JP2000181068A - Original plate of planographic printing plate and manufacture of printing plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an original plate of a planographic printing plate that enables a novel plate making method with which an image can be formed by irradiation with light in the offset printing field. SOLUTION: A petaloid alumina layer, a titanium dioxide layer and a coating of a polysiloxane containing silicon atoms to which organic groups bond are successively disposed on a glass, ceramic or metallic substrate to obtain the objective original plate of a planographic printing plate. The original plate is imagewise irradiated with an active light, high density energy light or radiation for manufacturing the objective 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 novel printing plate manufacturing method using the same.

[0002]

2. Description of the Related Art A lithographic printing plate precursor used in the field of offset printing is irradiated with an actinic ray or a high-density energy ray in an imagewise manner, and the irradiated portion is removed by solubilization in an alkaline developer. A method in which the non-image part is used for printing as an ink receiving part of a printing plate, or the ink receiving layer is burned and destroyed imagewise using high-density energy rays, and the remaining non-destructive part is used as an ink receiving part for printing. A method for providing such information is known.

[0003] Specific prior art is disclosed in, for example, Japanese Patent Application Laid-Open Nos. 57-212,436 and 57-212,437.
Nos. 58-87,555 and 61-245,154
No. 3,9,360, JP-A-3-211,555, etc., on a substrate whose surface has been subjected to hydrophilic treatment, an alkaline water-soluble or swellable polymer and an o-quinonediazide compound are used as main components. A photosensitive layer is provided, the irradiated area is solubilized in alkaline water by irradiation with actinic rays, and then the irradiated area is dissolved and removed with an alkaline developer to obtain a printing plate having the remaining non-image area as an ink receiving area. There is technology.

As another technique, for example, Japanese Patent Laid-Open No.
20,629, 7-271,029, 8-22
No. 0,752, No. 9-171,254, No. 9-21
No. 1,863, No. 9-211,864, No. 9-21
No. 1,865, No. 9-304,931, etc., on a substrate whose surface has been subjected to hydrophilic treatment, an alkali water-soluble or swellable polymer, a substance that absorbs light and generates heat, and generates an acid by heat Is provided with a heat-sensitive layer containing the compound as a main component, the irradiated portion is solubilized in alkaline water by high-density energy light irradiation, and then the irradiated portion is dissolved and removed with an alkaline developer, and the remaining non-image portion is removed. There is a technique for obtaining a printing plate as an ink receiving portion.

Further, for example, Japanese Patent Laid-Open No. 9-1,916,
No. 10-3, 164, No. 10-39, 498, etc., on a substrate having a hydrophilic surface, a binder resin, a substance which absorbs light and generates heat, and a compound which decomposes by heat. There is a technique of providing a resin layer as a component, burning and destroying an irradiated portion by high-density energy ray irradiation, removing the irradiated portion, and obtaining a printing plate having a remaining non-image portion as an ink receiving portion.

[0006] In any of these techniques, a resin layer is provided on a substrate having a surface subjected to hydrophilic treatment, and a compound which undergoes a chemical or physical change by receiving light in the resin layer is contained.
This is a technique for obtaining a printing plate by removing the irradiated portion using a chemical or physical change occurring in the irradiated portion of the resin layer after the irradiation of the light beam.

On the other hand, a film using photocatalytic titanium oxide is disclosed in, for example, JP-A-7-155,598 and JP-A-8-6.
Nos. 6,635, 8-131,834, 8-13
No. 1,842, No. 8-224,481, No. 9-57,
Nos. 912, 9-78, 791, 9-225, 38
No. 7, 9-227, 156, 9-227, 805
Nos. 9-227,829 and 9-227,831
Nos. 9-227,832 and 9-241,038
No. 10-81,840 and No. 10-85,608
No., No. 10-85,609, No. 10-85,610
No., 10-95,635 and 10-114,545
No. 10-114,546, International Publication No. 96-1
No. 4,932, No. 96-29,375, No. 97-2
No. 3,572 and the like disclose a member and a forming method using the same. That is, for example, the surface of a base material is first coated with amorphous titania by hydrolysis and dehydration condensation polymerization of an organic titanium compound such as tetraethoxytitanium, and then baked at a temperature of 400 to 600 ° C., thereby forming amorphous titania. Is changed to crystalline titania (anatase), whereby a substrate surface having a very small contact angle with water and excellent in abrasion resistance can be formed. Furthermore, there is another preferred method of incorporating silica or tin oxide into the photocatalytic titania. As another method, a coating composition obtained by dispersing a photocatalytic titanium oxide in a film-forming element made of uncured or partially cured silicone (organopolysiloxane) or a silicone precursor is applied to the surface of a substrate. After coating and curing the film-forming element to form a silicone coating, when the photocatalyst is photoexcited, the organic groups bonded to the silicon atoms of the silicone molecules are replaced with hydroxyl groups by photocatalysis, and the surface of the photocatalytic coating is super It is made hydrophilic. Furthermore, it is preferable to add a solid acid or a solid base as a surface energy enhancer in order to maintain hydrophilicity.

When the surface of the film using the photocatalytic titanium oxide thus produced is irradiated with light having a wavelength of light energy higher than the band gap energy of the photocatalyst,
The photoexcited surface becomes highly hydrophilic. Utilizing this property, for example, application to anti-fog action of mirrors, anti-fog action of window glass, anti-pollution action of ceramic surface, antibacterial action of ceramic surface, and the like has been attempted. However, the surface of the film using the conventional photocatalytic titanium oxide has a problem that the hydrophilicity gradually decreases when the photoexcitation is interrupted, and the hydrophilicity is high but the water retention on the surface is poor. It has never been used as a substrate surface material.

[0009]

SUMMARY OF THE INVENTION A first object of the present invention is a lithographic printing plate precursor utilizing hydrophilicity of titanium oxide by photoexcitation, which is excellent in maintaining hydrophilicity, water retention and ink receptivity. To provide a lithographic printing plate precursor for lithographic printing. A second object of the present invention is to provide a printing plate manufacturing method characterized by a very simple and clean plate making method of merely irradiating light using the printing plate precursor.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention provided a thin film of titanium oxide on a petal-like alumina layer to solve the problems when using it as a printing plate substrate, such as poor water retention. We have discovered that we can solve the problem, and found that by providing a polysiloxane coating layer containing silicon atoms with organic groups bonded on the titanium oxide layer, the ink receptivity was improved and it could be used as a lithographic printing plate precursor. Was. Furthermore, the lithographic printing plate precursor thus obtained is
A very simple method of irradiating light like an image, and
The present inventors have found that a printing plate can be made by a new method based on a principle completely different from the above-described conventional plate making technology, and have led to the present invention.

That is, the first structure of the present invention comprises a glass substrate, a ceramic substrate, a metal substrate, or the like as a base, a petal-like alumina layer, a titanium oxide layer, and a silicon atom to which an organic group is bonded. A lithographic printing plate precursor comprising a polysiloxane coating layer formed in this order. or,
The present invention provides the above-described petal-shaped alumina layer, an alumina film formed by drying and heat-treating a film with a coating solution comprising at least an aluminum alkoxide and a stabilizer on a substrate,
The planographic printing plate precursor, which is a petal-like alumina layer produced by hot water treatment or heat steam treatment, drying and baking, is included.

Further, according to the constitution of the present invention, in the above-mentioned polysiloxane coating layer containing a silicon atom having an organic group bonded thereto, the organic group is an alkyl group having 1 to 30 carbon atoms, an alkylene group or an aryl group. And a lithographic printing plate precursor that is at least one selected from the group consisting of heterocyclic groups. Furthermore,
According to the constitution of the present invention, the above-mentioned polysiloxane coating layer containing a silicon atom having an organic group bonded thereto has an organic group bonded to a silicon atom as an alkyl group having 1 to 30 carbon atoms, an alkylene group, an aryl group and a hetero group. Prepared from an alkoxysilane compound having at least one organic group selected from the group consisting of cyclic groups, a partial hydrolysis condensate of the alkoxysilane compound or a hydrolysis condensate of the alkoxysilane compound. Lithographic printing plate precursors.

According to a second aspect of the present invention, there is provided a printing plate, wherein the lithographic printing plate precursor is imagewise irradiated with actinic rays, high-density energy rays or radiation to prepare a printing plate. It is a manufacturing method.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A lithographic printing plate precursor according to the present invention will be described.

The first feature of the lithographic printing plate precursor according to the present invention is that a petal-like alumina layer is first provided on a substrate.
As a substrate that can be used in the present invention, in consideration of use as a lithographic printing plate, a glass substrate or a ceramic substrate or preferably an iron plate having a thickness of 1 mm or less, more preferably a thickness of 0.5 mm or less, a stainless steel plate, Galvanized sheet,
A thin metal substrate, such as a nickel-plated steel plate or a chrome-plated steel plate, which does not cause a change such as a phase change even under a heating and baking condition at 300 ° C. or more, is used.

The lithographic printing plate precursor according to the present invention is produced by providing a petal-like alumina layer on the above substrate. It is known to provide a petal-like alumina layer on a glass substrate. Ceram. Soc. Japan, V
ol. 103, no. 6, 582-585 (199
5). Proc. ofXVII, Inte
r. Congress on Glass, Vol.
4,445-449 (Beijing, China, 1
995). And Minami Tsutomu, New Glass, Vol. 1
2, No. 2, 42-45 (1996). , Minamitsuto, S
ol-Gel Optics IV, Proc. of
SPIE, Vol. 3136, 168-175 (San
Diego, USA, 1997). J. Minamitsuto et al. A
m. Ceram. Soc. , Vol. 80, no. 4,
1040-42 (1997). J. Minamitsuto et al. Am. C
eram. Soc. , Vol. 80, no. 12,32
13-16 (1997). , Minami Tsutomu, Surface Technology, Vo
l. 48, no. 3, 58-63 (1997). JP-A-9-202,649, JP-A-9-202,650, JP-A-9-202,651, etc. disclose a petal-like alumina layer and a method for forming the same.

In the present invention, the petal-shaped alumina layer is used not only on a glass substrate but also on a ceramic substrate or preferably on a metal substrate such as a stainless steel plate, a galvanized steel plate, a nickel-plated steel plate or a chrome-plated steel plate. Can be That is,
As a specific method of providing a petal-like alumina layer on a substrate, an alumina film formed by drying and heat-treating a film on a substrate with a coating solution containing at least an aluminum alkoxide and a stabilizer is subjected to hydrothermal treatment or It can be achieved by heating and steaming, drying and firing.

Examples of the aluminum alkoxide that can be used in the present invention include 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, for example, 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.

The diluting solvent used in the coating solution comprising at least the aluminum alkoxide and the stabilizer includes, 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 an effect of preventing aluminum alkoxide from reacting quickly with moisture in the air to cause gelation and cloudiness are prevented. Stabilizers such as ketoester compounds or alkanolamines may be added in a molar ratio of, for example, 1 or more, and diluted with a diluting solvent of various alcohols to a concentration that can be easily applied, for example, diluted 10 to 20 times to form a coating solution. Alternatively, a coating solution can be prepared after partial or complete hydrolysis by adding a small amount of water in advance. As a preferable mixing ratio, aluminum alkoxide: diluting solvent: stabilizing agent: water = 1: 10 to 1 in molar ratio.
100: 0.5-2: 0-5.

The coating method for applying the coating liquid 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 dried at room temperature to 100 ° C. or lower for several minutes to several hours, and then dried at about 600 ° C. Hereinafter, the amorphous alumina layer can be formed by baking at a temperature of preferably 550 ° C. or lower and 200 ° C. or higher for 1 minute 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, the surface of the amorphous alumina layer is decomposed by immersing the material having the amorphous alumina layer formed on the substrate in hot water at 50 to 150 ° C. for 10 seconds to 24 hours or exposing it to hot steam for 1 second or more. Under the agglomeration action, petal-shaped objects with unique and minute pore-shaped voids have a randomly aggregated surface layer surface, and can be used as a target lithographic printing plate substrate It is possible to obtain a structural film having voids and shapes.

Next, the substrate on which the petal-like structure film is formed is dried at room temperature to about 150 ° C. for 10 seconds or more, and then baked in a temperature range of 300 to 750 ° C. for 1 minute to 1 hour. It is possible to form the desired petal-like alumina film having a strong and unique microvoid structure. The petal-like alumina film has a thickness of 10 nm.
The thickness is preferably 10 μm or more and 10 μm or less. Further, the petal-like alumina film has an average surface roughness R obtained by expanding the center line average roughness.
a 'value is more than 17 nm, and the specific surface area S _R is is preferably 1.5 or more.

The titanium oxide layer of the present invention will be described.
The titanium oxide layer of the present invention is a titanium oxide film provided on the petal-like alumina layer described above, and is produced by the following method. That is, for example, an amorphous titania layer is coated on the surface of petal alumina by hydrolysis and dehydration condensation polymerization of an organic titanium compound such as titanium alkoxide. At this time, as a specific stabilizing chelating agent, 1,3-diketone (β
-Diketone) compounds and / or β-ketoester compounds. Further, the surface of the petal-like alumina may be coated with an amorphous titania layer after partial or complete hydrolysis by adding water in advance. Next, the amorphous titania provided on the surface of the petal-like alumina is heated and fired to form a titanium oxide layer.

Specific examples of the organic titanium compound used in the present invention include, for example, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-tert-butoxytitanium, tetramethoxytitanium Titanium and the like, and titanium chelates such as titanyl acetyl acetate and the like can be mentioned.

The method for coating the amorphous titania layer on the surface of the petal-like alumina of the present invention is as follows. First, an organotitanium compound and a chelating agent such as a β-diketone compound and / or a β-ketoester compound are mixed, for example, in a molar ratio. And dilute it with a diluting solvent such as various alcohols to a concentration that facilitates coating, for example, 10 to 20-fold, and further add a small amount of water as needed to obtain a coating solution. As a preferable mixing ratio, an organic titanium compound: a diluting solvent: a chelating agent: water = 1: 10 to 100: 0.5 to 2: 0 to 5 in a molar ratio.

Specific examples of the chelating agent used at this time include, for example, acetylacetone, dipyrroylmethane,
1,3-diketone (β-diketone) compounds such as trifluoroacetylacetone and hexafluoroacetylacetone and / or methyl acetoacetate, ethyl acetoacetate;
Allyl acetoacetate, benzyl acetoacetate, acetoacetic acid
iso-propyl, tert-butyl acetoacetate, iso-butyl acetoacetate, 2-methoxyethyl acetoacetate, methyl 2-keto-n-valerate, methyl 3-keto-2-keto-n-valerate, Β-ketoester compounds such as methyl 2-keto-capronate and methyl 2-keto-enantiate can be mentioned.

Examples of the diluting solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, butyl alcohol,
Ethylene glycol, ethylene glycol-mono-n-
Examples thereof include propyl ether, dimethylacetamide, methyl ethyl ketone, methyl isopropyl ketone, and the like, and a mixed solvent thereof.

The coating method for applying the amorphous titania layer coating solution on the petal-like alumina layer includes dipping, spin coating, nozzle flow coating, spraying, reverse coating, flexo, printing, and flow coating. A known coating means such as a coating method and a bar coating method can be appropriately used. The applied amorphous titania layer is dried at room temperature to 150 ° C. for several seconds to several hours.

Next, in order to bake the amorphous titania provided on the surface of the petal-like alumina layer according to the present invention, 200 to 200
This is achieved by firing at a temperature of 900 ° C., preferably 300 to 700 ° C. for 1 minute to 2 hours. The thickness of the titanium oxide layer according to the present invention is preferably from 10 nm to 10 μm.

As another method for providing a titanium oxide layer on the surface of the petal-like alumina layer, an alkaline aqueous solution is added to an acidic aqueous solution of titanium tetrachloride or titanium sulfate, if necessary, to form a coating solution. And dried at a temperature of 300 to 700 ° C. for 1 minute to 2 minutes.
There are a method in which a titanium oxide layer is formed by firing for a time, and a method in which a crystalline titanium oxide sol is applied to the surface of a petal-like alumina layer and dried. Either method can be used as the titanium oxide layer forming method of the present invention.

In the polysiloxane coating layer containing a silicon atom having an organic group bonded thereto according to the present invention, the organic group has 1 to 1 carbon atoms.
It is at least one selected from the group consisting of an alkyl group, an alkylene group, an aryl group and a heterocyclic group having 30 carbon atoms. The organic group is an alkyl group having 1 to 30 carbon atoms, an alkylene group, an aryl group and a heterocyclic group. Prepared from an alkoxysilane compound having at least one of at least one organic group selected from the group consisting of groups, a partial hydrolysis condensate of the alkoxysilane compound or a hydrolysis condensate of the alkoxysilane compound. Things.

The alkoxyl groups of the alkoxysilane compounds include lower alcohols having 10 or less carbon atoms such as methoxy, ethoxy, isopropoxy, n-propoxy, butoxy and β-methoxyethoxy. And an alkoxyl group derived from

Specific examples of the alkoxysilane compound containing a silicon atom to which an organic group is bonded according to the present invention include, for example, diallyldiethoxysilane, hexyltriethoxysilane, 1,2-bis (butyldiethoxysilyl) ethane, Bromophenyltrimethoxysilane, di (3-chloropropyl) dimethoxysilane, decyltriethoxysilane, diphenyldimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, diisobutyldiethoxysilane, 3- (methacryloxy)
Propyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, 4-tolyltrimethoxysilane, 3-
(Triethoxysilyl) propylcyclopentadiene, trivinylethoxysilane, and the like.

The method for providing a polysiloxane coating layer containing a silicon atom having an organic group bonded thereon according to the present invention on the titanium oxide layer according to the present invention comprises the steps of: Choose one or more from among them,
An organic solvent capable of dissolving them is selected and dissolved, and if necessary, other additives are added to form a coating solution.Dipping, spin coating, nozzle flow coating, spraying, reverse coating, flexo, It can be produced by coating by a known coating means such as a printing method, a flow coating method, and a bar coating method, followed by drying and baking. Organic solvents that can be used at this time include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol,
Ethylene glycol-mono n-propyl ether, 2-
Alcohols such as methoxyethanol, ketones such as acetone, methyl ethyl ketone and methyl isopropyl ketone, amides such as dimethylformamide and dimethylacetamide, esters such as methyl acetate, ethyl acetate, propyl acetate, methylcellosolve acetate, tetrahydrofuran and the like And the like. Other additives include various surfactants, coating aids, acid catalysts, and the like. In addition, the organic group of the present invention is excellent in hardness and durability by heating at 200 to 500 ° C. for 1 minute to 1 hour by drying at room temperature to 150 ° C. or lower for several minutes to several hours. To form a polysiloxane coating film layer containing a silicon atom to which is bonded. The thickness of the polysiloxane coating layer containing a silicon atom having an organic group bonded thereto is 5
nm to 10 μm is preferred.

A method for preparing a printing plate using the lithographic printing plate precursor according to the present invention will be described. As a light source capable of performing image writing on the lithographic printing plate precursor of the present invention, ultraviolet light of 300 nm or less as active light, second harmonic of excimer laser or semiconductor laser as high density energy light, third harmonic, and 300n emission line at 4th harmonic
m or less, and an electron beam or an X-ray can be used as the radiation. As a method of writing an image on a lithographic printing plate precursor, in the case of irradiating the entire surface with actinic rays or radiation, by irradiating the entire image with a mask or the like formed on a glass plate as a mask, the target image of the present invention can be used. It can be produced on a plate master. When a high-density energy ray or radiation beam is used as the light source, an image is formed by directly scanning and irradiating the lithographic printing plate precursor of the present invention with the light source beam using information digitized by a computer or the like in advance. . Irradiation conditions cannot be specified because they vary greatly depending on the thickness of the polysiloxane coating layer containing a silicon atom to which an organic group is bonded and the intensity of the light source power, but the time is within several seconds to several hours. The end point can be known by the fact that the contact angle of the light irradiation part with water becomes superhydrophilic of 5 degrees or less. That is, although the detailed mechanism is unknown, the contact angle with water of the polysiloxane coating layer portion containing the silicon atom to which the organic group is bonded is 5 degrees or less due to the photocatalytic action of titanium oxide in the portion irradiated with light. And become superhydrophilic. As described above, the printing plate manufacturing method according to the present invention only needs to irradiate light, and does not need to go through a cumbersome process such as a developing process using a developing solution.

In the printing plate obtained from the lithographic printing plate precursor according to the present invention, the above-mentioned hydrophilic portion becomes a non-image portion in printing, and the other portion becomes an ink receiving portion to become a printed image portion. The printing plate obtained at this time can be used as it is as a printing plate, but it is desirable that the printing plate be desensitized with a gum solution or the like before printing.

The desensitization is a pretreatment for printing which is generally performed widely in the printing industry today, and is performed for the purpose of preventing printing stains due to ink deposition on hydrophilic portions of a printing plate. . That is, water-based desensitizing agents (for example, natural water-soluble polymers such as gum arabic, dextrin, carboxymethylcellulose, and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid) in water and, if necessary, A gum solution prepared by adding an acid or a surfactant is applied to a printing plate to desensitize a hydrophilic portion, and then dried to form a printing plate, which is then provided for printing. The ink used at this time can be printed using exactly the same ink as printing performed using a normal photosensitive lithographic printing plate.

[0041]

EXAMPLES 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. While further stirring, 13 g of acetoacetic acid ethyl ester was added, and the mixture was stirred at room temperature for 1 hour. Then
A mixed liquid 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 liquid. 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, 4
After baking at 00 ° C for 10 minutes, 10 minutes in hot water at 90 ° C.
Soak for minutes. After the immersion, baking was performed again at 400 ° C. for 10 minutes to form a petal-like alumina layer. 1
It was confirmed that the surface had a peculiar shape of a petal by an electron microscope at a magnification of 0000.

To a solution of 3.4 g of titanium tetra-n-butoxide monomer dissolved in 46 g of ethanol was added a mixture of 1 g of acetylacetone and 14 g of ethanol with stirring. After stirring at room temperature for 3 hours after the addition, a mixed solution of 0.72 g of water and 14 g of ethanol was added, and the mixture was further stirred for 2 hours.
Stirred for hours. The titanium sol solution thus prepared was applied on a glass substrate provided with a petal-like alumina layer by using a spinner at 3000 rpm for 15 seconds.
After air drying, baking was performed at 500 ° C. for 30 minutes to form a titanium oxide layer. The thickness of the titanium oxide layer was 30 nm.

Next, octyltrimethoxysilane 5
A solution prepared by adding 0.7 g of a 0.01N hydrochloric acid aqueous solution to 200 g of a 200% methyl ethyl ketone solution,
The coating was performed on the titanium oxide layer under the conditions of 00 rpm and 15 seconds. After air drying, baking was performed at 400 ° C. for 10 minutes to obtain a lithographic printing plate precursor using the glass of the present invention as a substrate.

The lithographic printing plate precursor of the present invention is brought into close contact with a character image formed on a photographic plate made of glass and irradiated with a low-pressure mercury discharge lamp (253-310 nm, manufactured by Ishii Shoten) for 15 minutes. I got At this time, the contact angle of the light irradiated part on the printing plate was 5 degrees or less, and the unirradiated part was 135 degrees.

Next, the printing plate was wetted with a gum solution (UG1 was diluted two-fold; manufactured by Polychrome Japan) and dried. The printing plate was fixed on a metal plate with double-sided tape and printing was performed. The printing was performed using a fountain solution NA108W (1:50 dilution,
After applying ink (GEOS-G Red N, manufactured by Dainippon Ink and Chemicals, Inc.) with an ink roller in the presence of Dainippon Ink and Chemicals, the character image is transferred to a rubber roller and further printed on paper. This was performed by transferring a character image from a rubber roller. By the above procedure, a printed matter of one character was obtained. Thereafter, printing was continued in a cycle of dampening water → inking → rubber roller transfer → paper transfer to obtain 500 prints. During this time, the character quality of the printed matter was good.

Example 2 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 having a rod number of # 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.

Next, the titanium sol solution prepared in Example 1 was applied onto the petal-like alumina layer with a wire number rod # 8. After air drying, baking was performed at 500 ° C. for 30 minutes to form a titanium oxide layer. Next, 250 g of a 5% methyl ethyl ketone solution of octadecyltriethoxysilane
Was applied to the titanium oxide layer with a wire bar having a rod number of # 8 using a solution obtained by adding 1.0 g of a 0.01 N hydrochloric acid aqueous solution. After air drying, baking was performed at 300 ° C. for 10 minutes to obtain a lithographic printing plate precursor using the stainless steel plate of the present invention as a substrate.

The lithographic printing plate precursor of the present invention is brought into close contact with a character image formed on a photographic plate made of glass and irradiated with a low-pressure mercury discharge lamp (253-310 nm, manufactured by Ishii Shoten) for 30 minutes. I got Printing plate with gum (UG1 2
After dilution, polychrome Japan)
The printer was mounted on a printing machine (TOKO-820L; manufactured by Tokyo Aviation Instruments Inc.). 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 3 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 wire number rod # 12. After air-drying, it was baked at 250 ° C. for 30 minutes, and then immersed in hot water at 90 ° C. for 10 minutes. After the immersion, baking was again performed at 250 ° C. for 20 minutes to form a petal-like alumina layer.

Next, the titanium sol solution prepared in Example 1 was applied onto the petal-like alumina layer with a wire number rod # 8. After air drying, baking was performed at 250 ° C. for 1 hour to form a titanium oxide layer. Next, using a solution obtained by adding 1.0 g of a 0.01N hydrochloric acid aqueous solution to 250 g of a 5% solution of octadecyltriethoxysilane in methyl ethyl ketone,
It was applied on the titanium oxide layer with a wire bar of rod number # 8. After air drying, baking was performed at 250 ° C. for 15 minutes to obtain a lithographic printing plate precursor using the galvanized sheet of the present invention as a substrate.

The lithographic printing plate precursor of the present invention is brought into close contact with a character image prepared on a photographic plate made of glass and irradiated with a low-pressure mercury discharge lamp (253-310 nm, manufactured by Ishii Shoten) for 30 minutes. I got Printing plate with gum (UG1 2
After dilution, polychrome Japan)
The printer was mounted on a printing machine (TOKO-820L; manufactured by Tokyo Aviation Instruments Inc.). 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 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.

[0053]

According to the present invention, a lithographic printing plate precursor having a three-layer structure of a petal-like alumina layer, a titanium oxide layer, and a polysiloxane coating layer containing a silicon atom to which an organic group is bonded on a substrate is provided by a light-emitting plate. A lithographic printing plate can be manufactured by a simple and clean plate making method of simply irradiating the plate.

Continued on 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 AB03 AC01 AC04 AC05 AC06 AC08 BH03 DA18 DA19 DA40 EA04 EA10 2H096 AA06 BA16 CA05 CA12 CA20 EA02 EA03 EA04 EA05 EA06 EA07 2H114 AA04 AA15 BA01 DA04 DA08 DA14 DA38 GA38

Claims (6)

[Claims] A lithographic printing plate precursor comprising a petal-like alumina layer, a titanium oxide layer, and a polysiloxane coating layer containing a silicon atom to which an organic group is bonded on a substrate in this order. 2. The petal-shaped alumina layer is dried with a coating solution comprising at least an aluminum alkoxide and a stabilizer, and then heat-treated. The lithographic printing plate precursor according to claim 1, which is a petal-shaped alumina layer obtained by firing. 3. The organic group in the polysiloxane coating layer containing a silicon atom having an organic group bonded thereto,
At least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an alkylene group, an aryl group and a heterocyclic group
The lithographic printing plate precursor according to claim 1 or 2, which is a seed. 4. The polysiloxane coating layer containing a silicon atom to which an organic group is bonded, as the organic group,
At least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an alkylene group, an aryl group and a heterocyclic group
An alkoxysilane compound having at least one kind of organic group, a partially hydrolyzed condensate of the alkoxysilane compound or a hydrolyzed condensate of the alkoxysilane compound. The lithographic printing plate precursor according to any of the above. 5. The lithographic printing plate precursor according to claim 1, wherein the substrate is a glass substrate, a ceramic substrate, or a metal substrate. 6. A printing plate, comprising irradiating the lithographic printing plate precursor according to any one of claims 1 to 5 with actinic rays, high-density energy rays or radiation in an imagewise manner to produce a printing plate. Plate making method.