JP2000231196A - Lithographic printing master plate and production of lithographic printing plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing master plate having a new base body and a hydrophilic layer while not using an aluminum metal as a supporting body, and to provide a method for the production of the printing plate using this master plate. SOLUTION: The first constitution consits of forming a petaloid alumina layer as a hydrophilic layer on a supporting body using a glass substrate, ceramic substrate or metal substrate as the base body, and applying a negative or positive photosensitive layer thereon. In the second aspect, after an image is formed on the obtd. lithographic printing master plate by irradiation of active rays or high-density energy light, and if necessary, heat treated, the image is developed with an alkaline developer, washed with water, treated with gum, and dried to produce a printing plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate used in the field of offset printing, and more particularly to a lithographic printing plate precursor having a novel substrate and a hydrophilic layer, and a method for producing a printing plate using the same.

[0002]

2. Description of the Related Art A lithographic printing plate used in the field of offset printing is a lithographic printing plate that skillfully applies the principle that oily ink and water repel and do not mix with each other. No irregularities such as letterpress or gravure. However, there is a hydrophilic non-image area and a lipophilic image area on the surface, and when water is applied to the non-image area of the plate and the ink roller is rolled to perform inking, The line portion does not accept ink due to repulsion of water and ink, and the image portion repels water and accepts ink well. In this manner, printing is performed by transferring the ink on the image portion to a medium such as paper.

As a lithographic printing plate used for the above-mentioned purpose, an image receiving plate comprising an inorganic pigment, a water-soluble resin, a water-proofing agent and the like is provided on a supporting substrate made of water-resistant paper or a plastic film. There is a direct drawing type lithographic printing plate provided with a layer. In such a plate material for direct drawing type lithographic printing,
Using a lipophilic ink on the image receiving layer to form a lipophilic image by a typewriter or handwriting, or transferring the toner image formed on the electrophotographic photoreceptor to the image receiving layer and thermally fixing it. To form an lipophilic image, or heat-transfer an image from an ink ribbon by a thermal transfer printer to form a lipophilic image and use it as an ink receiving portion. In the direct drawing type lithographic printing plate on which the lipophilic image portion is formed, the non-image portion is rendered insensitive to oil by the treatment with an etching solution, and becomes a hydrophilic portion at the time of printing. The lithographic printing plate produced in this way has been used exclusively in the field of light printing, but it has the problem that the lipophilic image area is not strong enough to withstand large numbers of copies. In addition, there is a large problem in the hydrophilic portion such as the occurrence of printing stains due to insufficient desensitization of the hydrophilic portions, and the occurrence of background stains when printing is continued due to insufficient water retention. It has been desired to develop a method for forming a non-image portion which is large and has good water retention.

Another lithographic printing plate used in offset printing is a lithographic printing plate used in newspaper printing and commercial printing.
There is an S version. The PS plate is manufactured by using an aluminum plate as a substrate, performing various hydrophilic surface treatments such as graining, anodic oxidation, and chemical conversion treatment alone or in an appropriate combination, and then applying and drying a photosensitive solution. The produced PS plate forms an image by irradiation with actinic ray light or high-density energy light, and can be processed into a printing plate through a development treatment with an alkaline developer, washing with water, gum treatment and drying. The image portion of the obtained printing plate is extremely firm and has printing durability, and the non-image portion is a satisfactory printing plate with excellent hydrophilicity and water retention. However, it is a multi-energy consuming material, such as using aluminum, which is called a lump of electricity, and using a huge amount of electricity for a series of hydrophilizing substrate treatments such as anodic oxidation. There has been a demand for a substrate having hydrophilicity and water retention and a hydrophilizing system.

[0005] On the other hand, it is known to provide a petal-like alumina layer on a glass substrate. Ce
ram. Soc. Japan, Vol. 103, no.
6, 582-585 (1995). , Minami Tsutomu, Pro
c. ofXVII, Inter. Congress o
n Glass, Vol. 4,445-449 (Bei
jing, China, 1995). , Minami Tsutomu, New
Glass, Vol. 12, No. 2,42-45
(1996). , Minami Tsutomu et al., Sol-Gel Optic
s IV, Proc. of SPIE, Vol. 313
6, 168-175 (San Diego, USA, 1)
997). J. Minamitsuto et al. Am. Ceram. So
c. , Vol. 80, no. 4,1040-42 (19
97). J. Minamitsuto et al. Am. Ceram. Soc. ,
Vol. 80, no. 12, 3213-16 (199
7). Minami Tsutomu et al., Surface Technology, Vol. 48, no. 3,
58-63 (1997). JP-A-9-202,649
Nos. 9-202,650 and 9-202,651 disclose a petal-like alumina layer and a method for forming the same. The structure in which the petal-like alumina layer is provided on the glass substrate or the structure in which the super-water-repellent layer is further provided thereon is excellent in the underlayer film of the functional thin film or the reflection reducing film, and has excellent heat resistance and weather resistance. It has been shown that it can be used as a water-repellent, oil-repellent antifouling film and a hydrophilic film having a high antifogging function for vehicles, ships, aviation, various building materials, building materials and the like. As described above, the petal-like alumina layer provided on the substrate shows super water repellency, but it has not been known that it is useful as a hydrophilic layer of a lithographic printing plate in printing.

[0006]

Accordingly, a first object of the present invention is to provide a lithographic printing plate precursor using a glass substrate, a ceramic substrate or a metal substrate as a substrate. A second object of the present invention is to provide a lithographic printing plate precursor using a petal-like alumina layer as a hydrophilic layer of a printing plate. Further, a third object of the present invention is to provide a negative or positive photosensitive layer using a petal-like alumina layer as a hydrophilic layer of a substrate and using actinic rays or high-density energy light as a light source for image writing. To provide a lithographic printing plate precursor. A fourth object of the present invention is to provide a method for producing a printing plate using the lithographic printing plate precursor according to the present invention.

[0007]

Means for Solving the Problems The present inventors have found that the unique structure of the petal-like alumina layer has high hydrophilicity and is useful not only as a hydrophilic layer of a lithographic printing plate but also in actual printing. The present inventors have found that since the water retention is extremely high, it is possible to form a hydrophilic layer of an excellent lithographic printing plate, and have reached the present invention.

That is, a first constitution of the present invention is a lithographic printing plate precursor comprising a petal-like alumina film formed on a substrate, and a photosensitive ink receiving layer provided on the petal-like alumina film. It is. Further, the configuration of the present invention, the petal-like alumina film, the alumina film formed by applying a coating solution comprising at least an aluminum alkoxide and a stabilizer, and then drying and heat-treating the formed film, It is a lithographic printing plate precursor that is a petal-shaped alumina film obtained by hot water treatment or heat steam treatment, dried, and fired. Furthermore,
The composition of the present invention uses the above-described photosensitive ink-receiving layer, a coating solution containing a photosensitive composition for a negative or positive lithographic printing plate capable of utilizing actinic light or high-density energy light as a light source. And a lithographic printing plate precursor coated and dried on a petal-like alumina layer provided on a substrate. Furthermore, a configuration of the present invention is a lithographic printing plate precursor in which the base is a glass substrate, a ceramic substrate, or a metal substrate.

In the second aspect of the present invention, the lithographic printing plate precursor according to the first aspect of the present invention is used to form an image by irradiation with actinic rays or high-density energy light and, if necessary, heat-treat it. Thereafter, a printing plate preparation method is characterized in that a printing plate is obtained by passing through a development treatment with an alkaline developer, washing with water, gum treatment and drying.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The lithographic printing plate precursor according to the present invention is characterized in that a petal-like alumina layer is first provided on a substrate. As the substrate that can be used in the present invention,
In consideration of use as a lithographic printing plate, not only a glass substrate but also a ceramic substrate or preferably a glass substrate having a thickness of 1 mm or less, more preferably 0.5 mm or less, an iron plate, a stainless steel plate, a galvanized steel plate, and a nickel-plated steel plate Alternatively, a thin metal substrate such as a chromium-plated steel plate which does not undergo a change such as a phase change under heating and firing conditions at 300 ° C. or higher is selected and used.

The lithographic printing plate precursor according to the present invention is produced by providing a petal-like alumina layer on the above substrate. As a specific method of providing a petal-like alumina layer on a substrate, an amorphous liquid formed by applying a coating solution comprising at least an aluminum alkoxide and a stabilizer on a substrate, and then drying and heat-treating the formed film. This can be achieved by subjecting the alumina film to hot water treatment or hot steam treatment, followed by drying and firing.

The aluminum alkoxide which can be used in the present invention includes, for example, aluminum ethoxide, aluminum isopropoxide, aluminum-n
-Butoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, aluminum acetylacetonate and the like.

Specific examples of the stabilizer used in the present invention include 1,3-diketones (β-diketones) such as acetylacetone, dipyrroylmethane, trifluoroacetylacetone and hexafluoroacetylacetone.
Compounds and / or methyl acetoacetate, ethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, iso-butyl acetoacetate, 2-methoxyethyl acetoacetate, Methyl 2-keto-n-valerate, 3
Β-ketoester compounds such as methyl-methyl-2-keto-n-valerate, methyl 2-keto-capronate, and methyl 2-keto-enantiate can be mentioned. Still other stabilizers include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and stabilizers for commonly used metal alkoxides.

As a diluting solvent used in a coating solution comprising at least an aluminum alkoxide and a stabilizer, for example, methyl alcohol, ethyl alcohol, n
-Propyl alcohol, iso-propyl alcohol,
Examples thereof include butyl alcohol, ethylene glycol, ethylene glycol-mono-n-propyl ether, dimethylacetamide, methyl ethyl ketone, methyl isopropyl ketone, and the like, and a mixed solvent thereof.

As a method of preparing a coating solution, β-diketone compounds, β-diketone compounds and the like, which have the effect of preventing aluminum alkoxide from quickly reacting with moisture in the air to cause gelation and cloudiness, are prevented. Stabilizers such as ketoester compounds or alkanolamines are added, for example, in a molar ratio of 1 or more, diluted with a diluting solvent of various alcohols to a concentration that can be easily applied, for example, 10 to 20 times, and a small amount of water is further added. Thus, a coating liquid can be obtained. As a preferable mixing ratio, aluminum alkoxide: diluting solvent: stabilizer: water = 1: 10 to 100: 0.
5-2: 0-5.

The coating method for applying the coating solution on the substrate includes dipping, spin coating, nozzle flow coating, spraying, reverse coating, flexo coating, and the like.
Known coating means such as a printing method, a flow coating method, and a bar coating method can be appropriately used.

Next, the coating film is dried and heat-treated to form an amorphous alumina layer. First, the substrate on which the coating film is formed is kept at room temperature to 100 ° C. or below for several minutes.
After drying for several hours, the temperature is about 600 ° C. or less, preferably 55 ° C.
The amorphous alumina layer can be formed by firing at a temperature of 0 ° C. or lower and 300 ° C. or higher for 1 to 60 minutes.

Next, the material having the amorphous alumina layer formed on the substrate is subjected to hot water treatment or hot steam treatment. That is, by immersing a material having an amorphous alumina layer formed on a substrate in hot water of 50 to 150 ° C. for 10 seconds to 24 hours or exposing it to hot steam for 1 second or more, the surface of the amorphous alumina layer is Is subjected to peptization, and has a surface layer surface in which petal-like shapes with unique and minute pores are randomly aggregated, and can be used as a substrate for the target lithographic printing plate It is possible to obtain a structural film having unique voids and shapes.

Next, the substrate on which the petal-like structure film is formed is taken out of hot water, dried at room temperature to about 150 ° C. for 10 seconds or more, and then at a temperature range of 300 to 750 ° C. for 1 minute to 1 hour.
By firing for one hour, a desired petal-like alumina film having a strong and unique microvoid structure can be formed. The thickness of the petal-like alumina film is 1
0 nm to 10 μm is preferred. Further, the petal-like alumina film preferably has an average surface roughness Ra ′ value obtained by expanding the center line average roughness, which is 17 nm or more, and a specific surface area S _R of 1.5 or more.

The petal-like alumina layer formed on the substrate as described above may further include, if necessary, US Pat.
Nos. 4,066 and 3,181,461, silicate treatment described in U.S. Pat. No. 2,946,638, potassium fluorozirconate treatment, and U.S. Pat. No. 247, the treatment with alkyl titanate described in British Patent 1,108,559, and the treatment with German Patent 1,0.
No. 91,433, polyacrylic acid treatment,
German Patent 1,134,093 and British Patent 1,23
No. 0,447, a polyvinylphosphonic acid treatment described in JP-B-44-6,409, a phytic acid treatment described in U.S. Pat. No. 3,307,951, and the like. Treatment with a salt of a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18,291;
No. 101,651 which has been subjected to a hydrophilic treatment by undercoating of a water-soluble polymer having a sulfonic acid group, and which has been colored by an acid dye described in JP-A-60-64352. Can be subjected to a hydrophilic treatment.

Further, an undercoating may be applied on the petal-like alumina hydrophilic layer for the purpose of improving the adhesion to the photosensitive ink receiving layer, preventing stains during printing, improving the tone reproducibility of the lithographic printing plate, and the like. Examples of the compound used for the undercoat include phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, phenylphosphonic acid optionally having a substituent, naphthylphosphonic acid, and alkyl. Phosphonic acid,
Organic phosphonic acids such as glycerophosphonic acid, methylene diphosphonic acid and ethylene diphosphonic acid, organic phosphoric acids such as phenylphosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid which may have a substituent, having a substituent. Organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid, and glycerophosphinic acid; amino acids such as glycine and β-alanine;
And hydrochlorides of amines having a hydroxyl group, such as hydrochloride of triethanolamine, and JP-A-59-101,65.
Water-soluble polymers having a sulfonic acid group described in No. 1 and acid dyes described in JP-A-60-64352 are used. This undercoat layer can be provided by dissolving the above compound in water, methanol, ethanol, methyl ethyl ketone, or the like, or a mixed solvent thereof, and coating and drying the petal-like alumina hydrophilic layer. The coating amount of the undercoat layer after drying is suitably from ² to 200 mg / m ² .

The lithographic printing plate precursor according to the present invention has a structure in which a photosensitive ink receiving layer is provided on a petal-like alumina layer formed on a substrate. As the photosensitive ink receiving layer,
Structural single-layer or multi-layer, plate making method such as wet method, destructive method, one that does not require special operation other than exposure, etc. are considered. When used as a lower layer of an ink receiving layer, the petal-like alumina layer of the present invention can be suitably used as a good hydrophilic layer in any case, but preferably, a plate is made by a wet method. It is. Such a photosensitive ink receiving layer is a negative type photosensitive layer which forms an image of a printing plate by being insoluble in an alkaline developer under the action of actinic rays, and is subjected to alkaline development under the action of actinic rays. Positive type photosensitive layer that becomes soluble in liquid to form printing plate image, after receiving the action of high-density energy light, the relevant part becomes insoluble in alkaline developer and print plate image Negative type photosensitive layers to be formed, and positive type photosensitive layers which form a printing plate image after the action of high-density energy light, the corresponding portion becomes soluble in an alkaline developer. .

Representative examples of the photosensitive composition contained in the negative photosensitive layer which forms an image on a printing plate by being insoluble in an alkaline developer under the action of actinic rays used in the present invention. These include:

(1) A photosensitive composition comprising a photosensitive diazo resin and a binder resin:
There is a diazo resin typified by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and those which are insoluble in water and soluble in an organic solvent are preferable. Particularly preferred diazo resins are 4-diazodiphenylamine, 4-diazo-3
-Methyldiphenylamine, 4-diazo-4'-methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine, and formaldehyde , Paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'-
It is an organic acid salt or an inorganic acid salt of a condensate with bis (methoxymethyl) diphenyl ether or the like. As the organic acid salt, for example, methanesulfonic acid, benzenesulfonic acid,
Toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy −
4-methoxybenzophenone-5-sulfonic acid, 2,4
-Dihydroxybenzophenone, benzenephosphinic acid and the like, and as the inorganic acid, hexafluorophosphoric acid,
Tetrafulboric acid and the like. Other photosensitive diazo resins include diazo resins having a polyester group in the main chain described in JP-A-54-30121;
Also used are a diazo resin obtained by reacting a diazo compound having a hydroxyl group with a polymer having a carboxylic anhydride residue described in No. 3,538, and a diazo resin obtained by reacting a diazo compound having a hydroxyl group with a polyisocyanate compound. be able to. As the binder resin, for example, (meth) acrylic acid [hereinafter, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid. ], (Meth) acrylic acid ester copolymers, copolymers containing hydroxyalkyl (meth) acrylate and (meth) acrylonitrile having an acid value of 10 to 100 described in U.S. Pat. No. 4,123,276; Copolymers having an aromatic hydroxyl group described in JP-A-43-890, JP-B-57-51,6
No. 56 copolymers such as polymers having 2-hydroxy-3-phenoxypropyl (meth) acrylate units, epoxy resins, polyamide resins, vinyl halides, particularly polyvinyl chloride, polyvinylidene chloride, and polyvinyl acetate Polyester, formal resin, acetal resin such as butyral resin, soluble polyurethane resin sold by Goodrich Company in the United States under the trade name of Estane, polystyrene, styrene-maleic anhydride copolymer or a half ester thereof, cellulose derivative, Shellac, rosin or a modified form thereof can be used.

(2) Photosensitive composition containing photocrosslinkable resin:
As the photocrosslinkable resin, a photocrosslinkable resin having an affinity for an aqueous alkali developer is preferable.
A copolymer having a cinnamic acid group and a carboxyl group described in JP-A No. 4-15,711; a polyester resin having a phenylenediacrylic acid residue and a carboxyl group described in JP-A-60-165646; 60-203,630, a polyester resin having a phenylenediacrylic acid residue and a phenolic hydroxyl group.
No. 58, a polyester resin having a phenylenediacrylic acid residue and a sodium iminodisulfonyl group, and a polymer having an azide group and a carboxyl group in a side chain described in JP-A-59-208552 can be used. .

(3) Photosensitive composition containing addition-polymerizable unsaturated compound and photopolymerization initiator:
For example, U.S. Patent Nos. 2,760,863 and 3,062
No. 0,023, JP-A-62-121,448 and the like, there are compositions comprising an addition-polymerizable unsaturated compound having two or more terminal ethylene groups and a photopolymerization initiator. Further, as the binder resin, the binder resin described in the above (1), a copolymer having an unsaturated group in a side chain described in JP-A-61-285,449, and the like can be used.

The above-mentioned negative photosensitive composition is further added with a dye, a pigment, a stabilizer, a filler, a crosslinking agent and the like, if necessary, dissolved in an appropriate solvent, and coated on a petal-like alumina layer and dried. Thus, a negative photosensitive lithographic printing plate precursor for actinic rays of the present invention having a photosensitive layer of usually 0.5 to 5 g / m ² is obtained.

Representative examples of the photosensitive composition contained in the positive photosensitive layer, which is soluble in an alkaline developer under the action of actinic rays and forms a printing plate image, used in the present invention. Examples thereof include an o-quinonediazide compound, an acid-decomposable ether compound, and an ester compound. o
-Specific examples of the quinonediazide compound are disclosed in
-5,303, 48-63,802, 48-6
3,803, 49-38,701, 56-1,
No. 044, No. 56-1,045, Japanese Patent Publication No. 41-11
No. 222, No. 43-28, 403, No. 45-9, 61
No. 0, 49-17,481, U.S. Pat.
213, 3,046,120, 3,188,2
No. 10, 3,454, 400, 3,544, 32
No. 3, No. 3,573,917, No. 3,674,495
No. 3,785,825, British Patent 1,227,6
Nos. 02, 1,251,345 and 1,267,00
5, 1,329,888 and 1,330,932
And German Patent 854,890. Examples of the acid-decomposable compounds are described in JP-A-60-37,549 and JP-A-60-37549.
Nos. 0-10,247 and 60-3,625 can be mentioned. The present invention can be preferably applied at least to a photosensitive material in which these compounds are used alone or in combination as a photosensitive component. These photosensitive components include o-quinonediazidocarboxylic acid ester of an aromatic hydroxy compound and o-quinonediazidesulfonic acid of an aromatic amino compound or o-quinonediazidesulfonic acid.
Quinonediazidecarboxylic acid amides, and those using these o-quinonediazide compounds alone;
And an alkali-soluble resin, and the mixture is provided as a photosensitive layer.

As the alkali-soluble resin, a resin composed of a novolak type phenol resin and / or a polyvinyl phenol resin is used. Novolak resins include phenol, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol,
Aromatics such as resorcinol, pyrogallol, bisphenol, bisphenol-A, trisphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol and 2-naphthol Formaldehyde, paraformaldehyde, acetaldehyde, at least one kind of hydrocarbons under acidic catalyst
Aldehydes such as paraaldehyde, propionaldehyde, benzaldehyde, furfural and acetone,
Examples include those obtained by polycondensation with at least one aldehyde or ketone selected from ketones such as methyl ethyl ketone and methyl isobutyl ketone.

Preferred aromatic hydrocarbons of the novolak resin include phenol, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5
At least one selected from xylenol and resorcinol;
Those obtained by polycondensing a kind of phenol with at least one aldehyde selected from aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde and propionaldehyde are particularly preferably used.

As the molecular weight of the novolak resin, those having a weight average molecular weight in terms of polystyrene of 1,000 to 15,000, preferably 1,500 to 10,000 as measured by gel permeation chromatography are used.

As the polyvinyl phenol resin, o-
Hydroxystyrenes such as hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, and 2- (p-hydroxyphenyl) propylene; Two or more copolymers are included. Hydroxystyrenes have chlorine on the aromatic ring,
Halogen atom such as bromine, iodine, fluorine, etc.
4 may have a substituent such as a lower alkyl substituent. Accordingly, the polyvinyl phenol resin may have a substituent such as a halogen atom or a lower alkyl substituent having 1 to 4 carbon atoms on an aromatic ring. And a good polyvinyl phenol resin.

The polyvinyl phenol resin is usually obtained by anaerobically polymerizing hydroxystyrenes which may have a substituent alone or in combination of two or more kinds thereof in the presence of a radical polymerization initiator or a cationic polymerization initiator. Is obtained by Such a polyvinyl phenol resin may be partially hydrogenated. Further, a resin in which some OH groups of polyvinylphenols are protected with a t-butoxycarbonyl group, a pyranyl group, a furanyl group, or the like may be used. The weight average molecular weight of the polyvinyl phenol resin is 1,000 to 1
Those having a molecular weight of 00,000, preferably 1,500 to 50,000 are used.

The photosensitive layer containing the o-quinonediazide compound as a photosensitive component may further contain additives such as a dye, a plasticizer, a component for imparting printout performance, a surfactant, a dissolution adjusting agent, and a coating aid, if necessary. And dissolved in a suitable solvent,
0.5 to 5 g after coating and drying on the petal-like alumina layer
/ M ² , which is a positive-working photosensitive lithographic printing plate precursor for actinic rays of the present invention having a photosensitive layer of / m ² .

After being subjected to the action of high-density energy light used in the present invention, the relevant portion becomes insoluble in an alkaline developer and is typically contained in a negative photosensitive layer for forming a printing plate image. Examples thereof include substances that absorb light and generate heat, acid generators, acid-curable compounds or acid-crosslinkable compounds, and alkali-soluble resins.

The substance that absorbs light and generates heat is a compound that efficiently absorbs high-density energy light of a specific wavelength and generates heat, and various pigments and dyes can be selected and used.
Examples of the pigment used in the present invention include commercially available pigment and color index handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology" (CM
C Publishing, 1986), "Printing Ink Technology" (CMC
Publication, 1984) can be used. Examples of the type of the pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, and a polymer-bound dye. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments,
Carbon black or the like can be used.

These pigments may be used without surface treatment, or may be used after being subjected to a known surface treatment. Examples of the known surface treatment include a method of surface-coating a resin or wax, and a method of interfacial treatment. The method of attaching the activator, the reactive substance (for example, silane coupling agent, epoxy compound,
(Polyisocyanate etc.) may be bonded to the pigment surface. These surface treatment methods are described in "Properties and Applications of Metallic Soaps" (Koshobo), "Latest Pigment Application Technology"
(CMC Publishing, 1986), "Printing Ink Technology"
(CMC Publishing, 1984).

As the dyes used in the present invention, commercially available dyes and literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry,
Showa 45, “Color Material Engineering Handbook”, Color Material Association,
Asakura Shoten, 1989, "Technology and Market of Industrial Dyes"
Known ones described in CMC, 1983, "Chemical Handbook, Applied Chemistry", edited by The Chemical Society of Japan, published by Maruzen Shoten, 1986) can be used. Specifically, azo dyes, metal chain salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes,
Dyes such as quinone imine dye, methine dye, cyanine dye, indigo dye, quinoline dye, nitro dye, xanthene dye, thiazine dye, azine dye and oxazine dye are exemplified. Among these dyes, those that absorb infrared light or near infrared light are particularly preferred. Dyes that absorb infrared light or near infrared light include, for example,
8-125,246, 59-84,356, 5
Cyanine dyes described in JP-A Nos. 9-202,829 and 60-78,787;
Nos. 6, 58-181, 690, 58-194, 5
No. 95, etc., methine dyes described in JP-A-58-1
12,793, 58-224,793, 59-
Nos. 48,187, 59-73,996, 60-5
2,940 and 60-63,744; squarylium dyes described in JP-A-58-112,792; British Patent No. 4
Cyanine dyes described in U.S. Pat.
Near-infrared absorbers described in JP-A-56,938 can be mentioned. Further, substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924, trimethinethiapyrylium salts described in JP-A-57-142,645, and JP-A-58-181,051. 58-22
0,143, 59-41,363, 59-8
Nos. 4,248, 59-84, 249, 59-14
Nos. 6,063 and 59-146,061, pyrylium compounds described in JP-A-59-21614.
No. 6, cyanine dyes described in U.S. Pat. No. 4,283,47.
Pentamethine thiopyrylium salt described in No. 5,
Pyrylium compounds disclosed in U.S. Pat. Nos. 13,756 and 5,19,702.
The near-infrared absorbing dye described in No. 3 can also be mentioned.

Examples of the acid generator contained in the negative photosensitive layer for high-density energy light of the present invention include various diazonium salts, halogen compounds containing a trichloromethyl group, etc., thiopyrylium salts, phosphonium salts, iodonium Various onium salts such as salts, thionium salts and sulfonium salts, and complex compounds such as borates, aluminate complexes and iron-arlene complexes can be mentioned.

The acid curable compound contained in the negative photosensitive layer for high-density energy light of the present invention includes novolak resin, resol resin, unsaturated polyester resin, epoxy resin, urea resin, melamine resin, Examples include various thermosetting resins such as diallyl phthalate resin, and oligomers and polymers which are made alkali-soluble by chemically modifying these resins or copolymerizing them with alkali-water-soluble monomers.

The acid-crosslinkable compound contained in the negative photosensitive layer for high-density energy light of the present invention is a compound having two or more acid-crosslinkable substituents in the molecule. Examples of the substituent include an olefin group, an epoxy group, an acetal group, a ketal group, an aldehyde group, and an enol ether group.

The alkali-soluble resin contained in the negative photosensitive layer for high-density energy light of the present invention may be any of the alkali-soluble resins used for the negative or positive photosensitive ink receiving layer for actinic rays described above. Can be used. Preferred alkali-soluble resins include novolak resins, resol resins, and resins obtained by copolymerization of (meth) acrylic acid.

Another example which can be used as a negative photosensitive layer for forming a printing plate image after the action of the high-density energy light used in the present invention and the relevant portion becomes insoluble in an alkaline developer is formed. For example, for example,
Nos. 306,528 and 9-179,292, comprising a resin containing a diazonium group and carbon black; JP-A-9-274,317, using a quinonediazide compound; and JP-A-7-020. ,
Nos. 629, 7-271, 029 and 8-234, 4
No. 26, 9-185, 160, 9-197, 66
No. 8, 9-197, 671, 9-202, 873
No. 9-208, 925, 9-221, 652
Nos. 9-221,654 and 9-176,112
No. 9-183, 960, 9-183, 961
Nos. 9-222,731 and 9-239,945
Nos. 9-244, 226, 9-244, 233, etc. which use a heat-generating acid generator, etc., each of which is a negative photosensitive material for high density energy light according to the present invention. Can be used as a layer.

The negative photosensitive layer for high density energy light according to the present invention may further comprise a sensitizer, a plasticizer,
Add components that give printout performance, surfactants, dissolution regulators, additives such as coating aids, dissolve in a suitable solvent, apply and dry on petal-like alumina layer, usually 0.5
It is a negative photosensitive lithographic printing plate precursor for high density energy light of the present invention having a negative photosensitive layer of ５5 g / m ² .

After receiving the action of the high-density energy light used in the present invention, a representative portion contained in a positive photosensitive layer which forms a printing plate image by dissolving the relevant portion in an alkaline developing solution. Examples thereof include substances that absorb light and generate heat, acid generators, alkali-soluble resins, and acid-decomposable resins.

The substance and the acid generator that absorb light and generate heat contained in the positive photosensitive layer for high-density energy light are the same as those described above for the negative photosensitive material for high-density energy light according to the present invention. The same compounds as the substance that absorbs light and generates heat and the acid generator can be used.

As the alkali-soluble resin contained in the positive photosensitive layer for high-density energy light, any of the alkali-soluble resins used for the negative or positive photosensitive ink receiving layer for actinic rays described above may be used. Preferred examples of the alkali-soluble resin include a novolak resin, a resol resin, and a resin obtained by copolymerization of (meth) acrylic acid. Particularly preferred resins include a novolak resin and a resol resin.

Examples of the acid-decomposable resin contained in the positive photosensitive layer for high-density energy light include vinyl polymers having a graft group derived from orthocarboxylic acid esters, acetal and ketal.

Examples of the positive photosensitive layer for high-density energy light of the present invention include, for example, JP-A-7-20629, JP-A-7-271029, and JP-A-7-27129.
-220,752, 9-171,254, 9-
211,863, 9-211,864, 9-2
11,865, 9-304,931, 10-
No. 3,165, No. 10-10,735, No. 10-1
No. 0,737, No. 10-39,514, No. 10-8
No. 7,733, No. 10-123, 703, No. 10-1
No. 5,365 and the like, and any of them can be used as the positive photosensitive layer for high density energy light of the present invention.

The positive photosensitive layer for high density energy light according to the present invention may further contain a sensitizer, a plasticizer,
Add components that give printout performance, surfactants, dissolution regulators, additives such as coating aids, dissolve in a suitable solvent, apply and dry on petal-like alumina layer, usually 0.5 to
This is a positive photosensitive lithographic printing plate precursor for high-density energy light of the present invention having a positive photosensitive layer of 5 g / m ² .

The lithographic printing plate precursor according to the present invention is produced by applying each of the above-mentioned photosensitive composition coating solutions onto a petal-like alumina layer provided on a substrate by a known technique, followed by drying. Coating methods include spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating,
And a spray coating method. The negative photosensitive composition layer applied in this manner has a thickness of 40 to 15
It is dried at 0 ° C. for 30 seconds to 10 minutes using a hot air dryer, an infrared dryer, or the like.

On the negative or positive photosensitive layer used for actinic rays, it is desirable to provide a mat layer composed of protrusions provided independently of each other. The purpose of the matte layer is to improve the vacuum adhesion between the negative or positive image film and the photosensitive lithographic printing plate during contact exposure, shorten the vacuuming time, and reduce the loss of fine halftone dots during exposure due to poor adhesion. It is to prevent. As a method for applying the mat layer, there are a method of thermally fusing powdered solid powder, a method of spraying and drying polymer-containing water, and any method can be used. The mat layer is preferably composed of a substance which is dissolved in an aqueous developer substantially free of an organic solvent or which can be removed thereby.

Next, a method for producing a printing plate using the lithographic printing plate precursor of the present invention will be described.

The lithographic printing plate precursor according to the present invention is first subjected to image writing with actinic rays or high-energy rays. As the active light source that can be used in the lithographic printing plate precursor according to the invention, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like can be used. To perform image writing using actinic rays, for example, using a film on which an image has already been formed,
After the lithographic printing plate precursor for actinic light of the present invention is brought into close contact with the lithographic printing plate precursor, a necessary amount of light may be irradiated on the entire surface with an actinic light source.

The high-density energy light source that can be used in the present invention has an oscillation wavelength of 300 nm to 1 nm.
Various semiconductor lasers up to 250 nm, carbon dioxide laser (oscillation wavelength; 10.6 μm), YAG laser (oscillation wavelength; 1064 nm, SHG = 532 nm, THG = 3)
55 nm), excimer laser (oscillation wavelength; 193 nm)
308 nm / 351 nm), argon laser (oscillation wavelength: 488 nm), etc. In any case, an appropriate pigment or dye capable of absorbing a specific wavelength of the light source and causing heat or chemical reaction is added to the photosensitive layer. Can be used by To perform writing by high-density energy light, using digital image information by a computer or the like created in advance, directly irradiating the negative or positive type lithographic printing plate precursor of the present invention through a circuit from a high-density energy light source Image writing can be performed. As a device used at this time, a commercially available dedicated setter or printer can be used.

In the case of a negative type lithographic printing plate precursor for high-density energy light, the irradiation resistance with high-density energy light alone may not provide sufficient development resistance and printing resistance of the writing portion. In such a case, the image portion can be reinforced by appropriately performing a heat treatment before the development treatment. The heat treatment is performed by heating at 80 ° C. to 170 ° C. for several seconds to 5 minutes using a heat oven, an infrared heater or the like.

The lithographic printing plate precursor of the present invention, which has been subjected to image exposure and, if necessary, subjected to heat treatment, is then subjected to a developing treatment with an alkaline developing solution.

The negative aqueous alkaline developer used in the developing treatment includes, for example, sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, secondary or tertiary phosphoric acid as an alkaline agent. Sodium or ammonium salts, sodium metasilicate, sodium carbonate, inorganic alkali agents such as ammonia, mono, di, or trimethylamine, mono, di, or triethylamine;
Organic amine compounds such as mono- or diisopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine and the like are used. The content of these alkali agents in the developer is 0.005
10 to 10% by weight, preferably 0.05 to 5% by weight. If the amount is less than 0.005% by weight, the development becomes poor,
If the amount is more than 10% by weight, adverse effects such as attacking the negative-type photosensitive image forming layer are caused.

An organic solvent is added to the negative developer. Specific examples thereof include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, and butyl levulinate. , Ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methyl phenyl carbinol, n-amyl alcohol, methyl amyl alcohol, xylene, methylene dichloride, ethylene Examples thereof include dichloride and monochlorobenzene. The content of these organic solvents in the negative developer is 20% by weight or less, preferably 10% by weight or less.

Further, in the negative developer, if necessary, water-soluble sulfites such as lithium sulfite, sodium sulfite, potassium sulfite, magnesium sulfite, alkali-soluble pyrazolone compounds, alkali-soluble thiol compounds, methylresorcin, etc. Hydroxy aromatic compounds,
Water hardeners such as polyphosphates and aminopolycarboxylic acids,
Sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, N-methyl-N
-Anionic surfactants such as sodium pentadecylaminoacetate and sodium lauryl sulfate, amphoteric surfactants, antifoaming agents and the like can be used.

As the developer used in the positive developing treatment of the present invention, an alkaline aqueous solution substantially free of an organic solvent is preferable. As the alkaline agent, for example, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, water Lithium oxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate,
An aqueous solution of an inorganic alkali agent such as ammonia water or the like and an organic alkali agent such as tetraalkylammonium hydride is suitable, and the concentration thereof is 0.005 to 0.005.
It is added and used so as to be 20% by weight, preferably 0.01 to 5% by weight. In addition, the positive developer, if necessary, surfactants such as anionic activators, nonionic activators, cationic activators, amphoteric activators, fluorine activators and silicone activators, alcohols and the like. Such a water-soluble organic solvent can be added.

As the negative or positive developing solution used in the present invention, a commercially available negative or positive developing solution can be used by diluting it 1- to 200-fold in practice. It is also possible to dilute and use a developing solution for both positive and negative according to the conditions.

The development processing conditions in the present invention are as follows: the exposed lithographic printing plate precursor according to the present invention is immersed in a developing solution at a temperature of 15 ° C. to 40 ° C. for a time of 1 second to 2 minutes.
It is performed by washing with water. If necessary, the surface may be lightly rubbed.

The lithographic printing plate precursor according to the present invention after development processing is subjected to washing with water and / or treatment with a water-based desensitizing agent. Examples of the aqueous desensitizing agent include water-soluble natural polymers such as gum arabic, dextrin, and carboxymethyl cellulose; and aqueous solutions of water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid. According to the above, an acid, a surfactant and the like are added to these aqueous desensitizing agents. Then, after desensitization, it is dried and used as a printing plate for printing. In performing the plate making process, it is also effective to use an automatic developing machine or the like filled with a developing solution or a gum solution capable of simultaneously performing the developing, washing, gumming and drying steps at one time.

[0065]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Tributoxyaluminum 2
While stirring 4.3 g, 100 g of isopropyl alcohol
Add in. With further stirring, 13 g of acetoacetic acid ethyl ester was added, and the mixture was stirred at room temperature for 1 hour. Next, a mixed solution of 20 g of isopropyl alcohol and 7.2 g of water was added with stirring, and after the addition, the mixture was further stirred for 3 hours to obtain a coating solution.

An alumina sol layer was provided on a glass substrate by a dipping method in which a 2.5 × 2.5 cm pre-degreased glass plate was immersed in a coating solution and lifted. After air drying, baking was performed at 400 ° C. for 10 minutes, and then immersed in hot water at 90 ° C. for 10 minutes. After the immersion, baking was performed again at 400 ° C. for 10 minutes to form a petal-like alumina layer. It was confirmed by a 5,000 magnification electron microscope that the surface had a unique petal-like shape.

A binder resin having a weight average molecular weight of 70,000 obtained by copolymerizing 2-hydroxyethyl methacrylate: ethyl methacrylate: methacrylic acid: acrylonitrile at a ratio of 35: 30: 5: 30 was added to 10.0.
g, 1.3 g of diazo resin which is a hexafluorophosphate of a condensate of 4-diazodiphenylamine and paraformaldehyde, 0.15 g of "Victoria Pure Blue BOH; Hodogaya Chemical Industry Co., Ltd.", and 0.2 g of malic acid
And 0.05 g of Megafac F-177; manufactured by Dainippon Ink and Chemicals, Inc., and 170 g of methylcellosolve were dissolved to prepare a negative photosensitive ink receiving layer coating liquid for actinic rays.

The negative photosensitive ink receiving layer for actinic light is applied to the petal-like alumina layer on the glass substrate with a spinner and dried at 100 ° C. for 3 minutes. A negative type lithographic printing plate precursor was obtained.

A film having a character image was brought into close contact with the surface of the negative-working lithographic printing plate precursor for actinic rays of the present invention, and a 1 kW output metal halide lamp (manufactured by Iwasaki Electric Co., Ltd.) was provided at a position 1 m away from the film. Exposure was performed for 40 seconds using “Fin 1000”. Then, a 1: 3 dilution of developer ND-1 (manufactured by Polychrome Japan) at 25 ° C.
The plate was subjected to a development treatment for 1 minute, washed with water, treated with a gum solution (UG1 was diluted 2 times; manufactured by Polychrome Japan) and dried to obtain a printing plate (1).

The printing plate (1) was fixed to a metal plate with a double-sided tape and printing was performed. The printing was performed on the dampening solution NA108W (1:
After applying ink (GEOS-G Red N, manufactured by Dainippon Ink and Chemicals, Inc.) with an ink roller in the presence of 50 dilution, manufactured by Dainippon Ink and Chemicals, the character image was transferred to a rubber roller. Further, a character image was transferred from a rubber roller onto paper. By the above procedure, a printed matter of one character was obtained. In the following, printing is continued in the cycle of dampening water ⇒ inking ⇒ rubber roller transfer ⇒ paper transfer, and
00 prints were obtained. During this time, the character quality of the printed matter was good.

Example 2 3.0 g of an ester compound of naphthoquinone-1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin was placed on the petal-like alumina layer on the glass substrate obtained in Example 1. , 7.5 g of cresol-formaldehyde resin, 0.06 g of 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and "Oil Blue # 603;
Orient Chemical Industry Co., Ltd. "in 0.15 g and methylcellosolve acetate 90 g was coated with a positive photosensitive ink receiving layer coating solution for actinic ray obtained by spinner coating.
After drying at 0 ° C. for 1 minute, a positive working lithographic printing plate precursor for actinic light of the present invention was obtained.

A film having a character image was brought into close contact with the surface of the positive-working lithographic printing plate precursor for actinic rays of the present invention, and a 1 kW output metal halide lamp (manufactured by Iwasaki Electric Co., Ltd.) "Idol Exposure was performed for 40 seconds using “Fin 1000”. Then, a 1: 8 dilution of developer PD-1 (manufactured by Polychrome Japan) at 25 ° C.
The plate was subjected to a development treatment for 1 minute, washed with water, treated with a gum solution (UG1 was diluted 2 times; manufactured by Polychrome Japan) and dried to obtain a printing plate (2).

The printing plate (2) was fixed to a metal plate with a double-sided tape, and printing was performed. The printing was performed on the dampening solution NA108W (1:
After applying ink (GEOS-G Red N, manufactured by Dainippon Ink and Chemicals, Inc.) with an ink roller in the presence of 50 dilution, manufactured by Dainippon Ink and Chemicals, the character image was transferred to a rubber roller. Further, a character image was transferred from a rubber roller onto paper. By the above procedure, a printed matter of one character was obtained. In the following, printing is continued in the cycle of dampening water ⇒ inking ⇒ rubber roller transfer ⇒ paper transfer, and
00 prints were obtained. During this time, the character quality of the printed matter was good.

[Example 3] The alumina sol coating solution prepared in Example 1 was applied to a pre-degreased B4 wide size stainless steel sheet having a thickness of 0.3 mm with a wire bar of rod number # 12. After air drying, 10 at 400 ° C
After baking for 10 minutes, it was immersed in hot water at 90 ° C. for 10 minutes. After the immersion, baking was performed again at 400 ° C. for 10 minutes to form a petal-like alumina layer.

Then, the coating solution for the negative photosensitive ink receiving layer for actinic light similarly prepared in Example 1 was applied to a rod number #
6 was applied onto the petal-like alumina layer using a wire bar, and dried at 100 ° C. for 3 minutes to obtain a negative working lithographic printing plate precursor for actinic rays of the present invention. A negative image film is brought into close contact with the negative-working lithographic printing plate precursor for actinic light of the present invention, and exposed with 35 units using a printer “P-806-G; manufactured by Dainippon Screen Co., Ltd.” to obtain a developer ND1 (Polychrome Japan) 1: 3 dilution and finishing gum NF2
(Polychrome Japan Co., Ltd.) A printing plate (3) was obtained by processing at 30 ° C. for 19 seconds in an automatic developing machine PD-912P (Dainippon Screen Co., Ltd.) filled with a 1: 2 diluent. .

The printing plate (3) is transferred to a printing machine (TOKO-82).
0L; manufactured by Tokyo Aviation Instruments Co., Ltd.), and a printing test was performed. As printing conditions, printing speed; 1,000 sheets / hour, printing paper; Jujo diamond coat B4, ink; GEO
SG Red S (manufactured by Dainippon Ink and Chemicals, Inc.), fountain solution; N
A printing test of 3,000 sheets was performed under the conditions of A108W (1:50 dilution, manufactured by Dainippon Ink and Chemicals, Inc.).
The obtained 3,000 prints were good prints without any problem of quality or the like.

Example 4 92.3 g of methylcellosolve
And 4.0 g of an unsaturated polyester resin soluble in an alkaline aqueous solution, and 2.0 g of methylenebis (-N-maleimide).
0 g, 1.0 g of p-toluenesulfonic acid salt of a condensate of 4-diazophenylamine and paraformaldehyde,
0.5 g of 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and 0.1 g of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.)
g and Megafac F-144D (manufactured by Dainippon Ink and Chemicals, Inc.) were dissolved to prepare a negative photosensitive ink receiving layer coating liquid for actinic rays.

The prepared negative-type photosensitive light-sensitive ink-receiving layer coating liquid for actinic rays was applied to the petal-like alumina layer having the stainless steel plate as a substrate obtained in Example 3 using a wire bar having a rod number of # 12. And dried at 100 ° C. for 3 minutes to obtain a negative working lithographic printing plate precursor for actinic rays of the present invention.

A negative image film was brought into close contact with the negative-working lithographic printing plate precursor for actinic light of the present invention, and a printer “P-8” was used.
06-G: manufactured by Dainippon Screen Co., Ltd.] with 35 units, and developer ND1 (manufactured by Polychrome Japan)
Automatic developing machine P filled with 1: 3 dilution and finishing gum NF2 (manufactured by Polychrome Japan)
D-912P (manufactured by Dainippon Screen) at 30 ° C, 1
This was processed under the condition of 9 seconds to obtain a printing plate (4).

The printing plate (4) is transferred to a printing machine (TOKO-82).
0L; manufactured by Tokyo Aviation Instruments Co., Ltd.), and a printing test was performed. As printing conditions, printing speed; 1,000 sheets / hour, printing paper; Jujo diamond coat B4, ink; GEO
SG Red S (manufactured by Dainippon Ink and Chemicals, Inc.), fountain solution; N
A printing test of 5,000 sheets was performed under the conditions of A108W (1:50 dilution, manufactured by Dainippon Ink and Chemicals, Inc.).
The obtained 5,000 prints were good prints without any problems such as quality.

[Example 5] The coating liquid for the positive photosensitive ink receiving layer for actinic light prepared in Example 2 was applied onto the petal-like alumina layer having a stainless steel plate as a substrate obtained in Example 3 by rod number # 12. Apply using a wire bar of 120 ° C
For 1 minute to obtain a positive working lithographic printing plate precursor for actinic light of the present invention.

A positive image film was brought into close contact with the positive-working lithographic printing plate precursor for actinic light of the present invention, and a printer “P-8” was used.
06-G: manufactured by Dainippon Screen Co., Ltd. and exposed for 35 units, and developer PD1 (manufactured by Polychrome Japan)
Automatic developing machine P filled with 1: 8 dilution and finishing gum PF2 (manufactured by Polychrome Japan)
D-912P (manufactured by Dainippon Screen) at 30 ° C, 1
This was processed under the condition of 2 seconds to obtain a printing plate (5).

The printing plate (5) is transferred to a printing machine (TOKO-82).
0L; manufactured by Tokyo Aviation Instruments Co., Ltd.), and a printing test was performed. As printing conditions, printing speed; 1,000 sheets / hour, printing paper; Jujo diamond coat B4, ink; GEO
SG Red S (manufactured by Dainippon Ink and Chemicals, Inc.), fountain solution; N
A printing test of 3,000 sheets was performed under the conditions of A108W (1:50 dilution, manufactured by Dainippon Ink and Chemicals, Inc.).
The obtained 3,000 prints were good prints without any problem of quality or the like.

Example 6 The alumina sol coating solution prepared in Example 1 was applied to a pre-degreased B4 wide size 0.27 mm thick galvanized steel plate with a rod number # 12 wire bar. After air drying, baking was performed at 290 ° C. for 10 minutes, and then immersed in hot water at 90 ° C. for 10 minutes. After the immersion, baking was performed again at 290 ° C. for 10 minutes to form a petal-like alumina layer.

Next, 25 ml of methyl ethyl ketone and 1 ml of
-In a mixed solution of 20 ml of propanol, 3.0 g of UCAR phenolic resin BKS-5928 (manufactured by Union Carbide), 3.0 g of novolak resin ZH-8011 (manufactured by Dainippon Ink and Chemicals, Inc.), and IRDYE830
0.2 g of 4,4′-di-t-butyldiphenyliodonium hexafluorophosphate and 0.2 g of terephthalaldehyde are dissolved in the negative photosensitive material for high density energy light. An ink receiving layer coating solution was prepared.

The prepared coating solution for the negative photosensitive ink receiving layer for high-density energy light was applied to the petal-like alumina layer based on the galvanized iron plate using a wire numbered rod # 20 at 100 ° C. For 3 minutes to obtain a negative type lithographic printing plate precursor for high density energy light of the present invention.

The negative type lithographic plate for high density energy light of the present invention
Trend setter 3244F (Cleo)
Using an infrared laser (830 nm, 150 mJ)
/ Cm ^Two), And then heat orb
After heating at 135 ° C. for 30 seconds, the post-treatment was completed. Next
And developer PD1 (manufactured by Polychrome Japan) 1:
3.5 diluent and finishing gum PF2 (polyclo
Automatic developing machine P filled with 1: 2 diluent
D-912P (manufactured by Dainippon Screen) at 30 ° C, 1
This was processed under the condition of 5 seconds to obtain a printing plate (6).

The printing plate (6) is transferred to a printing machine (TOKO-82).
0L; manufactured by Tokyo Aviation Instruments Co., Ltd.), and a printing test was performed. As printing conditions, printing speed: 3,000 sheets / hour, printing paper: Jujo diamond coat B4, ink; GEO
SG Red S (manufactured by Dainippon Ink and Chemicals, Inc.), fountain solution; N
A printing test of 6,000 sheets was performed under the conditions of A108W (1:50 dilution, manufactured by Dainippon Ink and Chemicals, Inc.).
The obtained 6,000 prints were good prints without any problems such as quality.

Example 7 Methyl ethyl ketone 25 ml
And 20 g of 1-propanol in a mixed solution of 6.0 g of novolak resin ZH-8011 (manufactured by Dainippon Ink and Chemicals), 0.5 g of novolak resin ZH-8020 (manufactured by Dainippon Ink and Chemicals), and IRDYE830 (Manufactured by Panchim Co.) and 0.2 g of 4,4′-di-t-butyldiphenyliodonium hexafluorophosphate.
2 g and 0.2 g of diethanolamine are dissolved,
A positive photosensitive ink receiving layer coating solution for high density energy light was prepared.

The prepared coating solution for the positive-type photosensitive ink receiving layer for high-density energy light was applied to the petal-like alumina layer having the base of the galvanized iron plate obtained in Example 6 by using a wire number rod # 16. And dried at 120 ° C for 1 minute,
A positive type lithographic printing plate precursor for high density energy light of the present invention was obtained.

The positive type lithographic plate for high density energy light of the present invention
Trend setter 3244F (Cleo)
Using an infrared laser (830 nm, 150 mJ)
/ Cm ^Two), And then the developer P
D1 (Polychrome Japan) 1: 8 diluent and filter
Nothing gum PF2 (manufactured by Polychrome Japan)
Automatic developing machine PD-912P filled with 1: 2 diluent (large
Nippon Screen Co., Ltd.) at 30 ° C for 12 seconds.
To obtain a printing plate (7).

The printing plate (7) is transferred to a printing machine (TOKO-82).
0L; manufactured by Tokyo Aviation Instruments Co., Ltd.), and a printing test was performed. As printing conditions, printing speed: 3,000 sheets / hour, printing paper: Jujo diamond coat B4, ink; GEO
SG Red S (manufactured by Dainippon Ink and Chemicals, Inc.), fountain solution; N
A printing test of 6,000 sheets was performed under the conditions of A108W (1:50 dilution, manufactured by Dainippon Ink and Chemicals, Inc.).
The obtained 6,000 prints were good prints without any problems such as quality.

[0094]

According to the present invention, a petal-like alumina layer is formed as a hydrophilic layer on a support using a glass substrate, a ceramic substrate or a metal substrate as a base, and an actinic ray or high-density energy light is formed thereon as a light source for image writing. A lithographic printing plate precursor comprising a negative or positive photosensitive layer to be used is prepared, an image is formed on the resulting lithographic printing plate precursor by irradiation with actinic light or high-density energy light, and heating is performed if necessary. After processing, development processing with an alkaline developer, washing with water,
After gum treatment and drying, a new and good printing plate having a petal-like alumina layer as a hydrophilic layer on the substrate was obtained.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Seiji Tadanaga 6-998-3 Nakamozu Toricho, Sakai City, Osaka (72) Inventor Atsunori Matsuda 12-5 Midorigaoka Nakamachi, Kawachinagano City, Osaka F-term (reference) 2H025 AA12 AA13 AB03 AC01 AC08 AD01 AD03 BA03 BC13 BC31 CC11 DA18 DA19 DA36 DA40 FA12 FA17 FA29 FA39 2H084 AA30 AA32 BB01 BB13 CC05 2H096 AA06 BA05 BA09 CA03 CA20 EA02 EA04 FA01 GA08

Claims (9)

[Claims] A petal-like alumina film formed on a substrate;
A lithographic printing plate precursor comprising a photosensitive ink receiving layer provided on the petal-like alumina film. 2. The petal-like alumina film according to claim 1,
An alumina film formed by applying a coating solution comprising at least an aluminum alkoxide and a stabilizer and then drying and heat-treating the formed film is subjected to hot water treatment or heated steam treatment, followed by drying and firing. The lithographic printing plate precursor according to claim 1, wherein the lithographic printing plate precursor is a petal-like alumina film. 3. The photosensitive ink-receiving layer according to claim 1, wherein the photosensitive ink-receiving layer is a negative photosensitive layer which becomes insoluble in an alkaline developer under the action of actinic light to form a printing plate image. The lithographic printing plate precursor according to 1. 4. The photosensitive ink-receiving layer according to claim 1, wherein the photosensitive ink-receiving layer is a positive photosensitive layer which is soluble in an alkaline developer under the action of actinic light to form a printing plate image. The lithographic printing plate precursor according to 1. 5. A negative type in which the photosensitive ink receiving layer according to claim 1 is subjected to the action of high-density energy light, and the corresponding portion becomes insoluble in an alkaline developer to form a printing plate image. The lithographic printing plate precursor according to claim 1, which is a photosensitive layer. 6. A positive-working type wherein the photosensitive ink-receiving layer according to claim 1 is subjected to the action of high-density energy light, and the corresponding portion becomes soluble in an alkaline developer to form a printing plate image. The lithographic printing plate precursor according to claim 1, which is a photosensitive layer. 7. The substrate according to claim 1, wherein the substrate is a glass substrate,
The lithographic printing plate precursor according to any one of claims 1 to 6, which is a ceramic substrate or a metal substrate. 8. A printing plate using the lithographic printing plate precursor according to claim 1, forming an image by irradiating with actinic light, subjecting it to a developing treatment with an alkaline developer, washing with water, gumming and drying. A method for producing a printing plate, comprising: obtaining a printing plate. 9. Using the lithographic printing plate precursor according to any one of claims 1, 2, 5 and 6, an image is formed by irradiation with high-density energy light and, if necessary, heat-treated, and then an alkaline developer is used. A method for producing a printing plate, comprising obtaining a printing plate through development, washing, gumming, and drying.