JPH08324144A - Support for lithographic printing plate, manufacture thereof and photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE: To provide the hydrophilic property and water retention characteristics and the excellent stickiness to a photosensitive layer for the printability. CONSTITUTION: (1) The mean opening diameter of a micropore formed by anodizing after sealing is 4nm or less, (2) the surface of aluminum of the side for providing a photosensitive composition layer has 0.2 to 1.2mg/min of dissolving velocity in chromium phosphoric acid aqueous solution and 0.40mg/sec of dissolving velocity in sodium hydroxide aqueous solution, where the chromium phosphoric acid aqueous solution is (20g of chromium acid anhydride +35ml of 85wt.% phosphoric acid)/1000ml, and the sodium hydroxide aqueous solution is 0.5wt.%, or (3) the opening area of the micropore formed by the anodizing is 0.5 to 5% of the total support surface area after sealing.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a support for a lithographic printing plate, a method for producing the same, and a photosensitive lithographic printing plate. Particularly, from the viewpoint of printability, hydrophilicity, water retention and adhesiveness with a photosensitive layer are provided. And a method for producing the same, and a photosensitive lithographic printing plate.

[0002]

BACKGROUND OF THE INVENTION The lithographic printing method is a printing method which utilizes the fact that water and oil are essentially immiscible, and the printing plate surface receives non-image areas that repel water and repel ink, and water repels water. Then, an image portion that receives the ink is formed, and water and ink are supplied from the printing machine to transfer only the ink received in the image portion onto the paper. In a printing machine, an offset printing method is generally used in which the ink received in the image area of the printing plate surface is once transferred to a rubber blanket and then transferred to paper.

Conventionally, a support used for a photosensitive lithographic printing plate is required to have excellent hydrophilicity, water retention and adhesiveness to a photosensitive layer in view of printability, and from such a viewpoint, a normal surface is required. An aluminum plate that has been subjected to a roughening treatment called graining is used. The surface roughening treatment is performed by mechanical surface roughening such as ball polishing, brush polishing, blast polishing, buff polishing, honing polishing, etc., and electrolytic treatment of the surface of the support by alternating current or direct current in an acidic electrolytic solution such as hydrochloric acid or nitric acid. There are known electrochemical roughening methods and the like. The aluminum plate that has been grained by such a method is relatively soft and easily abraded as it is, so an oxide film is formed by anodizing the aluminum plate. The surface of the aluminum plate thus treated is hard and has excellent wear resistance.

[0004]

2. Description of the Related Art However, even an aluminum plate which has been subjected to such a treatment is not sufficient to satisfy stains and printing durability of a non-image area under various printing conditions. In order to solve such a problem, in order to improve the stain on the non-image area, a hydrophilic treatment is performed after the anodizing treatment. JP-A-56-21126 discloses a method of providing an undercoat layer composed of a hydrophilic resin and a water-soluble salt, and JP-A-64-14090 discloses a method of providing an undercoat layer composed of a carboxylate.
No. 130391, a method of providing a hydrophilic layer comprising at least one selected from an inorganic acid salt and an organic acid salt of a compound having at least one amino group and at least one group selected from a carboxyl group and a sulfo group. Japanese Patent Laid-Open No. 63-165183 proposes a method of providing a hydrophilic layer containing at least one amino group and a phosphon group or a salt of a phosphon group, and the like. It was not sufficient to improve the stain resistance without deteriorating. Further, regarding the rough surface shape, US Pat. No. 4,301,229 defines the cumulative frequency distribution of the pit diameter and the center line average roughness, and German Patent No. 1,81
No. 3,443 defines the height difference of a rough surface.
No. 32294 defines the average depth.
No. 6 defines the pit diameter and the maximum depth in the direction perpendicular to the diameter.
However, even with these techniques, the printing durability and the stain resistance of the non-image area were insufficient. Also, during development, aluminum is eluted by alkali, white crystal matter is attached to the non-image area or the back surface of the support, and the fatigue of the developer is accelerated,
There was also the problem of the generation of sludge-like precipitates.

[0005]

A common object of the present invention is to provide a support for a lithographic printing plate which is excellent in hydrophilicity, water retention and adhesiveness to a photosensitive layer from the viewpoint of printability. The first object of the present invention is to
(EN) It is intended to provide a support for a lithographic printing plate which is excellent in printing durability and stain resistance, particularly stain resistance when a plate is reused, and a method for producing the same. A second object of the present invention is to provide a photosensitive lithographic printing plate which has both printing durability and stain resistance and is excellent in tone reproducibility. A third object of the present invention is to provide a photosensitive lithographic printing plate which has both printing durability and stain resistance, has excellent tone reproducibility, and is less likely to elute aluminum during development.

[0006]

The common objects of the invention are achieved by claims 1-10. The first object of the present invention is achieved by claims 1 and 2. The second object of the present invention is achieved by claims 3 to 5. The third object of the present invention is claims 6 to 10.
Is achieved by

That is, the above-mentioned object of the present invention is formed by (1) a lithographic printing plate support comprising an aluminum plate which has been roughened, anodized and sealed. A support for a lithographic printing plate, characterized in that the average opening diameter of the micropores after sealing is 4 nm or less, (2) the two-dimensional perpendicularity of the micropores in the cross section of the anodized film is 85 degrees or more. 2. The lithographic printing plate support according to claim 1, wherein (3) the lithographic printing plate support comprising an aluminum plate that has been roughened, anodized and sealed. The aluminum surface on the side where the layer of the conductive composition is provided has a dissolution rate of 0.2 to 1.2 mg / mi in the aqueous solution of chromium phosphoric acid.
n. , Dissolution rate in sodium hydroxide aqueous solution is 0.
40 mg / sec. A lithographic printing plate support characterized by the following, provided that the chromic phosphoric acid aqueous solution is (chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 ml and the sodium hydroxide aqueous solution is 0.5 wt%

(4) The lithographic printing plate support according to claim 3, wherein the oxide film formed by the anodizing treatment has a thickness of 500 to 1200 nm, and (5) at least nitric acid by the roughening treatment. 5. A method for producing a lithographic printing plate support according to claim 4, further comprising the step of performing an electrochemical reaction in a system electrolyte solution, which is (6) roughened, anodized and sealed. In the lithographic printing plate support made of an aluminum plate, the opening area of the micropores formed by the anodizing treatment is 0.5 to 5% of the total surface area of the support after the sealing treatment. A lithographic printing plate support characterized by: (7) a lithographic printing plate support comprising an aluminum plate that has been subjected to surface roughening, anodization treatment, and sealing treatment; Density (A) [ / [Mu] m ^2] and anodized film thickness (B) [and [mu] m], sealing treatment after the micropores mean opening diameter (C) [μm] and, by roughening treatment Rz (D)
[Μm] satisfies the following relational expression (I): 0.02 <A × B × π × (0.5 × C) ² × D <0. 10 (I)

(8) The support for a lithographic printing plate according to claim 6 or 7, wherein the density of the micropores formed by the anodizing treatment is 500 to 1500 pieces / µm ^2. The support for a lithographic printing plate according to claim 8, wherein the oxide film formed by the oxidation treatment has a thickness of 500 to 1200 nm. (10) Electrochemical in at least a nitric acid-based electrolytic solution in the roughening treatment. A method for producing a lithographic printing plate support, which comprises the steps of:
(11) A photosensitive lithographic printing plate characterized in that a photosensitive layer containing a photosensitive composition is coated on the lithographic printing plate support according to any one of claims 1 to 10. To be done.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, for example, alloys of aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium and iron.

The aluminum support is preferably subjected to a degreasing treatment in order to remove rolling oil on the aluminum surface prior to roughening. As degreasing treatment, trichlene,
A degreasing treatment using a solvent such as thinner, an emulsion degreasing treatment using an emulsion such as kesilon and triethanol, and the like are used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which cannot be removed only by the above degreasing treatment.

As a graining treatment method carried out for improving the adhesion to the photosensitive layer and improving the water retention,
There are a so-called mechanical surface-roughening method for mechanically roughening the surface and a so-called electrochemical surface-roughening method for electrochemically roughening the surface. Examples of the mechanical surface roughening method include ball polishing, brush polishing, blast polishing, and buff polishing. The electrochemical surface roughening method includes, for example, a method of electrolytically treating the support with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid, nitric acid, or the like. One of these
One or a combination of two or more methods makes it possible to grain the support.

The electrolytic surface-roughening treatment is described in, for example, Japanese Patent Publication No. 48-123123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507, and these methods are used in the present invention. Can be used.

The voltage applied in electrolytic graining is 1
It is preferably -50 V, more preferably 2-30 V. The current density is preferably 10 to 150 A / dm ² ,
20-100 A / dm ² is more preferable. The amount of electricity is 1
00 to 20000 c / dm ² , preferably 100 to 10
000 c / dm ² , more preferably 200 to 5000 c
/ Dm ² . The temperature is preferably 10 to 50 ° C., and 1
5 to 45 ° C is more preferable. The concentration of hydrochloric acid or nitric acid is
0.01 to 5% by weight is preferable. If necessary, the electrolyte may contain nitrates, chlorides, amines, aldehydes, phosphoric acid,
Chromic acid, boric acid, etc. can be added.

Smoothing a grained aluminum plate,
It is preferable to chemically treat the surface of the aluminum plate with an aqueous solution of acid or alkali for the purpose of homogenization. Specific examples of the above-mentioned acid or alkali aqueous solution include, for example, acids such as hydrofluoric acid, fluorozirconic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid and sodium hydroxide, potassium hydroxide, sodium triphosphate, sodium aluminate, An alkaline aqueous solution such as sodium silicate or sodium carbonate is used. These acid or alkaline aqueous solutions may be used alone or in combination of two or more. The chemical treatment is carried out using a 0.05 to 40% by weight aqueous solution of these acids or alkalis at a liquid temperature of 40 to 100 ° C. for 5 to 300 seconds.

Since smut is formed on the surface of the obtained support, it is generally preferable to appropriately perform washing with water or alkali etching in order to remove the smut. Examples of such treatment include a treatment method such as an alkali etching method described in JP-B-48-28123 and a sulfuric acid desmutting method described in JP-A-53-12739.

Further, an anodizing treatment is applied in order to improve water retention and wear resistance of the surface. As the electrolyte used for the anodizing treatment of the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally, the concentration of the electrolyte is 1 to 80 wt% solution,
The liquid temperature is appropriately 1 to 70 ° C., the current density is 1 to 60 A / dm ² , the voltage is 1 to 100 V, and the electrolysis time is 10 seconds to 5 minutes. In the particularly preferred sulfuric acid method, the treatment is usually performed with a direct current, but an alternating current can be used. The sulfuric acid is used at a concentration of 5 to 30%, and is electrolyzed at a temperature range of 20 to 60 ° C. for 5 to 250 seconds. The electrolytic solution preferably contains aluminum ions. Further, the current density at this time is preferably 1 to 20 A / dm ² .

The support preferably used in the present invention may be subjected to a pore-sealing treatment after the anodizing treatment. Examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment. Further, the support preferably used in the present invention may be provided with a hydrophilic undercoat layer. Examples of the hydrophilic undercoat layer include alkali metal silicates described in US Pat. No. 3,181,461 and US Pat. No. 1,860,426.
Hydrophilic cellulose described in JP-A-60-14
9491 and 63-165183, amino acids and salts thereof, hydroxyl group-containing amines and salts thereof described in JP-A-60-232998, JP-A-6-62.
Phosphates described in JP-A-2-19494, JP-A-59-1
Examples thereof include polymer compounds containing a monomer unit having a sulfo group described in JP-A No. 01651.

Further, in order to prevent scratches on the photosensitive layer when the photosensitive lithographic printing plates are stacked, and to prevent the elution of the aluminum component in the developing solution during development, JP-A-50-
151136, 57-63293, 60-73.
No. 538, No. 61-67863, JP-A-6-3517.
The treatment of providing a protective layer on the back surface of the support described in No. 4 or the like can be performed.

Next, a photosensitive layer containing the photosensitive composition is applied onto the surface-treated support to obtain a photosensitive lithographic printing plate preferably used in the present invention. The photosensitive substance used in this photosensitive layer is not particularly limited, and various substances usually used in photosensitive lithographic printing plates can be used. Hereinafter, this point will be described.

(Photosensitive Layer) The photosensitive lithographic printing plate of the present invention can be obtained by coating the surface-treated support of the present invention with a photosensitive layer of a photosensitive composition. The photosensitive substance used in this photosensitive layer is not particularly limited as long as it is an o-quinonediazide compound when a positive photosensitive lithographic printing plate is to be obtained, and usually, for example, various kinds of compounds such as those described below are used. Stuff used.

(Photosensitive composition containing o-quinonediazide compound) In the photosensitive composition containing an o-quinonediazide compound used, an o-quinonediazide compound and an alkali-soluble resin are used in combination. Examples of the o-quinonediazide compound include ester compounds of o-naphthoquinonediazidesulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and dihydric compounds such as catechol, resorcinol and hydroquinone. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred of these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin. To be OH of phenols of the o-naphthoquinonediazide compound
The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the group (reaction rate with respect to one OH group) is preferably 15 to 80%, and more preferably 20 to 45%.

Further, as the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, 1, 2
-Benzoquinone diazide sulfonate, 1,2-
Known 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc.
Quinone diazide compounds, more specifically J. Kosar "Light-Sensitive Systems" (Light-Sensitive System)
ems) pp. 339-352 (1965), John.
Willie & Sons (John Willey &
Sons, Inc. (New York) and W. S. De Forest, "Photoresist", Volume 50 (1975), McGraw H
ill) (New York) 1,2-
Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2
-Benzoquinonediazide-4- (N-ethyl-M-β-
Naphthyl) -sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-
(1,2-naphthoquinonediazide-5-sulfonyl)-
3,5-Dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfone-4'-hydroxydiphenyl-
4'-azo-β-naphthol-ester, N, N-di-
(1,2-naphthoquinonediazide-5-sulfonyl)-
Aniline, 2 '-(1,2-naphthoquinonediazide-5
-Sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-5-sulfone-
2,4-dihydroxybenzophenone ester, 1,2
-Naphthoquinonodiazide-5-sulfonic acid-2,3,4
-Trihydroxybenzophenone ester, a condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone,
Condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4′-dihydroxy-1,1′-diphenylsulfone, 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride Examples thereof include a 1,2-quinonediazide compound such as a condensate of 1 mol of purpurogallin and 1,2-naphthoquinonediazide-5- (N-dihydroabietyl) -sulfonamide. In addition, Japanese Examined Patent Publications No. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, 45-27.
No. 345, No. 51-13013, JP-A-48-965.
The 1,2-quinonediazide compounds described in JP-A No. 75, 48-63802 and 48-63803 can also be mentioned.

Of the above o-quinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more kinds. The proportion of the o-quinonediazide compound in the photosensitive composition is preferably 5 to 60% by weight, and particularly preferably 10 to 50% by weight.

(Diazo Compound) On the other hand, when a negative photosensitive lithographic printing plate is to be obtained, a known photosensitive composition containing a diazo compound may be used.

The diazo compound in the photosensitive composition is, for example, preferably a diazo resin represented by a condensation product of an aromatic diazonium salt and formaldehyde or acetaldehyde. Particularly preferably, the reaction product of a salt of a condensate of p-diazophenylamine with formaldehyde or acetaldehyde, such as hexafluoroborophosphate, tetrafluoroborate, perchlorate or periodate, and the condensate is formed. Examples thereof include diazo resin inorganic salt which is a product, and diazo resin organic salt which is a reaction product of the condensate and sulfonic acids as described in US Pat. No. 3,300,309. . Furthermore, diazo resins are preferably used with binders. As the binder, various polymer compounds can be used, but preferably, a monomer having an aromatic hydroxyl group as described in JP-A-54-98613, such as N- (4 -Hydroxyphenyl) acrylamide, N-
(4-hydroxyphenyl) methacrylamide, o-,
Copolymers of m- or p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate with other monomers, described in U.S. Pat. No. 4,123,276. Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units, such as shellac,
Natural resins such as rosin, polyvinyl alcohol, linear polyurethane resins as described in US Pat. No. 3,751,257, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin , Cellulose acetate, cellulose acetate phthalate, and other cellulose derivatives.

In addition to the above, the following photosensitive composition can be used. 1) Photocrosslinking-type photosensitive resin composition The photosensitive component in the photocrosslinking-type photosensitive resin composition is composed of a photosensitive resin having an unsaturated double bond in the molecule. For example, US Pat. No. 3,030, No. 208, 3,43
Nos. 5,237, 3,622,320 and the like have a photosensitive group in the polymer main chain.

[0030]

Embedded image

Examples thereof include a photosensitive resin containing, and polyvinyl cinnamate having a photosensitive group in the side chain of the polymer.

2) Photopolymerizable Photosensitive Resin Composition A photopolymerizable composition containing an addition polymerizable unsaturated compound, which comprises a monomer having a double bond or a monomer having a double bond. A typical example of such a composition comprising a polymer binder is disclosed in, for example, US Pat. No. 2,760,8.
63 and 2,791,504, JP-A-59-42684, JP-B-6-76444, JP-A-5-85562 and the like.

As an example, a composition containing methyl methacrylate, a composition containing methyl methacrylate and polymethyl methacrylate, a composition containing methyl methacrylate, polymethyl methacrylate and polyethylene glycol methacrylate monomers, methyl methacrylate, an alkyd resin. A photopolymerizable composition such as a composition containing a polyethylene glycol dimethacrylate monomer is used.
This photopolymerization type photosensitive resin composition includes a photopolymerization initiator usually known in this technical field (for example, benzoin derivative such as benzoin methyl ether, benzophenone derivative such as benzophenone, thioxanthone derivative, anthraquinone derivative, acridone derivative, etc. ) Is added.

(Alkali-Soluble Resin) As the alkali-soluble resin, a novolac resin, a vinyl polymer having a phenolic hydroxyl group, a condensation of a polyhydric phenol and an aldehyde or a ketone described in JP-A-55-57841. Resin etc. are mentioned.

Examples of the novolak resin used in the present invention include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-57841.
Phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-127
Examples thereof include copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 553.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × (polystyrene standard).
10 ^{2 to} 7.50 × 10 ³ , and the weight average molecular weight Mw is 1.
00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn
Is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.0.
It is 0 × 10 ^{3 to} 2.00 × 10 ⁴ . The above novolak resins may be used alone or in combination of two or more.

The proportion of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight. Further, the vinyl copolymer having a phenolic hydroxyl group preferably used in the present invention is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and has the following general formula [I]
Polymers containing at least one structural unit of [V] are preferred.

[0038]

Embedded image

[In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents
Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ]

The polymer used in the present invention preferably has a copolymer type structure, and is represented by the above general formula [I].
~ Examples of the monomer unit that can be used in combination with the structural unit represented by the general formula [V] include ethylenically unsaturated offylenes such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene and α-. Styrenes such as methylstyrene, p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, and unsaturated aliphatic dicarboxylic acids such as itacone, maleic acid and maleic anhydride,
For example, methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, Α such as ethyl methacrylate
-Esters of methylene aliphatic monocarboxylic acid, for example, nitriles such as acrylonitrile, methacrylonitrile, etc., amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc. Anilides such as vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl benzoate and vinyl acetate,
For example, methyl vinyl ether, ethyl vinyl ether,
Isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1 -Dimethoxycarbonylethylene, ethylene derivatives such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N
There are N-vinyl type monomers such as -vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention. These monomers may be bound to the polymer used in the present invention in either a block or random state.

The proportion of the vinyl polymer used in the present invention in the photosensitive composition is preferably 0.5 to 70% by weight. As the vinyl polymer, the above polymers may be used alone or in combination of two or more kinds.
It can also be used in combination with other polymer compounds.

(Organic Acid / Inorganic Acid / Anhydride) The photosensitive composition of the present invention may contain an organic acid / inorganic acid / anhydride. Examples of the acid used in the present invention include organic acids described in JP-A No. 60-88942 and Japanese Patent Application No. 63-293107, and "Chemical Handbook New Edition" edited by The Chemical Society of Japan, No. 92-158. The inorganic acids described on the page can be mentioned.
Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid,
Sulfonic acids such as m-benzenedisulfonic acid, sulfinic acids such as p-toluenesulfinic acid, benzylsulfinic acid and methanesulfinic acid, phosphonic acids such as phenylphosphonic acid, methylphosphonic acid and chloromethylphosphonic acid,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid and heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, o-, m-, p -Hydroxybenzoic acid,
o-, m-, p-methoxybenzoic acid, o-, m-, p-
Aromatic monocarboxylic acids such as methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid and 3,5-dimethylbenzoic acid can be mentioned. Also,
Saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid, malic acid, tetrahydro Phthalic acid, 1,1-cyclobutanedicarboxylic acid,
1,1-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

Among the above organic acids, more preferable one is p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Examples include sulfonic acid such as mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid, and m-benzenedisulfonic acid, cis-1,2-cyclohexanedicarboxylic acid, and syringic acid. Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, silicic acid, phosphoric acid and the like, more preferably sulfuric acid and phosphoric acid.

When an acid anhydride is used, the type of acid anhydride is also arbitrary, and those derived from aliphatic / aromatic monocarboxylic acids such as acetic anhydride, propionic anhydride, benzoic anhydride, and succinic anhydride. , Maleic anhydride, glutaric anhydride, phthalic anhydride, and the like, and the like derived from aliphatic / aromatic dicarboxylic acids. Preferred acid anhydrides are glutaric anhydride and phthalic anhydride. These compounds may be used alone or in combination of two or more. The content of these acids is generally 0.05 to 5% by weight, and preferably 0.1 to 3% by weight, based on the total solid content of the entire photosensitive composition.

(Surfactant) The photosensitive composition of the present invention may contain a surfactant. As the surfactant, an amphoteric surfactant, an anionic surfactant, a cationic surfactant,
Nonionic surfactants, fluorine-based surfactants and the like can be mentioned. Examples of the amphoteric surfactant include lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl, and imidazolinium betaine.

As the anionic surfactant, a fatty acid salt,
Alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkyl allyl sulfate salt, naphthalene Sulfonic acid formalin condensate,
Examples include polyoxyethylene alkyl phosphate ester.
Examples of cationic surfactants include alkylamine salts and
Examples include primary ammonium salts and alkyl betaines.

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene. There are sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide and the like.

Examples of the fluorinated surfactants include copolymers of acrylates or methacrylates containing a fluoroaliphatic group and (polyoxyalkylene) acrylates or (polyoxyalkylene) methacrylates. These compounds may be used alone or in combination of two or more. Particularly preferably FC-430
(Sumitomo 3M Co., Ltd.) Fluorine-based polyethylene glycol # -2000 (Kanto Chemical Co., Inc.). The proportion in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

(Printout Material) A printout material capable of forming a visible image upon exposure can be added to the photosensitive composition. The printout material comprises an organic dye which changes its color tone by interacting with a compound which forms an acid or a free radical upon exposure. Examples of the compound which forms an acid or a free radical upon exposure include, for example, JP-A-50- O described in Japanese Patent No. 36209
-Naphthoquinonediazide-4-sulfonic acid halogenide,
An ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride and an electron-withdrawing substituent phenol or aniline acid described in JP-A-53-36223, JP-A-55-
Examples thereof include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A 77742, JP-A-57-148784 and the like.

(Compound which produces an acid or a free radical upon exposure to light) Examples of the compound which produces an acid or a free radical upon exposure to light which can be used in the photosensitive composition of the present invention include, for example, halomethyloxadiazole compounds, A halomethyl-s-triazine compound or the like is used. The halomethyl oxadiazole compound is a compound having halomethyl group, preferably trichloromethyl group, in oxadiazoles.

These compounds are known, for example, Japanese Patent Publication Nos. 57-6096 and 61-51788,
Japanese Patent Publication No. 1-28369, JP-A-60-13853
No. 9, JP 60-177340, and JP 60-24.
It is described in Japanese Patent No. 1049. In addition, the halomethyl-s-triazine compound is a compound having one or more halomethyl groups, preferably a trichloromethyl group, in the s-triazine ring.

In the photosensitive composition of the present invention, the addition amount of the compound capable of generating an acid or a free radical upon exposure to light is 0.
01 to 30% by weight is preferable, and 0.1 is more preferable.
10 to 10% by weight, particularly preferably 0.2 to 3% by weight. These compounds may be used alone or in combination of two or more.

(Dye) A dye may be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

As the dye, those which change color tone by reacting with free radicals or acids can be preferably used.
Here, "the color tone changes" includes both a change from colorless to a color tone, and a change from a colored to a colorless or different color tone. Preferred dyes are those which form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue #
603 (manufactured by Orient Chemical Industry Co., Ltd.), patent pure blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), crystal violet,
Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Pesic Fuchsin, Malachite Green, Oil Red, m
-Cresol purple, rhodamine B, auramine,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes such as 4-p-diethylaminophenyliminaquinoquine and cyano-p-diethylaminophenylacetanilide are colored to colorless. Alternatively, it may be mentioned as an example of a color changing agent that changes to a different color tone.

On the other hand, as a discoloring agent that changes from colorless to colored, leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p ′ -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′,
p ″ -tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p, Examples thereof include primary or secondary arylamine dyes represented by p ′, p ″ -triaminotriphenylmethane.

The proportion of the above-mentioned color changing agent in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight. These compounds may be used alone or in combination of two or more. Particularly preferred dyes are Victoria Pure Blue BOH and Oil Blue # 603.

(Oil-sensitizer) An oil-sensitizer for improving the oil-sensitivity of the image area (for example, a half-esterified product of an alcohol of a styrene-maleic anhydride copolymer described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partial esterification products of these with o-quinonediazide compounds, fluorine-based surfactants, p-hydroxystyrene 5
0% fatty acid ester, etc.) are preferably used. The amount of these additives added varies depending on the object of use and purpose, but is generally 0.01 to 30% by weight based on the total solid content.

(Inclusion Compound) The inclusion compound that can be used in the present invention is not particularly limited as long as it is a compound that can include water or an organic molecule, but it is soluble in the solvent used for preparing the composition. Organic compounds are preferred. Examples of such organic compounds include, for example, “Host Guest Chemistry” (Michio Hiraoka et al., Kodansha 1984).
Years, Tokyo) etc. and "Tetrahedron Report"
(No. 226 (1987) P5725A. Colle
t), "Chemical industry April issue" ((1991) P278 Shinkai et al.), "Chemical industry April issue ((1991) P288 Hiraoka et al.), and the like.

Inclusion compounds which can be preferably used in the present invention include, for example, cyclic D-glucans, cyclophanes, neutral polyligands, cyclic polyanions, cyclic polycations, cyclic peptides, SPHERANDS, CAVITAND
NDS) and their acyclic analogs. Among these, cyclic D-glucans and non-cyclic analogs thereof, cyclophanes, and neutral polyligands are more preferable. Examples of cyclic D-glucans and acyclic analogs thereof include compounds in which α-D-glucopyranose is linked by a glycolide bond.

Examples of the compound include sugars such as starch, amylose and amylopectone, which are composed of D-glucopyranose groups, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and D-glucopyranose group. A cyclodextrin having a degree of 9 or more, and SO ₃ C ₆ H ₄ CH ₂ C and the like.
₆ H ₄ SO ₃ group, NHCH ₂ CH ₂ NH group, NHCH ₂
CH ₂ NHCH ₂ CH ₂ NH group, SC ₆ H ₅ group, N ₃
Group, NH ₂ group, NEt ₂ group, SC (NH ₂ ⁺ ) NH
_Two groups, SH group, SCH ₂ CH ₂ NH ₂ group, imidazole group, ethylenediamine group and the like are introduced the following formula

[0062]

Embedded image

Examples include modified D-glucans represented by: Further, the following general formula [VI] and general formula [VI
And a branched cyclodextrin, a cyclodextrin polymer, etc.

[0064]

[Chemical 4]

In the general formula [VI], R _{1 to} R ₃ are
They may be the same or different and each represents a hydrogen atom, an alkyl group or a substituted alkyl group. In particular, those in which R _{1 to} R ₃ are a hydrogen atom or a hydroxyethyl group or a hydroxypropyl group are preferable, and those in which the content of the substituted alkyl group in one molecule is 15% to 50% are more preferable. n ₂ represents a positive integer of 4 to 10.

[0066]

Embedded image

[0067] In the general formula [VII], R represents a hydrogen ^{_{atom, -R 2 -CO 2 H, -R}} 2 -SO 3 H, -R 2 -N
H ₂ or ^{_{-N- (R 3) 2 (R}} 2 represents a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms, ^{R 3} is linear or branched alkyl having 1 to 5 carbon atoms Represents a group.

A production example of cyclodextrin is described in "J
ounal of the American Che
"Mical Society" Vol. 71, pp. 354 1
949, "Cheimish Berichte", Volume 90, page 2561, 1949, Volume 90, volume 256
The first page is described in 1957, but is not limited to these.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine, or a water-soluble substance such as disaccharide is branched or added. And preferably,
Maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of bound molecules in maltose may be 1, 2, 3 or the like) or glucosyl cyclodextrin in which glucose is bound to cyclodextrin (number of bound molecules in glucose Is 1 molecule, 2 molecules,
3 molecules or the like may be used).

Specific methods for synthesizing these branched cyclodextrins are described in, for example, Starch Chemistry, Vol. 33, No. 2, 1
Pp. 19-126 (1986), pp. 127-132 (1)
986), Starch Chemistry, Volume 30, No. 2, 231-23.
9 (1983) and the like, and can be synthesized by referring to these known methods. For example, maltosyl cyclodextrin uses cyclodextrin and maltose as raw materials and uses enzymes such as isoamylase and pullulanase. Then, it can be produced by a method of binding maltose to cyclodextrin. Glucosylcyclodextrin can be produced in the same manner.

These clathrate compounds may be added as a simple substance, but they improve the solubility of the clathrate compound itself or the clathrate compound incorporating the molecule in a solvent and the compatibility with other additives. For this reason, a polymer in which a substituent having an inclusion ability is suspended as a pendant substituent may be added together with the polymer.

Each of these components was dissolved in the following solvent,
By coating and drying the support surface according to the present invention,
By providing a photosensitive layer, the photosensitive lithographic printing plate of the present invention can be manufactured.

(Solvent) As a solvent which can be used when the photosensitive composition used in the present invention is dissolved, methanol,
Ethanol, n-propanol, i-propanol, n
-Aliphatic alcohols such as butanol, n-pentanol and hexanol, allyl alcohol, benzyl alcohol, anisole, phenetole, n-hexane, cyclohexane, heptane, hydrocarbons such as octane, nonane and decane, diacetone alcohol, 3 -Methoxy-1
-Butanol, 4-methoxy-1-butanol, 3-ethoxy-1-butanol, 3-methoxy-3-methyl-
1-butanol, 3-methoxy-3-ethyl-1-1-pentanol-4-ethoxy-1-pentanol, 5-methoxy-1-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, Methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-butanone, 4-hydroxy-2- Pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-
Pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (MC, EC , Butyl cellosolve,
Phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate, EC acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, Diethylene glycol monomethyl ether acetate, etc.), diethylene glycol dialkyl ethers (DMDG, DEDG, D
BDG, MEDG), triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether) , Monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate, monoethyl ether acetate, etc.), dipropylene glycol alkyl ethers (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether), ethyl formate , Propyl formate,
Carboxylic esters such as butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, methyl lactate ,
Examples thereof include ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer made of a water-insoluble organic solvent-soluble polymer compound capable of forming a film can be formed on the photosensitive layer. A matte layer is preferably provided on the surface of the photosensitive layer provided as described above, in order to shorten the vacuuming time during contact exposure using a vacuum baking frame and prevent baking blur. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986.
The method of providing a mat layer as described in each of the publications, the method of heat-bonding a solid powder as described in JP-B-62-62337 and the like can be mentioned.

(Matting Agent) The purpose of the matte layer is to improve the vacuum adhesion between the image film and the photosensitive lithographic printing plate in contact exposure, thereby shortening the vacuuming time, and further, the fine mesh during exposure due to poor adhesion. It is to prevent the dots from collapsing. As a coating method of the matte layer, there is disclosed in Japanese Patent Laid-Open No. 55-
No. 12974 includes a method of heat-sealing powdered solid powder and a method of spraying polymer-containing water described in JP-A No. 58-182636 and drying, and any method may be used. It is desirable that the matte layer itself be soluble in an alkaline developer or be removable by this.

(Coating) As a coating method used for coating the surface of the support with the photosensitive composition or the coating layer or the mat layer, there are conventionally known methods such as spin coating, wire bar coating, dip coating and air knife. Coating, roll coating,
Blade coating and curtain coating are used.

(Exposure) In using the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original image having a line image, a halftone image or the like can be applied to the photosensitive surface. A relief image is obtained by exposing the film in close contact with it and then removing the photosensitive layer in the non-image area with a suitable developing solution. Suitable light sources for exposure include mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps, carbon arc lamps, etc. are used.

(Processing) In the present invention, the developing solution and the developing replenishing solution used for processing (developing) the photosensitive lithographic printing plate both contain an alkali metal silicate. The alkali metal of the alkali metal silicate includes lithium, sodium and potassium, and potassium is the most preferable.

At the time of development, it is preferable that the development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate. A preferred developing solution and developing replenishing solution are [SiO ₂ ] /
[M] (in the formula, [SiO ₂ ] indicates the molar concentration of SiO ₂ , and [M] indicates the molar concentration of alkali metal) is 0.5.
To 2.0, especially 0.15 to 1.0, and an aqueous solution of an alkali metal silicate having a SiO ₂ concentration of 0.5 to 5.0% by weight based on the total weight. Further, particularly preferably, [SiO ₂ ] / [M] of the developer is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and [SiO ₂ ] of the developer replenisher. / [M] is 0.15 to 0.5, and S
The iO ₂ concentration is 1.0 to 3.0% by weight.

The above-mentioned developing solution and developing replenishing solution may contain water-soluble or alkali-soluble organic and inorganic reducing agents. Examples of the organic reducing agent include hydroquinone, metol, phenol compounds such as methoxyquinone, phenylenediamine, amine compounds such as phenylhydrazine, and the like, examples of inorganic reducing agents include sodium sulfite, potassium sulfite, and the like. Sulfites such as ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, potassium dihydrogen phosphite Phosphite, hydrazine, sodium thiosulfate, etc.
Examples thereof include sodium dithionite.

The water-soluble or alkali-soluble reducing agent can be contained in the developing solution and the developing replenishing solution in an amount of 0.05 to 10% by weight. In addition, the developer and development replenisher are
Organic acids carboxylic acids can be included. These organic acid carboxylic acids include aliphatic carboxylic acids having 6 to 20 carbon atoms and aromatic carboxylic acids having a benzene ring or a naphthalene ring substituted with a carboxyl group.

The aliphatic carboxylic acid has 6 to 2 carbon atoms.
Alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mistyric acid, palmitic acid,
Stearic acid and the like can be mentioned, with carbon number 6 being particularly preferred.
~ 12 alkanoic acids. Further, the aliphatic carboxylic acid may be a fatty acid having a double bond in the carbon chain or a fatty acid having a branched carbon chain. The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

Specific examples of the aromatic carboxylic acid include benzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, gallic acid, 1-hydroxy-
2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-
Naphthoic acid and the like can be mentioned.

The aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt. The content of the aliphatic carboxylic acid and the aromatic carboxylic acid may be at least 0.1 to 30% by weight. The developer and development replenisher may contain various anionic, nonionic and cationic surfactants and organic solvents. Furthermore, the developer and development replenisher should be
Known additives can be added.

[0085]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Example 1 An aluminum plate having a thickness of 0.3 mm (material 1050, temper H16) was immersed in a 10% sodium hydroxide aqueous solution kept at 85 ° C., degreased for 1 minute, and then washed with water. The degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, this aluminum plate is
% Nitric acid aqueous solution, temperature 30 ℃, current density 80
The surface was roughened for 30 seconds under the condition of A / dm ² . Then 70
It was immersed in a 1% aqueous sodium hydroxide solution kept at 0 ° C for 10 seconds and then washed with water. Then kept at 25 ° C. 10
% Aqueous solution of sulfuric acid for 10 seconds and then washed with water. Then, in a 30% sulfuric acid aqueous solution, the temperature is 35 ° C. and the current density is 3 A.
After anodic oxidation treatment for 1 minute under the condition of / dm ² , it was washed with water. After that, it was immersed in a 3.0% aqueous solution of ammonium acetate kept at 80 ° C for 1 minute for sealing treatment, washed with water, and
Aluminum support 1 was obtained by drying at 0 ° C. for 5 minutes.

When the surface of the obtained aluminum support 1 was photographed and observed by an electron microscope at a magnification of 200,000, it was confirmed that the average opening diameter of the micropores was 3.5 nm. Moreover, the fracture surface is examined with an electron microscope.
When photographed and observed at 0000 times, it was confirmed that the two-dimensional verticality of the micropore was approximately 90 degrees.

Next, a photosensitive composition coating liquid having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, the dry weight of the photosensitive composition coating liquid was set to 2.0 g / m ² .

Novolak resin (phenol / m-cresol / p-cresol molar ratio is 10/54/36 and Mw is 4000) 6.70 g Pyrogallolacetone resin (Mw: 3000) and o-naphthoquinonediazide-5-sulfonyl Condensate with chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g Methyl cellosolve 100 ml

The photosensitive lithographic printing plate thus obtained was used as a light source using a 4 kW metal halide lamp to obtain 8 mW / cm ²
Exposure for 60 seconds. This exposed photosensitive lithographic printing plate is used as a commercially available developer (SDR
-1, Konica Corp., 6 times diluted, development time 20 seconds,
Development was performed at a development temperature of 27 ° C. When the lithographic printing plate thus obtained was printed, the results shown in Table 1 were obtained.

Example 2 An aluminum support 2 was obtained in the same manner as in Example 1 except that electrolytic graining was carried out in a 2.0% hydrochloric acid solution. When the surface of the obtained aluminum support 2 was photographed and observed by an electron microscope at a magnification of 200,000, it was confirmed that the average opening diameter of the micropores was 3.5 nm.
When the fracture surface was photographed and observed with an electron microscope at a magnification of 50,000, it was confirmed that the two-dimensional perpendicularity of the micropore was approximately 75 degrees. In the same manner as in Example 1, the photosensitive composition was applied, exposed, developed and printed.

Comparative Example 1 An aluminum support 3 was obtained in the same manner as in Example 1 except that the sealing treatment was carried out by dipping in hot water kept at 90 ° C. for 1 minute. When the surface of the obtained aluminum support 3 was photographed and observed by an electron microscope at a magnification of 200,000, it was confirmed that the average opening diameter of the micropores was 6.0 nm. In addition, the fracture surface is 50
It was confirmed that the two-dimensional perpendicularity of the micropores was approximately 90 degrees when observed by photographing at 000 times. In the same manner as in Example 1, the photosensitive composition was applied, exposed, developed and printed.

Comparative Example 2 Electrolytic surface roughening was performed in a 2.0% hydrochloric acid solution, and sealing treatment was performed.
An aluminum support 4 was obtained in the same manner as in Example 1 except that the aluminum support 4 was immersed in hot water kept at 90 ° C. for 1 minute. When the surface of the obtained aluminum support 4 was photographed and observed by an electron microscope at a magnification of 200,000, it was confirmed that the average opening diameter of the micropores was 6.0 nm. When the fracture surface was photographed and observed with an electron microscope at a magnification of 50,000, the two-dimensional perpendicularity of the micropores was almost 7
It was confirmed to be 5 degrees. In the same manner as in Example 1, the photosensitive composition was applied, exposed, developed and printed.

[0093]

[Table 1]

Example 21 An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was immersed in a 10% sodium hydroxide aqueous solution kept at 85 ° C. and degreased for 1 minute. Washed with water. The degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, this aluminum plate is
% Nitric acid aqueous solution, temperature 30 ℃, current density 80
The surface was roughened for 30 seconds under the condition of A / dm ² . Then 70
It was immersed in a 1% aqueous sodium hydroxide solution kept at 0 ° C for 10 seconds and then washed with water. Then kept at 25 ° C. 10
% Aqueous solution of sulfuric acid for 10 seconds and then washed with water. Then, in a 30% sulfuric acid aqueous solution, the temperature is 35 ° C. and the current density is 4 A
After anodic oxidation treatment for 1 minute under the condition of / dm ² , it was washed with water. Then, it was immersed in a 3.0% aqueous solution of ammonium acetate kept at 80 ° C for 30 seconds for sealing treatment, washed with water, and dried at 80 ° C for 5 minutes to obtain an aluminum support 21.

The surface of the obtained aluminum support 21 was
When photographed and observed with an electron microscope at a magnification of 50,000 by a conventional method, it was confirmed that the thickness of the oxide film was 1000 nm.

The back surface is sealed and a chromium phosphoric acid aqueous solution ((chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 is used.
The surface dissolution rate is 1.0 mg /
min. Met. When immersed in a 0.5 wt% sodium hydroxide aqueous solution, the dissolution rate of the surface was 0.3 mg / se
c. Met.

Next, a photosensitive composition coating liquid having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, the dry weight of the photosensitive composition coating liquid was set to 2.0 g / m ² .

Novolac resin (molar ratio of phenol / m-cresol / p-cresol of 10/54/36 and Mw of 4000) 6.70 g of pyrogallolacetone resin (Mw: 3000) and o-naphthoquinonediazide-5-sulfonyl Condensate with chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g Methyl cellosolve 100 ml

The obtained photosensitive lithographic printing plate was used as a light source with a 4 kW metal halide lamp to obtain 8 mW / cm ²
Exposure for 60 seconds. This exposed photosensitive lithographic printing plate is used as a commercially available developer (SDR
-1, Konica Corp., 6 times diluted, development time 20 seconds,
Development was performed at a development temperature of 27 ° C. When the lithographic printing plate thus obtained was printed, the results shown in Table 2 were obtained.

Example 22 An aluminum support 22 was obtained in the same manner as in Example 21 except that electrolytic surface roughening was performed in a 2.0% hydrochloric acid solution. When the surface of the obtained aluminum support 22 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 1000 nm.

The back surface was sealed and a chromium phosphoric acid aqueous solution ((chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 was used.
The surface dissolution rate is 1.0 mg /
min. Met. When immersed in a 0.5 wt% sodium hydroxide aqueous solution, the dissolution rate of the surface was 0.3 mg / se
c. Met. A photosensitive composition was applied in the same manner as in Example 21, exposed and developed, and printed.

Example 23 An aluminum support 23 was obtained in the same manner as in Example 21 except that the anodizing time was 30 seconds. When the surface of the obtained aluminum support 23 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 400 nm.

The back surface was sealed and an aqueous solution of chromium phosphoric acid ((chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 was used.
The surface dissolution rate is 1.0 mg /
min. Met. When immersed in a 0.5 wt% sodium hydroxide aqueous solution, the dissolution rate of the surface was 0.3 mg / se
c. Met. A photosensitive composition was applied in the same manner as in Example 21, exposed and developed, and printed.

Example 24 An aluminum support 24 was obtained in the same manner as in Example 1 except that the electrolytic surface roughening was carried out in a 2.0% hydrochloric acid solution and the anodizing time was 30 seconds. Obtained aluminum support 2
When the 4 surfaces were photographed and observed with an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 400 nm.

The back surface is sealed and an aqueous solution of chromium phosphoric acid ((chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 is used.
The surface dissolution rate is 1.0 mg /
min. Met. When immersed in a 0.5 wt% sodium hydroxide aqueous solution, the dissolution rate of the surface was 0.3 mg / se
c. Met. A photosensitive composition was applied in the same manner as in Example 21, exposed and developed, and printed.

Comparative Example 21 An aluminum support 25 was obtained in the same manner as in Example 21, except that the sealing treatment was carried out by immersing the material in hot water kept at 80 ° C. for 30 seconds. When the surface of the obtained aluminum support 25 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 1000 nm.

The back surface was sealed and a chromium phosphoric acid aqueous solution ((chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 was used.
The surface dissolution rate is 2.0 mg /
min. Met. When immersed in a 0.5 wt% sodium hydroxide aqueous solution, the dissolution rate of the surface was 0.5 mg / se
c. Met. A photosensitive composition was applied in the same manner as in Example 21, exposed and developed, and printed.

Comparative Example 22 Electrolytic surface roughening was performed in a 2.0% hydrochloric acid solution, and sealing treatment was performed at 80 ° C.
An aluminum support 26 was obtained in the same manner as in Example 21 except that the aluminum support 26 was dipped in hot water kept for 30 seconds. When the surface of the obtained aluminum support 26 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 1000 nm.

The back surface is sealed and a chromium phosphoric acid aqueous solution ((chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1000 is used.
The surface dissolution rate is 2.0 mg /
min. Met. When immersed in a 0.5 wt% sodium hydroxide aqueous solution, the dissolution rate of the surface was 0.5 mg / se
c. Met. A photosensitive composition was applied in the same manner as in Example 21, exposed and developed, and printed.

[0110]

[Table 2]

Example 31 An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was immersed in a 10% sodium hydroxide aqueous solution kept at 85 ° C. and degreased for 1 minute. Washed with water. The degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, this aluminum plate is
% Nitric acid aqueous solution, temperature 30 ℃, current density 80
The surface was roughened for 30 seconds under the condition of A / dm ² . Then 70
It was immersed in a 1% aqueous sodium hydroxide solution kept at 0 ° C for 10 seconds and then washed with water. Then kept at 25 ° C. 10
% Aqueous solution of sulfuric acid for 10 seconds and then washed with water. Then, anodizing treatment was performed for 1 minute in a 30% aqueous solution of sulfuric acid at a temperature of 35 ° C. and a voltage of 10 V, and then washed with water.
After that, it is immersed in a 3.0% ammonium acetate aqueous solution kept at 80 ° C for 1 minute for sealing treatment, washed with water, and then at 80 ° C.
After drying for 5 minutes, an aluminum support 31 was obtained.

The surface of the obtained aluminum support 31 was
When photographed and observed with an electron microscope at a magnification of 50,000 by a conventional method, it was confirmed that the thickness of the oxide film was 1000 nm. Also, when photographed and observed at 200,000 times, the number of micropores was 1000 / μm ² and the ratio of surface area to pores was 0.8%.

Next, a photosensitive composition coating liquid having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, the dry weight of the photosensitive composition coating liquid was set to 2.0 g / m ² .

Novolac resin (phenol / m-cresol / p-cresol molar ratio of 10/54/36 and Mw of 4000) 6.70 g Pyrogallolacetone resin (Mw: 3000) and o-naphthoquinonediazide-5-sulfonyl Condensate with chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g Methyl cellosolve 100 ml

The obtained photosensitive lithographic printing plate was used as a light source with a 4 kW metal halide lamp to obtain 8 mW / cm ^2.
Exposure for 60 seconds. This exposed photosensitive lithographic printing plate is used as a commercially available developer (SDR
-1, Konica Corp., 6 times diluted, development time 20 seconds,
Development was performed at a development temperature of 27 ° C. When the lithographic printing plate thus obtained was printed, the results shown in Table 3 were obtained.

Example 32 An aluminum support 32 was obtained in the same manner as in Example 31 except that electrolytic graining was carried out in a 2.0% hydrochloric acid solution. When the surface of the obtained aluminum support 32 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 1000 nm. 20
When photographed and observed at a magnification of 0000, the number of micropores was 1000 / μm ² , and the ratio of pores in the surface area was 0.
It was 8%. In the same manner as in Example 31, the photosensitive composition was applied, exposed, developed and printed.

Example 33 An aluminum support 33 was obtained in the same manner as in Example 31 except that the anodizing time was 30 seconds. When the surface of the obtained aluminum support 33 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 400 nm. Again 200,000
The number of micropores was 1000 when photographed and observed at double magnification.
The number of holes / μm ² was 0.8%. The photosensitive composition was applied in the same manner as in Example 31,
It was exposed, developed and printed.

Example 34 An aluminum support 34 was obtained in the same manner as in Example 31 except that the electrolytic surface roughening was conducted in a 2.0% hydrochloric acid solution and the anodizing time was 30 seconds. When the surface of the obtained aluminum support 34 was photographed and observed by an electron microscope at a magnification of 50,000, it was confirmed that the thickness of the oxide film was 400 nm. Also, when photographed and observed at 200,000 times, the number of micropores was 1000 / μm ² and the ratio of surface area to pores was 0.8%. Example 31
The photosensitive composition was applied in the same manner as above, exposed, developed and printed.

Example 35 An aluminum support 35 was obtained in the same manner as in Example 31 except that the voltage condition of the anodizing treatment was 30 V and the sealing treatment time was 30 seconds. Obtained aluminum support 3
When 5 surfaces were photographed and observed by an electron microscope at a magnification of 50,000, it was confirmed that the thickness of the oxide film was 1000 nm. Also, when photographed and observed at 200,000 times, the number of micropores was 400 / μm ² , and the ratio of pores in the surface area was 0.8%. In the same manner as in Example 31, the photosensitive composition was applied, exposed, developed and printed.

Comparative Example 31 An aluminum support 36 was obtained in the same manner as in Example 31 except that the sealing treatment was conducted for 2 minutes. The surface of the obtained aluminum support 36 was observed with an electron microscope at 5000 by an ordinary method.
The thickness of the oxide film is 1000n when observed by photographing at 0 times.
m was confirmed. Also, when photographed and observed at 200,000 times, the number of micropores is 1000 / μm.
² , the surface area occupied by pores was 0.4%. In the same manner as in Example 31, the photosensitive composition was applied, exposed, developed and printed.

Comparative Example 32 An aluminum support 37 was prepared in the same manner as in Example 31 except that electrolytic roughening was carried out in a 2.0% hydrochloric acid solution under the conditions of anodizing voltage of 30 V and processing time of 30 seconds. Got When the surface of the obtained aluminum support 37 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 400 nm. Also, when photographed and observed at 200,000 times, the number of micropores was 400 / μm ² , and the ratio of pores in the surface area was 0.4%. In the same manner as in Example 31, the photosensitive composition was applied, exposed, developed and printed.

[0122]

[Table 3]

Example 36 An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was immersed in a 10% sodium hydroxide aqueous solution kept at 85 ° C., and degreasing treatment was performed for 1 minute. Washed with water. The degreased aluminum plate was immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute, desmutted, and washed with water. Then, this aluminum plate is
% Nitric acid aqueous solution, temperature 30 ℃, current density 80
The surface was roughened for 30 seconds under the condition of A / dm ² . Then 70
It was immersed in a 1% aqueous sodium hydroxide solution kept at 0 ° C for 10 seconds and then washed with water. Then kept at 25 ° C. 10
% Aqueous solution of sulfuric acid for 10 seconds and then washed with water. Then, anodizing treatment was performed for 1 minute in a 30% aqueous solution of sulfuric acid at a temperature of 35 ° C. and a voltage of 10 V, and then washed with water.
Then, it is immersed in a 4.0% ammonium acetate aqueous solution kept at 90 ° C for 1 minute for sealing treatment, washed with water, and then at 80 ° C.
After drying for 5 minutes, an aluminum support 38 was obtained.

The surface of the obtained aluminum support 38 was
When photographed and observed with an electron microscope at a magnification of 50,000 by a conventional method, it was confirmed that the thickness of the oxide film was 1000 nm. When photographed and observed at 200,000 times, it was confirmed that the number of micropores was 1000 / μm ² and the average opening diameter was 5 nm. When the surface roughness was measured by a conventional method, Rz was 4.2 μm.

Next, a photosensitive composition coating liquid having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate. At this time, the dry weight of the photosensitive composition coating liquid was set to 2.0 g / m ² .

Novolak resin (phenol / m-cresol / p-cresol molar ratio 10/54/36 and Mw 4000) 6.70 g Pyrogallolacetone resin (Mw: 3000) and o-naphthoquinonediazide-5-sulfonyl Condensate with chloride (esterification rate 30%) 1.50 g Polyethylene glycol # 2000 0.20 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (P-Methoxystyryl) -s-triazine 0.15 g Fluorosurfactant FC-430 (Sumitomo 3M Co., Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.02 g Methyl cellosolve 100 ml

The obtained photosensitive lithographic printing plate was used as a light source using a 4 kW metal halide lamp, and 8 mW / cm ²
Exposure for 60 seconds. This exposed photosensitive lithographic printing plate is used as a commercially available developer (SDR
-1, Konica Corp., 6 times diluted, development time 20 seconds,
Development was performed at a development temperature of 27 ° C. When the lithographic printing plate thus obtained was printed, the results shown in Tables 4 and 5 were obtained.

Example 37 An aluminum support 39 was obtained in the same manner as in Example 36 except that electrolytic graining was carried out in a 3.0% hydrochloric acid solution. When the surface of the obtained aluminum support 39 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 1000 nm. 20
When photographed and observed at 0000 times, it was confirmed that the number of micropores was 1000 / μm ² and the average opening diameter was 5 nm. When the surface roughness was measured by a conventional method, Rz was 4.9 μm. A photosensitive composition was applied in the same manner as in Example 36, exposed, developed and printed.

Comparative Example 33 An aluminum support 40 was obtained in the same manner as in Example 36 except that the voltage condition of the anodic oxidation treatment was 30 V and the treatment time was 30 seconds. When the surface of the obtained aluminum support 40 was photographed and observed by an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 400 nm. When photographed and observed at 200,000 times, it was confirmed that the number of micropores was 400 / μm ² and the average opening diameter was 5 nm. When the surface roughness was measured by a conventional method, Rz was 4.2 μm. A photosensitive composition was applied in the same manner as in Example 36, exposed, developed and printed.

Comparative Example 34 An aluminum support 41 was prepared in the same manner as in Example 36 except that electrolytic surface roughening was carried out in a 3.0% hydrochloric acid solution, and anodizing treatment was carried out under the conditions of voltage of 30 V and treatment time of 30 seconds. Got When the surface of the obtained aluminum support 41 was photographed and observed with an electron microscope at a magnification of 50,000 times, it was confirmed that the thickness of the oxide film was 400 nm. When photographed and observed at 200,000 times, it was confirmed that the number of micropores was 400 / μm ² and the average opening diameter was 5 nm. When the surface roughness was measured by a conventional method, Rz was 4.9 μm. A photosensitive composition was applied in the same manner as in Example 36, exposed, developed and printed.

[0131]

[Table 4]

[0132]

[Table 5]

<Evaluation Method> Evaluation of Printing Durability The lithographic printing plate thus obtained was printed on a printing machine (D manufactured by Mitsubishi Heavy Industries, Ltd.).
AIYA1F-1) coated paper, dampening water (Tokyo Ink Co., Ltd. etchant SG-51 concentration 1.5%), ink (Toyo Ink Mfg. Co., Ltd. high plus M red) printing Printing was carried out until ink inking defects appeared in the image area of the printed matter or ink adhered to the non-image area, and the number of printed sheets at that time was determined to evaluate printing durability.

-Recovery property of whole surface stain Under the same printing condition, ink was applied to the whole surface to stain it, and then printing was started, and the number of sheets where a clean and complete image was obtained was evaluated.

[0135] Contamination of the plate, under the same printing conditions, ink was applied to the entire surface at the next point after printing 5,000 sheets, the plate was removed from the printing machine, and left for one day and night.
It was printed again and the degree of stain was confirmed. ○: Dirt is recovered and a clean image is obtained ×: Dirt is not recovered

Dot gain: When the printing is carried out under the same printing conditions with the density of the image portion being 1.6, the number of screen lines on the printed matter is 150 lin.
The area of 50% halftone dot of e / inch was measured, and the amount of gain from the area of 50% halftone dot on the printing plate was evaluated. The area was measured with a Macbeth densitometer.

K value When the printing is performed with the density of the image portion being 1.6 under the same printing condition, the screen ruling on the printed matter is 150 lin
The density of 80% halftone dot of e / inch was measured and evaluated using the following formula. The concentration was measured with a Macbeth densitometer. K value = (image area density-80% halftone dot density) / image area density The larger the K value, the better the reproducibility of the high density halftone dot area.

* Backside Adhesion Material The adhesion state of white crystalline material on the back surface of the developed lithographic printing plate was observed. ◯: No adhered matter was observed ×: Adhered matter was observed The following negative type photosensitive composition coating solution was used in place of the positive type photosensitive composition coating solution in Example 1, and other similar experiments were conducted. As a result, the same effect as in Example 1 was obtained.

Example 38 <Negative-type photosensitive composition coating solution> Copolymer (p-hydroxyphenylmethacrylamide / acrylonitrile / ethyl acrylate / methacrylic acid = 10/25/57/8 Mw = 60,000) 5. 0 g Diazo resin (shown below) 0.5 g

[0140]

[Chemical 6] Julimer AC-10L (manufactured by Nippon Pure Chemical Industries, Ltd.) 0.05 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.1 g Methyl Cellosolve 100.0 ml

[0141]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a lithographic printing plate support excellent in hydrophilicity, water retention and adhesiveness to a photosensitive layer for printability, a method for producing the same, and a photosensitive lithographic printing plate. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C25D 11/08 C25D 11/08 11/16 301 11/16 301 11/18 301 11/18 301A G03F 7/00 503 G03F 7/00 503 (72) Inventor Yasuhisa Sugi 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company

Claims (11)

[Claims] 1. A support for a lithographic printing plate comprising an aluminum plate which has been roughened, anodized and sealed, after the pores of the micropores formed by the anodizing treatment have been sealed. A support for a lithographic printing plate, having an average opening diameter of 4 nm or less. 2. The lithographic printing plate support according to claim 1, wherein the two-dimensional perpendicularity of the micropores in the cross section of the anodized film is 85 degrees or more. 3. In a lithographic printing plate support comprising an aluminum plate which has been roughened, anodized and sealed, the aluminum surface on the side where the layer of the photosensitive composition is provided is an aqueous solution of chromium phosphoric acid. The dissolution rate is 0.2-1.
2 mg / min. , Dissolution rate in aqueous sodium hydroxide solution is 0.40 mg / sec. A support for a lithographic printing plate characterized by being: However, the chromic phosphoric acid aqueous solution is (chromic anhydride 20 g + 85 wt% phosphoric acid 35 ml) / 1
000ml sodium hydroxide aqueous solution is 0.5wt% 4. The lithographic printing plate support according to claim 3, wherein the oxide film formed by anodizing has a thickness of 500 to 1200 nm. 5. The method for producing a lithographic printing plate support according to claim 4, further comprising a step of electrochemically performing the surface roughening treatment in at least a nitric acid-based electrolytic solution. 6. A support for a lithographic printing plate comprising an aluminum plate which has been roughened, anodized and sealed, wherein the opening area of the micropores formed by the anodized treatment is a sealing treatment. Of the total surface area of the support.
A lithographic printing plate support characterized by being 5 to 5%. 7. A support for a lithographic printing plate comprising an aluminum plate which has been roughened, anodized and sealed, and has a density (A) of micropores formed by anodization [units / μm]. ² ] and anodized film thickness (B)
[Μm], micropore average opening diameter (C) [μm] after the sealing treatment, and Rz (D) [μ by the roughening treatment.
m] satisfies the following relational expression (I): a lithographic printing plate support. 0.02 <A × B × π × (0.5 × C) ² × D <0.10 (I) 8. The lithographic printing plate support according to claim 6, wherein the density of the micropores formed by the anodizing treatment is 500 to 1500 pieces / μm ² . 9. The lithographic printing plate support according to claim 8, wherein the oxide film formed by anodizing has a thickness of 500 to 1200 nm. 10. A method for producing a support for a lithographic printing plate, comprising a step of electrochemically performing the surface roughening treatment in at least a nitric acid-based electrolytic solution. 11. A photosensitive lithographic printing plate comprising a support for a lithographic printing plate according to claim 1 and a photosensitive layer containing a photosensitive composition coated on the support.