention are shown below.

(A) Photosensitive layer consisting of o-quinonediazide compound:
Particularly preferred 0-quinonediazide compounds are 0-naphthoquinonediazide compounds, such as U.S. Pat.
6.118, 2,767.092, 2,77
No. 2.972, No. 2,859.112, No. 2.9
No. 07,665, No. 3,046.110, No. 3.
No. 046,111, No. 3.046,115, No. 3
, 046,118, 3,046.119, 3,046.120, 3,046.121, 3.046,122, 3.046,123 ,
3,061,430, 3,102,809, 3,106.465, 3,635.709
No. 3,647,443, and many other publications, which can be suitably used. Among these, 0-naphthoquinonediazide sulfonic acid ester or 0-naphthoquinonediazidecarboxylic acid ester of an aromatic hydroxy compound, and 0-naphthoquinonediazide sulfonic acid amide or 0-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound are particularly preferred. , especially U.S. Pat. No. 3,635,70
No. 9 describes a condensate of pyrogallol and acetone subjected to ester reaction with 0-naphthoquinone diazide sulfonic acid, and U.S. Pat. O-naphthoquinonediazide sulfonic acid or O-naphthoquinonediazidecarboxylic acid is ester-reacted with a polyester having or a copolymer of this and other copolymerizable monomers with 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid, as described in U.S. Pat. No. 3,759,711. A very good example is a copolymer of p-aminostyrene and another copolymerizable monomer, such as the one described above, which is subjected to an amide reaction with 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid.

Although these 0-quinonediazide compounds can be used alone, it is preferable to use them in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak-type phenolic resins, and specifically include phenol formaldehyde resins, 0-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. Furthermore, as described in U.S. Pat. No. 4,123,279, in addition to the above-mentioned phenolic resins, phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin can be used. It is even more preferable to use a condensate of formaldehyde and formaldehyde together. The alkali-soluble resin has an amount of about 50 to about 8 based on the total weight of the composition constituting the photosensitive layer.
It can be contained in an amount of 5% by weight, more preferably 60 to 80% by weight.

(B) Photosensitive layer consisting of diazo resin and binder: As a negative-acting photosensitive diazo compound, U.S. Pat.
Diphenylamine, which is a reaction product of a diazonium salt disclosed in the specifications of No. 63,631 and No. 2,667.415, and an organic condensing agent containing a reactive carbonyl group such as an aldol or an acetal. A condensation product of p-diazonium salt and formaldehyde (so-called photosensitive diazo resin) is preferably used. Other useful condensed diazo compounds are disclosed in Japanese Patent Publication No. 49-48001 and Japanese Patent Publication No. 49-48001.
It is disclosed in publications such as No. 45322 and No. 49-45323. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts and can therefore be coated from aqueous solution. Further, these water-soluble diazo compounds are reacted with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups, or both by the method disclosed in Japanese Patent Publication No. 47-1167, The reaction product, a substantially water-insoluble photosensitive diazo resin, can also be used.

In addition, these water-soluble diazo compounds were
It can also be used as a reaction product with hexafluorophosphate or tetrafluoroborate as described in Japanese Patent No. 1031.

Examples of substantially water-insoluble photosensitive diazo resins that are reaction products of compounds having phenonylic hydroxyl groups include hydroxybenzophenone, 4,4-bis((4'-hydroxyphenyl)pentanoic acid, resorcinol, or Examples include diphenolic acids such as resorcinol,
These may further have a substituent. Hydroxybenzophenone includes 2.4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2.
Included are 2'-dihydroxy-44'-dimethoxybenzophenone or 2,2',4,4-tetrahydroxybenzophenone. Preferred sulfonic acids include aromatic sulfonic acids such as sulfonic acids such as benzene, toluene, xylene, naphthalene, phenol, naphthol, and benzophenone, or soluble salts thereof, such as ammonium salts and alkali metal salts. . Sulfonic acid group-containing compounds may generally be substituted with lower alkyl, nitro groups, halo groups, and/or another sulfonic acid group. Preferred examples of such compounds include benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, sodium benzenesulfonate, naphthalene-2-sulfonic acid, 1-naphthol-2-( or 4)-
Sulfonic acid, 2,4-dinitro-1-naphthol-7-
Sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 4-dodecylbenzenesulfonic acid, sodium m-(p'-anilinophenylazo)benzenesulfonate, alizarinsulfonic acid, 0-toluidine to m- Examples include sulfonic acid and ethanesulfonic acid.

Sulfonic esters of alcohols and their salts are also useful. Such compounds are usually readily available as anionic surfactants. Specific examples thereof include ammonium salts or alkali metal salts such as lauryl sulfate, alkylaryl sulfate, p-nonylphenyl sulfate, 2-phenylethyl sulfate, and isooctylphenoxyjethoxyethyl sulfate.

These substantially water-insoluble photosensitive diazo resins are isolated as a precipitate by mixing the water-soluble photosensitive diazo resin and an aqueous solution of the aromatic or aliphatic compound, preferably in approximately equal amounts. It will be done.

Also preferred are the diazo resins described in British Patent No. 1,312,925.

Also preferred are alkali-soluble diazo resins such as those described in JP-A-2-29650.

The most preferred diazo resin is 2-methoxy-4-condensate of p-diazodiphenylamine and formaldehyde.
Hydroxy-5-benzoylbenzene sulfonate.

The appropriate content of the diazo resin in the photosensitive layer is 5 to 50% by weight. As the amount of diazo resin decreases, photosensitivity naturally increases, but stability over time decreases. The optimum amount of diazo resin is about 8 to 20 weight percent.

On the other hand, various polymer compounds can be used as the binder, but in the present invention, hydroxy, amino,
Carboxylic acids, amides, sulfonamides, activated methylene,
Those containing groups such as thioalcohol and epoxy are desirable. Such preferred binders include those described in British Patent Nos.
350,521, British Patent Box L 460,978 and U.S. Patent Box 4,123.
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit as described in each specification of U.S. Patent No. 3,751.257, and polyamide resins described in U.S. Pat. , phenolic resins and polyvinyl acetal resins such as polyvinyl formal resins, polyvinyl butyral resins, as described in British Patent No. 1.074,392, US Pat. No. 3,660,0
Linear polyurethane resins, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, polymers containing amino groups such as polyaminostyrene and polyamino(meth)actolate, as described in No. 97. Cellulose derivatives such as cellulose acetate, cellulose alkyl ether, and cellulose acetate phthalate, JP-A-61-26704
2, 6258242, and 61-128123; polyurethane resins described in JP-A-62-1.23453 and JP-A-62-123452; is included.

(C) Azide compound and binder (photosensitive layer consisting of a polymer compound) For example, British Patent No. 1,235,281, British Patent No. 1.49
In addition to the compositions comprising an azide compound and a water-soluble or alkali-soluble polymer compound described in the specification of No. 5,861 and the publications of JP-A-51-32331 and JP-A-51-36128, Kaisho 50-5102, same 50
-84302, 50-84303, 53-12
Included are compositions consisting of a polymer containing an azide group and a polymer compound as a binder, which are described in various publications such as No. 984.

(D) Other photosensitive resin layers For example, polyester compounds disclosed in JP-A-52-96696, British Patent No. 112,277, British Patent No. 1,313,390, British Patent No. 1,341,004 Polyvinyl cinnamate resins described in the specifications of U.S. Patent No. 4,072,528 and U.S. Patent No. 4,072,527 Polymerizable photopolymer compositions are included. or,
This also includes the use of the electrophotographic light-sensitive material disclosed in JP-A-60-107042.

Various additives can be further added to the photosensitive layers (A) to (D). For example, alkyl ethers (e.g., ethyl cellulose, methyl cellulose) and fluorine-based surfactants to improve coating properties, plasticizers (e.g., tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol), acridine dye, cyanine dye, styryl dye, triphenyl as a coloring substance to visualize the image area after development. Pigments such as methane dyes and phthalocyanines, and other stabilizing agents (phosphoric acid,
Phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid, benzenesulfonic acid, toluenesulfonic acid, malic acid, dipicolinic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers combination, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-
Methyl-pyrazolone sulfonate, 2-phosphonobutanetricarboxylic acid-1, 24.1-phosphonoethanetricarboxylic acid-122,1-hydroxyethane-1, and agedisulfonic acid) can be added. The amount of these additives added varies depending on the purpose for which they are used, but is generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer.

The coating amount of the photosensitive composition in the present invention is preferably 0.1 to 7 g/m2 as solid content, more preferably 0.5 g/m2.
~5g/m2. For these photosensitive layers, if necessary,
An acrylic silicone resin used for the intermediate layer may be added. The amount of this acrylic silicone resin added varies depending on the type of photosensitive composition, but is suitably 0.01 to 10% by weight, preferably 0.01 to 10% by weight based on the total solid content of the photosensitive layer.
．． 05 to 5% by weight.

The above photosensitive composition is dissolved in a suitable solvent and applied onto a support. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, -methoxy 2
-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol,
Examples include isopropanol and diethylene glycol dimethyl ether, and these solvents can be used alone or in combination.

The solid content concentration in the solution is usually 2 to 50% by weight.

Conventionally known methods for applying the photosensitive composition solution onto the aluminum plate include roll coating,
Methods such as bar coating, spray coating, curtain coating, and spin coating can be used.

The surface of the photosensitive layer provided as described above was prepared in accordance with Japanese Patent Application Laid-open No. 125805 (1973) and Japanese Patent Publication No. 125805, in order to shorten the evacuation time during contact exposure using a vacuum printing frame and to prevent blurring. A method of providing a matte layer as described in Japanese Patent Publication No. 57-6582 and Japanese Patent Publication No. 61-28986, a method of heat-sealing solid powder as described in Japanese Patent Publication No. 62-62337, etc. can be given.

As a plate-making method for producing a lithographic printing plate from the photosensitive lithographic printing plate of the present invention, a conventional method can be used as is. That is, exposure through a transparent original having a line image and/or halftone image and subsequent treatment with a developer removes the photosensitive layer in the non-image areas. Suitable light sources used during exposure include mercury lamps, xenon lamps,
Chemical lamps, metal halide lamps, strobes, etc. are used. Further, as a developer, an appropriate developer may be used depending on the composition of the photosensitive layer. For example, for a photosensitive layer consisting of a diazo compound and an organic polymer binder,
U.S. Patent No. 3,475,171, U.S. Patent No. 3,669,6
An aqueous alkaline developer described in No. 60, No. 4,186,006, etc. is used.

[Effects of the Invention] The photosensitive lithographic printing plate of the present invention has excellent rigidity, resistance to various chemicals, developability, etc. required in the field for high-performance printing plates, and is highly hydrophilic and resistant to contamination. In particular, the adhesion between the support and the photosensitive layer is improved, it has high printing durability even under the high speed and harsh printing conditions of rotary offset printing presses, and it has significantly improved resistance to chemicals such as cleaners. can.

<Examples> Hereinafter, the present invention will be described in detail based on Examples, but the embodiments of the present invention are not limited thereby.

The percentages in the examples are by weight unless otherwise specified.

Synthesis Example 1 (Synthesis of Resin Composition 1 for Intermediate Layer) Polyurethane "Sunbren LQ-39" manufactured by Sanyo Chemical Industries, Ltd.
0” (methyl ethyl ketone/isopropyl alcohol-
Solution 7 (solid content 42% by weight dissolved in 2F 1% by weight solvent)
1.4 g was heated to about 80°C, and monomers and a thermal polymerization initiator having the following composition were added dropwise over about 30 minutes.

(1) Methyl methacrylate 30g (2)
T-methacryloxypropyltriethoxysilane 18g (3) 2.2
'-Azobis(2,4-dimethylvaleronitrile) 1.80mg was added dropwise, heated at 80°C for about 2 hours, 180mg of azobis(2°4-dimethylvaleronitrile) was added, and further heated to 80°C.
The mixture was heated for 3 hours to obtain intermediate layer resin composition 1.

Synthesis Example 2 (Synthesis of Resin Composition 2 for Intermediate Layer) The following acrylic resin copolymer, the synthesis method of which is described in JP-A-51-99810, was dissolved in 60.4 g of methyl ethyl ketone. Next, γ-glycidoxypropyltrimethoxysilane 2.3
After adding 6 g, the mixture was heated at 80°C for 2 hours to obtain intermediate layer resin composition 2.

Example 1 Aluminum plate with a thickness of 0.24111I (JIS A
1050 material) in a 10% aqueous sodium hydroxide solution.
After degreasing/cleaning was performed by immersion at °C for 20 seconds, it was washed with water and then neutralized with a 10% nitric acid aqueous solution. After washing with water, particle size is 10-80 μm, average 301! A rotating nylon brush (thickness 480 μm, number of rotations 30 Orpm) was used as an abrasive using a 20% suspension of Bamisu m in water as an abrasive.
The surface was sand-grained. The surface roughness (center line average roughness) at this time was 0.5 μm. After washing with water, etching was carried out by immersing it in a 10% aqueous solution of caustic soda heated to 70°C for 12 seconds so that the amount of aluminum dissolved was 6 g/m. After washing with water, it was immersed in a 10% aqueous solution of nitric acid at room temperature for 12 seconds. It was soaked for a minute to neutralize it and thoroughly washed with water.

Next, an electrolytic surface roughening treatment was performed using an aqueous nitric acid solution having a concentration of 9 g/2 as an electrolyte and an alternating waveform current described in JP-A-51-152302. The electrolytic conditions were a frequency of 60Hz,
Electrolytic surface roughening treatment was performed for 10 seconds at an anode current density of 40 A/dra''.Then, the smut generated by the electrolytic surface roughening treatment was immersed in a 20% sulfuric acid aqueous solution at 60°C for 1 minute to dissolve and remove it. .

This aluminum plate was anodized using direct current in a 15% sulfuric acid aqueous solution at 30°C for 1.5 minutes at 3 A/dm so that the anodic oxide film weight was 2 g/m, and after washing with water, It was immersed in a 0% sodium silicate aqueous solution at 70°C for 30 seconds, washed with water, and dried with hot air at 100° for 60 seconds.

Subsequently, Synthesis Example 1 was applied onto the obtained aluminum support.
Intermediate layer resin composition 1 was diluted with a toluene solution to give 0.
The dry coating amount was 50% using a wheeler coater using a 2% coating solution.
12 mg/m” with hot air at 100°C.
The intermediate layer was formed by drying for 0 seconds.

A photosensitive liquid having the following composition was applied onto the thus obtained intermediate layer provided on the support and dried to provide a photosensitive layer.

The dry coating weight of the photosensitive layer was 2.0 g/m''.

Photosensitive liquid N-(4-hydroxyphenyl)methacrylamide/2
-Hydroxyethyl methacrylate/acrylonitrile/methyl methacrylate/methacrylic acid (=15:10
:30:38 near molar ratio) copolymer (average molecular weight 600
00) 5.0g 4-diazodiphenylamine and formaldehyde condensate hexafluorophosphate 0.5g phosphorous acid
0.05 g Victoria Pure Blue BOH (manufactured by Odogaya Chemical Co., Ltd.) 0.1. g2-Methoxyethanol 100g The photosensitive lithographic printing plate thus prepared was exposed through a negative image film using a metal halide lamp as a light source, and then developed with a standard solution of negative PS plate developer DN-3C manufactured by Fuji Photo Film Co., Ltd. , and further gummed to make a lithographic printing plate.

After 30 minutes, ink (manufactured by Toyo Ink - eb King)
ink) and soaking water (EU-3100 manufactured by Fuji Photo Film)
Using Komori Printing Co., Ltd.'s offset rotary press (model system 18 L R-418), the standard printing pressure was applied to rough paper made by Shin'etsu Pulp ■ at a speed of 40,000 sheets/hour. Printed. The printing life of the lithographic printing plate thus obtained was 120,000 sheets (hereinafter referred to as printing durability 120,000 sheets).

In addition, after every 10,000 sheets were printed, the printing press was stopped, and plate cleaner CN-4 manufactured by Fuji Photo Film ■ was applied to the image area with a sponge, and after 1 minute, it was wiped with water.

In this way, we investigated the resistance of the image area to cleaners and found that it was possible to print up to 100,000 sheets (
(hereinafter referred to as cleaner suitability 100,000 sheets).

Example 2 The surface of an aluminum plate was roughened and anodized in the same manner as in Example 1, and then treated with an aqueous sodium silicate solution. Intermediate layer resin composition 2 of Synthesis Example 2 was diluted with a toluene solution to 0.2
% coating liquid with a wheeler coating machine with a dry coating amount of 5Qm.
g/m” and apply it to 120 g/m with hot air at 100°C.
After drying for a few seconds, an intermediate layer was formed.

After coating the photosensitive layer, the process described in Example 1 was repeated.

The printing durability was 120,000 sheets. Further, the suitability for cleaning was 100,000 sheets.

Example 3 The surface of an aluminum plate was roughened and anodized in the same manner as in Example 1, and then treated with an aqueous sodium silicate solution. On the thus obtained aluminum support, Synthesis Example 1
The dry coating amount of intermediate layer resin composition 1 was 500 vag/
An intermediate layer was formed by applying the coating to a thickness of 100 m''.

After coating the photosensitive layer, the process described in Example 1 was repeated.

The printing durability was 120,000 sheets. Further, the suitability for cleaning was 100,000 sheets.

In Examples 1 to 3 above, the case of a photosensitive layer made of a diazo resin and a binder was shown, but a photosensitive layer made of an 0-quinonediazide compound, a photosensitive layer made of an azide compound and a binder, and a photosensitive layer made of a photopolymerizable photopolymer composition were used. A similar effect was obtained in the case of the photosensitive layer.

Comparative Example 1 The surface of an aluminum plate was roughened and anodized in the same manner as in Example 1, and then treated with an aqueous sodium silicate solution. Thereafter, no intermediate layer was provided on the resulting aluminum support.

After coating the photosensitive layer, the process described in Example 1 was repeated.

The printing durability was 80,000 sheets. Further, the suitability for cleaning was 30,000 sheets.

Comparative Example 2 The surface of an aluminum plate was roughened and anodized in the same manner as in Example 1. After that, the obtained aluminum support was
．． It was immersed in a 0% by weight polyvinylphosphonic acid aqueous solution at 25°C for 30 seconds and then dried at 100°C. Thereafter, no intermediate layer was provided on the resulting aluminum support.

After coating the photosensitive layer, the process described in Example 1 was repeated.

The number of printing sheets was so, ooo. Further, the suitability for cleaning was 40,000 sheets.

Comparative Example 3 The surface of an aluminum plate was roughened and anodized in the same manner as in Example 1, and then treated with an aqueous sodium silicate solution. Polyacrylic acid (manufactured by Nippon Pure Chemical Industries Ltd., trade name Jurimer AC-1OL) was placed on the aluminum support thus obtained.
) was applied in a dry coating amount of 100 mg/m'' to form an intermediate layer.

After coating the photosensitive layer, the process described in Example 1 was repeated.

The printing durability was 70,000 sheets. Further, the suitability for cleaning was 30,000 sheets.

1. Indication of the case 2. Name of the invention 3. Relationship between the person making the amendment and the case 4. 1990 Patent Application No. 20 10,000 photosensitive lithographic printing plate Fuji Photo Film Co., Ltd. 5. Date system of the amendment order 6. , Column 7 of Detailed Description of the Invention of the Specification Subject to Amendment, Contents of the Amendment (1) Insert "ra" after "Kore" on page 3, line 16 of the specification.

(2) Delete "ra" before "easy" in line 18 of the same page of the same book.

(3) On page 25, line 20 of the same book, insert ``It is preferable to make it matte.Specifically'' before ``JP-A-Sho''.

Claims (1)

[Scope of Claims] In a photosensitive lithographic printing plate comprising a non-silicone photosensitive layer on a support, a polymer having a repeating unit represented by the following general formula is provided between the support and the non-silicone photosensitive layer. A photosensitive lithographic printing plate characterized by having an intermediate layer containing coalescence. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1:H or CH_3R^2, R^3:H,
Alkyl group or aryl group n: an integer of 1 to 10 m: 1
, 2 or 3. ]