JPH1020506A - Photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing plate improved in printing resistance even in the case of using a cleaner without deteriorating sweeping stains at the time of printing by using a photosensitive material for a lithographic printing plate having an aluminum support obtained by anodizing it and treating it with an aqueous solution of and further with an aqueous solution of an alkali metal silicate. SOLUTION: This photosensitive material for the lithographic printing plate has the aluminum support obtained by anodizing it and treating it with an aqueous solution of the polyvinyl-solfonic acid and further with an aqueous solution of an alkali metal silicate. The aqueous solution of the polyvinyl- sulfonic acid to be used has a concentration of, preferably, 0.1-5weight% and a temperature of 30-60 deg.C and it is treated for an immersion time of 1-20sec. The anodized film of the aluminum plate thus treated is immersed in an aqueous solution of the alkali metal silicate in an amount of 1-30weight%, preferably, 2-15weight%, in a pH of 10-13 at 25 deg.C, for 0.5-40sec, preferably, 1-20sec, for example, at 50 deg.C-90 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive lithographic resin, and more particularly, to a photosensitive lithographic printing plate obtained by post-treating an anodized aluminum plate and further providing a photosensitive layer.

[0002]

2. Description of the Related Art Hitherto, a lithographic printing plate is obtained by developing a photosensitive lithographic printing plate obtained by coating a photosensitive composition in a thin layer on an aluminum plate after image exposure. The aluminum plate is usually subjected to a surface roughening treatment such as a mechanical method such as a brush grain method or a ball grain method, an electrochemical method such as an electrolytic grain method, or a method combining the both, and the surface thereof is made into a satin finish. Thereafter, it is etched with an aqueous solution of an acid or an alkali, and further subjected to an anodizing treatment and, if desired, subjected to a hydrophilic treatment to form a support for a lithographic printing plate. A photosensitive layer is provided on the support to provide a photosensitive layer. The planographic printing plate (so-called PS plate) is used. This PS version is
Usually, a lithographic printing plate is subjected to image exposure, development, correction, and gumming steps, and is mounted on a printing press for printing.

There are a positive type and a negative type photosensitive lithographic printing plate used for preparing a lithographic printing plate. As the positive photosensitive composition, those comprising an o-quinonediazide compound are widely used, and such a photosensitive substance is used alone or mixed with an alkali-soluble resin such as a novolak-type phenol resin or a cresol resin on a support. Painted. When a support having a hydrophilic surface is used, the exposed portion is decomposed by the o-quinonediazide compound and changes to alkali-soluble, so that the exposed portion is easily removed with an alkali developing solution to expose the hydrophilic surface of the support. Accepts water and repels ink. On the other hand, unexposed portions remaining as images are lipophilic and accept ink. Many negative photosensitive compositions use a diazonium salt, an azide compound or a photopolymerizable compound, and such a photosensitive substance is used alone or mixed with an additive such as a suitable resin and coated on a support. Is established. If a support having a hydrophilic surface is used, the unexposed portions are removed with a developer to expose the hydrophilic surface of the support, which receives water and repels the ink. On the other hand, the portion that is cured by exposure and remains as an image during development is lipophilic and accepts ink.

As a method for obtaining such a support having a hydrophilic surface, a method of treating an anodic oxide film with an aqueous solution of an alkali metal silicate described in US Pat. No. 3,181,461 is disclosed in Japanese Patent Application Laid-Open No. 2-185493. No. 46-356, in which an anodized aluminum plate is treated with an aqueous solution of an alkali metal silicate containing hydroxide.
No. 85, a method of treating an anodized aluminum plate with an aqueous solution of polyvinyl phosphonic acid, and further, a method of treating an anodized aluminum material described in JP-A-60-194096 with an aqueous alkali silicate solution. A method for treating an aqueous solution of at least one organic polymer having vinylphosphonic acid units and / or vinylmethylphosphinic acid units is known.

[0005]

The study by the present inventors has revealed that these methods for hydrophilizing the surface also have some problems. In other words, when the number of prints is large, the non-image portions on the printing plate gradually become hydrophobic and become contaminated with ink as printing progresses, so that the printed matter becomes dirty. To recover this, for example,
It is common practice to use cleaners based on a support etchant such as phosphoric acid and an ink dissolving agent such as an aliphatic hydrocarbon. However, for example, when a negative-type photosensitive lithographic printing plate is formed by treating the anodic oxide film with an aqueous alkali metal silicate solution to form a support, the adhesion between the photosensitive layer and the support when using a cleaner deteriorates. And the printing durability deteriorates. When a negative photosensitive lithographic printing plate is formed by treating an anodized aluminum plate with a polyvinylphosphonic acid aqueous solution to form a support, the printing durability when using a cleaner is sufficient, The so-called "wiping stain" that makes it difficult to remove the ink attached to the image area worsens. Further, JP-A-60-19409
As described in Example 1 of No. 6, after the anodic oxide film is treated with an aqueous solution of an alkali metal silicate, it is post-treated with an aqueous solution of polyvinylphosphonic acid to form a support to form a negative photosensitive lithographic printing plate. Also in this case, as in the case of treating with the alkali metal silicate aqueous solution alone, the wiping stain does not deteriorate, but the printing durability when the cleaner is used deteriorates, and the problem cannot be solved. Accordingly, an object of the present invention is to provide a lithographic printing plate having good printing durability when a cleaner is used, without deteriorating wiping stains during printing.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have obtained an aluminum support which has been anodized, treated with an aqueous solution of polyvinyl phosphonic acid, and treated with an aqueous solution of an alkali metal silicate. With the photosensitive lithographic printing plate having
The present invention has been completed. The present invention provides, by the above-described treatment method, a state in which polyvinylphosphonic acid and alkali metal silicate coexist in a well-balanced manner on the surface of the support.
Since the penetration of the cleaner into the interface between the photosensitive layer and the support is suppressed by polyvinylphosphonic acid, the adhesion to the photosensitive layer does not deteriorate, so that the printing durability does not deteriorate, and at the same time, the non-image area is formed by the coexisting alkali metal silicate. Is able to maintain sufficient hydrophilicity, so that it can also solve stains caused by wiping.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below step by step. (Polyvinylphosphonic acid aqueous solution treatment) The aqueous solution used for the polyvinylphosphonic acid aqueous solution treatment after the anodizing treatment has a concentration of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 0.1 to 5% by weight. 2 to 2.5
% By weight, at a temperature of 10 ° C. to 70 ° C., preferably 30 ° C. to 60 ° C., and suitably by immersion in this aqueous solution for 0.5 to 40 seconds, more preferably 1 to 20 seconds. . When the concentration of the aqueous solution of polyvinyl phosphonic acid is lower than 0.01% by weight, the amount of polyvinyl phosphonic acid adsorbed on the anodic oxide film is reduced, and sufficient printing durability cannot be obtained. On the other hand, when the concentration is higher than 10% by weight, The amount of phosphonic acid adsorbed is too large, and the soiling is reduced. On the other hand, if the treatment temperature is lower than 10 ° C., the amount of polyvinyl phosphonic acid adsorbed on the anodic oxide film decreases, and sufficient printing durability cannot be obtained. On the other hand, if the processing temperature is higher than 70 ° C., the amount of adsorbed polyvinyl phosphonic acid increases. It is too much and the dirt on payment deteriorates. Furthermore, if the immersion time is shorter than 0.5 seconds, the amount of polyvinylphosphonic acid adsorbed on the anodic oxide film is reduced, and sufficient printing durability cannot be obtained. Is too much, and the dirt on payment deteriorates.

(Alkali metal silicate treatment) The alkali metal silicate is used in an amount of 1 to 30% by weight, preferably 2 to 15% by weight of the anodic oxide film on the aluminum plate which has been treated as described above.
In an aqueous solution having a pH of 10 to 13 at 25 ° C,
For example, immersion is performed at 50 to 90 ° C. for 0.5 to 40 seconds, more preferably 1 to 20 seconds. PH of aqueous solution of alkali metal silicate
If it is lower than 10, the liquid gels, and if it is higher than 13, the oxide film will be dissolved. When the alkali metal silicate treatment temperature is lower than 50 ° C., partial desorption of polyvinyl phosphonic acid and adsorption of alkali metal silicate are not sufficiently performed during the treatment, and the surface is no different from the case where only polyvinyl phosphonic acid treatment is performed. , And the dirt is not improved. On the other hand, 9
If the temperature is higher than 0 ° C., almost all of the adsorbed polyvinyl phosphonic acid is removed, and the printing durability is not improved as in the case of only the alkali metal silicate treatment. Similarly, when the concentration is lower than 1% by weight and / or when the treatment time is shorter than 0.5 second, partial desorption of polyvinylphosphonic acid and adsorption of alkali metal silicate are not sufficiently performed, The surface is no different from the case where only the polyvinylphosphonic acid treatment is performed, and the soiling does not improve. On the other hand, if the concentration is higher than 30% by weight and / or
When the time is longer than seconds, the adsorbed polyvinyl phosphonic acid is almost completely removed, and the printing durability is not improved as in the case of only the alkali metal silicate treatment.

As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used, and among them, sodium silicate and potassium silicate are preferable. Hydroxides used to raise the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and preferably sodium hydroxide and potassium hydroxide. In addition, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned processing solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and aqueous solutions of sulfates, hydrochlorides, phosphates, acetates, oxalates, borates and the like. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, and the like. be able to.
Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. A photosensitive layer can be provided on the aluminum plate which has been subjected to the above treatment, and a hydrophilic undercoat layer can be further provided if necessary. A photosensitive layer can be provided on the aluminum plate which has been subjected to the above treatment, and a hydrophilic undercoat layer can be further provided if necessary.

(Aluminum Plate) The aluminum plate used in the present invention is a plate-like body made of pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. 10% by weight as alloy composition
It has the following heteroatom content. Aluminum which is suitable for the present invention is pure aluminum. However, since pure aluminum is difficult to produce due to smelting technology, it is preferable that aluminum contains as little foreign atoms as possible. In addition, any aluminum alloy having the above-described heteroatom content can be said to be a material that can be used in the present invention. As described above, the composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. The preferred material is JI
SA 1050, 1100, 1200, 300
3, 3103, and 3005. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.5 mm
It is about. Before anodizing the aluminum plate,
For removing rolling oil on the surface, for example, a degreasing treatment by treating with a surfactant or an alkaline aqueous solution, and a graining treatment are performed as desired.

(Graining treatment) The graining method includes:
There are a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of chemically selectively dissolving the surface. As a method for mechanically roughening the surface, known methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. As an electrochemical surface roughening method, there is a method of performing electrolysis in a hydrochloric acid or nitric acid electrolytic solution by alternating current or direct current to roughen the surface. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as necessary.

(Anodic Oxidation Treatment) As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte can be used as long as it can form a porous oxide film. Generally, sulfuric acid, phosphoric acid, and oxalic acid are used. , Chromic acid, or a mixed acid thereof is used, and the concentration of the electrolyte is appropriately determined depending on the type of the electrolyte. The anodizing treatment conditions vary depending on the electrolyte used and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ² ,
It is appropriate that the voltage is in the range of 1 to 100 V and the electrolysis time is in the range of 10 seconds to 50 minutes. Among these anodizing treatments,
In particular, the method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768 and the method of anodizing at a low concentration as described in US Pat. No. 4,211,619. Anodizing in sulfuric acid is preferred. Most preferably, it is a method of anodizing with a direct current having a current density of 5 to 20 A / dm ^{2 in} an electrolytic solution containing 5 to 20% by weight of sulfuric acid and 3 to 15% by weight of aluminum ions at a temperature of 25 to 50 ° C. . The amount of the anodic oxide film is 0.1 to 10 g / m ²
It can be.

(Hydrophilic undercoat layer) A preferred hydrophilic undercoat layer used in the present invention is described in JP-A-60-1494.
No. 91, comprising a compound having at least one amino group and at least one group selected from the group consisting of a carboxyl group and a salt group thereof, and a sulfo group and a salt group thereof. Hydrophilic layer, JP-A-60-23
A hydrophilic layer comprising a compound selected from a compound having at least one amino group and at least one hydroxyl group and a salt thereof disclosed in Japanese Patent Application Laid-Open No. Sho.
No. 19494, a hydrophilic layer containing a phosphate, and a polymer compound containing at least one monomer unit having a sulfo group disclosed in JP-A-59-101651 as a repeating unit in the molecule A hydrophilic layer, which is disclosed in JP-A-4-282637.
A substituted or unsubstituted aliphatic or aromatic compound represented by R ¹ (PO (OH) ₂ ) _n or R ^1- (PO (OH) (R ² )) _n (n is 1
Or 2, when n = 1, R ¹ and R ² represent a substituted or unsubstituted alkyl group, alkoxy group, aryloxy group, aryl group, acyl group, acyloxy group, and when n = 2, R ¹ is Represents a substituted or unsubstituted alkylene group or an arylene group, and R ² is as defined above), and an organic layer containing at least one compound selected from the group consisting of

(Photosensitive layer) As the composition of the photosensitive layer used in the present invention, any composition can be used as long as its solubility or swelling property in a developer changes before and after exposure. Hereinafter, typical ones will be described. (A) Photosensitive layer composed of o-quinonediazide compound Examples of the photosensitive compound of the positive photosensitive composition include o-quinonediazide compounds, and representative examples thereof include o-naphthoquinonediazide compounds. As the o-naphthoquinonediazide compound, an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403 is preferable. Other suitable o-quinonediazide compounds include U.S. Pat. No. 3,046,12.
There is an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and a phenol-formaldehyde resin described in JP-A Nos. 0 and 3,188,210. Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303,
8-63802, 48-63803, 48-9
No. 6575, No. 49-38701, No. 48-1335
No. 4, Japanese Patent Publication No. 37-18015, and No. 41-11222
No. 45-9610, No. 49-17481,
U.S. Pat. Nos. 2,797,213 and 3,454,4
No. 00, No. 3,544,323, No. 3,573
No. 917, No. 3,674,495, No. 3,78
5,825, British Patent Nos. 1,227,602, 1,251,345, 1,267,005, 1,329,888, and 1,330,932 ,
Examples described in each specification such as German Patent No. 854,890 can be given.

An o-naphthoquinonediazide compound obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride can also be used. Specific examples of such compounds are described in JP-A-51-139402 and JP-A-58-15094.
No. 8, No. 58-203434, No. 59-165053
No., No. 60-112445, No. 60-134235
No., No. 60-163443, No. 61-118744
Nos. 62-10645, 62-10646, 62-153950, 62-178562, and 6
4-76047, U.S. Pat. No. 3,102,809,
No. 3,126,281, No. 3,130,047
No. 3,148,983, No. 3,184,31
No. 0, No. 3,188,210, No. 4,639, 4
No. 06 and other publications or specifications.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound.
More preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent.
As the 1,2-diazonaphthoquinonesulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferable, but 1,2-diazonaphthoquinone-4-chloride is preferred.
Sulfonyl chloride can also be used. The obtained o-naphthoquinonediazide compound is a mixture of various compounds having different positions and amounts of 1,2-diazonaphthoquinonesulfonic acid ester groups, but all of the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. The proportion of the compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

As the photosensitive compound which acts positively without using an o-naphthoquinonediazide compound, for example, a polymer compound having an o-nitrocarbinol ester group described in JP-B-56-2696 is also included in the present invention. Can be used. Further, a compound capable of generating an acid by photolysis and a —CO—C— group or —C dissociated by the acid.
A combination system with a compound having an -O-Si group can also be used in the present invention. For example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90303), a combination of an orthoester or an amide acetal compound (JP-A-51-1983)
120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429).
No.), a combination with an enol ether compound (Japanese Unexamined Patent Publication No.
-12995), a combination with an N-acylimino carbon compound (JP-A-55-126236), and a combination with a polymer having an orthoester group in the main chain (JP-A-56-1).
No. 7345), a combination with a silyl ester compound (JP-A-60-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12).
No. 1446). The amount of these positive-acting photosensitive compounds (including the above combinations) in the photosensitive composition of the present invention is suitably from 10 to 50% by weight, more preferably from 15 to 40% by weight. It is.

Although the o-quinonediazide compound alone can constitute the photosensitive layer, it is preferably used together with a resin soluble in alkaline water as a binder. Examples of such resins soluble in alkaline water include novolak resins having this property, such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, and m- / p-.
Mixed cresol formaldehyde resin, cresol formaldehyde resin such as phenol / cresol (m-, p- or m- / p-mixed) mixed formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene Acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, an acrylic resin having a sulfonamide group described in JP-A-2-866, and a urethane-based resin. Various alkali-soluble polymer compounds can be contained. These alkali-soluble polymer compounds have a weight average molecular weight of 500-20,000 and a number average molecular weight of 200-6.
000 is preferred. Such an alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

Further, as described in U.S. Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin is used as a substituent. It is preferable to use a condensate of phenol and formaldehyde or an o-naphthoquinonediazidosulfonic acid ester of these condensates (for example, those described in JP-A-61-243446) in order to improve the oil sensitivity of an image.

In the photosensitive composition of the present invention, a cyclic acid anhydride for enhancing the sensitivity, a printing-out agent for obtaining a visible image immediately after exposure, a dye or other filler as an image coloring agent, and the like are included. Can be added. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, and the like as described in US Pat. No. 4,115,128.
Hexahydrophthalic anhydride, 3,6-endooxy-Δ
⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. By containing these cyclic anhydrides in an amount of 1 to 15% by weight based on the total weight of the composition, the sensitivity can be increased up to about three times. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. More specifically,
And combinations of o-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dyes described in JP-A-36209 and JP-A-53-8128.
No. 36223, No. 54-74728, No. 60-36
No. 26, No. 61-143748, No. 61-15164
No. 4, 63-58440, and combinations of trihalomethyl compounds and salt-forming organic dyes. Other dyes besides the above-mentioned salt-forming organic dyes can be used as image coloring agents. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink #
312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Viewer Blue, Crystal Violet (CI42555), Ethyl Violet (CI42600), methyl violet (C
I42535), rhodamine B (CI45170B),
Malachite green (CI42000), methylene blue (CI52015) and the like can be mentioned. Also,
Dyes described in JP-A-62-293247 are particularly preferred.

In the present invention, the photosensitive composition is dissolved in a solvent capable of dissolving each of the above-mentioned components and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, toluene , Ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide,
Examples include dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol, and dimethyl ether. These solvents are used alone or in combination. The concentration (solid content) of the above components in the solution is 2 to 50.
% By weight. The coating amount varies depending on the application, but, for example, in the case of a photosensitive lithographic printing plate, generally, the solid content is preferably 0.5 to 3.0 g / m ² . As the amount of coating decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate. In the photosensitive composition of the present invention, a surfactant for improving coating properties, for example, JP-A-62-17095
No. 0 can be added. A preferable addition amount is 0.01 to 1% by weight of the total photosensitive composition, more preferably 0.05 to 1% by weight.
~ 0.5% by weight.

(B) Photosensitive Layer Consisting of Diazo Resin and Binder A negative working photosensitive diazo compound is disclosed in US Pat.
Diphenylamine which is a reaction product of a diazonium salt and an organic condensing agent containing a reactive carbonyl salt such as aldol or acetal disclosed in the specifications of JP-A Nos. 063,631 and 2,667,415. A condensation product of a p-diazonium salt and formaldehyde (a so-called photosensitive diazo resin) is preferably used. Other useful condensed diazo compounds are disclosed in JP-B-49-48001 and JP-B-49-48001.
-45322 and 49-45323. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts and can therefore be applied from aqueous solutions. Further, these water-soluble diazo compounds are reacted with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups or both by a method disclosed in Japanese Patent Publication No. 47-1167,
A substantially water-insoluble photosensitive diazo resin, which is the reaction product, can also be used. Also, JP-A-56-12
It can also be used as a reaction product with hexafluorophosphate or tetrafluoroborate as described in JP-A-1031.

Examples of reactants having a phenolic hydroxyl group include diphenolic acids such as hydroxybenzophenone, 4,4-bis (4'-hydroxyphenyl) pentanoic acid, resorcinol, or diresorcinol. Further, it may have a substituent. Hydroxybenzophenone includes 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone or 2,2 ', 4,4'-tetrahydroxybenzophenone. It is. Preferred sulfonic acids include, for example, aromatic sulfonic acids such as sulfonic acids such as benzene, toluene, xylene, naphthalene, phenol, naphthol and benzophenone, or soluble salts thereof, for example, ammonium and alkali metal salts. The sulfonic acid group-containing compound may be generally substituted with a lower alkyl, a nitro group, a halo group, and / or another sulfonic acid group. Preferred examples of such compounds include benzene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid, 2,5-dimethylbenzene sulfonic acid, sodium benzene sulfonate, naphthalene-2-sulfonic acid, 1-naphthol-2 (or 4) -sulfonic acid, 2,4-dinitro-1-natol-
7-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, sodium m- (p'-anilinophenylazo) benzenesulfonic acid, alizarin sulfonic acid, o-toluidine-m-sulfonic acid and ethanesulfone Acids and the like. Also useful are the sulfonic esters of alcohols and their salts. Such compounds are usually readily available as anionic surfactants.
Examples include lauryl sulfate, alkylaryl sulfate, p-nonylphenyl sulfate, 2
Ammonium salts such as phenylethyl sulfate and isooctylenoxydiethoxyethyl sulfate or alkali metals.

These substantially water-insoluble photosensitive diazo resins can be precipitated by mixing the water-soluble photosensitive diazo resin with the aqueous solution of the aromatic or aliphatic compound, preferably in substantially equal amounts. Isolated as Further, diazo resins described in British Patent No. 1,312,925 are also preferable. Also, a diazo resin containing an oxygen acid group of phosphorus described in JP-A-3-253857 and a diazo resin condensed with a carboxyl-containing aldehyde or an acetal compound thereof described in JP-A-4-18559. Further, a diazo resin copolymerized with a carboxy group-containing aromatic compound such as phenoxyacetic acid described in Japanese Patent Application No. 3-23031 is also preferable.
The most preferred diazo resin is 2-methoxy-4- condensate of p-diazodiphenylamine and formaldehyde.
Hydroxy-5-benzoylbenzenesulfonate. The content of the thiazo resin is 5 to 50% by weight in the photosensitive layer.
It is appropriate that it is included. When the amount of the diazo resin decreases, the photosensitivity naturally increases, but the stability with time decreases. The optimal amount of diazo resin is about 8-20% by weight.

On the other hand, various polymer compounds can be used as the binder. In the present invention, those containing groups such as hydroxy, amino, carboxylic acid, amide, sulfonamide, active methylene, thioalcohol and epoxy are used. Is desirable. Such preferred binders include shellac, described in GB 1,350,521, GB 1,460,973 and US Pat. No. 4,123,276. A polymer containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit, a polyamide resin described in U.S. Pat. No. 3,751,257, a British patent 1,07
Phenolic resins described in U.S. Pat. No. 4,392, and polyvinyl acetal resins such as, for example, polyvinyl formal resins and polyvinyl butyral resins, linear polyurethane resins described in U.S. Pat. No. 3,660,097. Phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, polymers containing amino groups such as polyaminosulfone and polyalkylamino (meth) acrylate, cellulose acetate, cellulose alkyl ether, cellulose acetate phthalate, etc. Cellulose derivatives and the like are included. Compositions comprising a diazo resin and a binder further include a pH indicator as described in GB 1,041,463, U.S. Pat.
Additives such as phosphoric acid and dyes described in 236,646 can be added.

(C) Photosensitive layer comprising azide compound and binder (high molecular compound) For example, British Patent Nos. 1,235,281 and 1,491
5,861 and JP-A-51-32331.
And the compositions comprising an azide compound and a water-soluble or alkali-soluble polymer compound described in JP-A Nos. 51-36128 and 50-84, and JP-A-50-5102 and 50-84.
No. 302, No. 50-84303, No. 53-12984
And compositions comprising a polymer containing an azide group and a polymer compound as a binder described in each of the above publications. (D) Other photosensitive resin layers For example, polyester compounds disclosed in JP-A-52-96696, British Patent No. 1,112,277
No. 1,313,390 and 1,341,00
No. 4,377,747, etc., polyvinyl cinnamate-based resins described in U.S. Pat.
No. 2,528, 4,072,527 and JP-A-2-244050, the photopolymerizable photopolymer composition described in each specification and the like, and silver trigger polymerization described in JP-A-7-28248. A mold composition is included. (E) Electrophotographic photosensitive layer The electrophotographic photosensitive layer is mainly composed of a photoconductive compound and a binder, but for the purpose of improving sensitivity, obtaining a desired photosensitive wavelength range, and the like, known pigments and dyes as necessary. , A chemical sensitizer, and other additives. The photosensitive layer can be composed of a single layer or a plurality of layers having separate functions of charge generation and charge transport. A lithographic printing plate can be obtained by forming a toner image on a photosensitive layer by a known electrophotographic process, using this as a resist layer, and decoding a non-image portion. Such a photosensitive layer is described, for example, in JP-B-37-17162 and JP-B-38-6.
No. 961, JP-A-56-107246, and JP-A-60-25
No. 4142, JP-B-59-36259, and 59-25
No. 217, JP-A-56-146145, JP-A-62-19
No. 4257, No. 57-147656, No. 58-100
Nos. 862, 57-161863, and many other publications, all of which can be suitably used.

The thickness of the photosensitive layer can be 0.1 to 30 μm, more preferably 0.5 to 10 μm. The amount of the photosensitive layer provided on the support (fixed frequency) from about 0.1 to about 7 g / m ^2, preferably in the range of 0.5-4 g / m ^2. The surface of the photosensitive layer provided as described above is preferably matted in order to shorten the time for evacuation during contact exposure using a vacuum printing frame and to prevent printing blur. Specifically, a method of providing a mat layer as described in JP-A-50-125805, JP-B-57-6582 and JP-B-61-28986 is described in JP-B-62-62337. And a method of thermally fusing such a solid powder. After the imagewise exposure of the photosensitive lithographic printing plate of the present invention, the lithographic printing plate is made into a lithographic printing plate by a process including development by a conventional method. For example, the photosensitive layer
In the case of a positive planographic printing plate having (A), after image exposure,
U.S. Pat. No. 4,259,434 and JP-A-3-903.
By developing with an aqueous alkali solution as described in JP-A-88-88, the exposed portion of the photosensitive layer is removed to obtain a lithographic printing plate. In the case of a negative type lithographic printing plate having a photosensitive layer (B) composed of a diazo resin and a binder, after image exposure, the plate is developed with a developing solution as described in, for example, US Pat. No. 4,186,006. By doing
The lithographic printing plate is obtained by removing the unexposed portion of the photosensitive layer.

The photosensitive lithographic printing plate of the present invention is disclosed in
JP-A-8002, JP-A-55-115045 and JP-A-59-15045.
It goes without saying that the plate-making process may be performed by the method described in each of the publications of No. 58431. That is, after the development processing,
A desensitization treatment after washing with water, a desensitization treatment as it is, a treatment with an aqueous solution containing an acid, or a treatment with an aqueous solution containing an acid may be followed by a desensitization treatment. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. The processing capacity is reduced. At this time, a fresh unused developer (replenisher) is added, or the processing capacity is increased by using a replenisher having a high alkalinity as described in JP-A-54-62004. May be recovered. In this case, a method of adding a replenisher in an amount proportional to the length of one piece of the PS plate to be processed or US Pat.
It is preferred to replenish by the method described in 2,246. Further, the plate making process as described above is disclosed in
It is preferably carried out using an automatic developing machine as described in JP-A Nos. 054 and 2-32357. Further, when the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary image portions are erased, it is described in JP-B-2-13293. It is preferable to use such an erasing liquid. Further, as the desensitized gum to be applied as required in the final step of the plate making step, Japanese Patent Publication Nos. 62-16834, 62-25118, and 6
3-52600, JP-A-62-7595 and JP-A-62-7595
Those described in JP-A-11693 and JP-A-62-83194 are preferable. Furthermore, when the photosensitive lithographic printing plate of the present invention is image-exposed, developed, rinsed or rinsed, optionally erased, and washed with water before burning, the Japanese Patent Publication No. 61-2518 before burning. JP-A-55-28062, JP-A-62-31859, and JP-A-62-21859.
It is preferable to carry out treatment with a surface conditioning solution as described in each publication of 1-159655.

[0029]

The present invention will be specifically described below with reference to examples. The percentages in the examples are% by weight unless otherwise specified. (Example 1) The surface of a JIS 1050 aluminum sheet was grained with a rotating nylon brush using a pumice water suspension as an abrasive. At this time, the surface roughness (center line average roughness) was 0.5 μm. After washing with water, a 10% aqueous solution of caustic soda was immersed in a solution heated to 70 ° C., and etching was performed so that the amount of aluminum dissolved was 6 g / m ² .
After washing with water, it was immersed in a 30% aqueous nitric acid solution for 1 minute for neutralization, and washed sufficiently with water. Thereafter, electrolytic roughening is performed for 20 seconds in a 0.7% nitric acid aqueous solution using a rectangular wave alternating voltage of 13 volts at the anode and 6 volts at the cathode, and immersed in a 50% solution of 20% sulfuric acid. After washing the surface, it was washed with water.
Further, a porous anodic oxide film forming treatment was performed in a 20% sulfuric acid aqueous solution using a direct current. Electrolysis was performed at a current density of 5 A / dm ² and the electrolysis time was adjusted to adjust the anodic oxide film weight to 2.5 g / g.
m ² ] substrate (I). 0.5% of this substrate (I)
The mixture was treated with an aqueous solution of polyvinyl phosphonic acid at 60 ° C. for 5 seconds, washed with water, and then treated with a 2.5% aqueous solution of sodium silicate at 70 ° C. for 12 seconds and washed with water. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer.

Table 1 Photosensitive composition ・ 5 g of polyurethane resin (a) obtained by the following synthesis method ・ 1.2 g of dodecylbenzenesulfonate of a condensate of 4-diazophenylamine and formaldehyde ・ propane-1, 2,3-tricarboxylic acid 0.05 g, phosphoric acid 0.05 g, 4-sulfophthalic acid 0.05 g, tricresyl phosphate 0.25 g, half-ester of styrene-maleic anhydride copolymer with n-hexanol 0.1 g, Victoria Pure Naphthalene sulfonate of blue BOH 0.18 g ・ [C ₆ F ₁₇ CH ₂ CH ₂ O] _1.7 Compound represented by PO [OH] _1.3 0.015 g ・ MegaFac F-177 (Dainippon Ink & Chemicals, Inc.) 0.06 g ・ 1-methoxy-2-propanol 20 g ・ Methanol 40 g ・ Methylethyl Luketone 40g ・ Ion exchange water 1g

Synthesis Method of Polyurethane Resin (a) In a 500 ml three-neck round bottom flask equipped with a condenser and a stirrer, 11.5 g (0.0860 mole) of 2,2-bis (hydroxymethyl) propionic acid and 7. 26 g (0.0684 mole) and 1,4-
4.11 g (0.0456 mole) of butanediol was added and dissolved in 118 g of N, N-dimethylacetamide. 30.8 g (0.123 mole) of 4,4'-diphenylmethane diisocyanate, 13.8 g (0.0819 mole) of hexamethylene diisocyanate and 0.1 g of di-n-butyltin dilaurate as a catalyst were added thereto, and the mixture was stirred. Heated at 90 ° C. for 7 hours. 100 ml of N, N-dimethylacetamide, 50 ml of methanol and 50 ml of acetic acid were added to the reaction solution, and the mixture was stirred and then poured into 4 liters of water with stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under reduced pressure to obtain 62 g of a polymer (polyurethane resin (a)).

The lithographic printing plate obtained is shown in Table 3 showing the cleaning stains and the printing durability when using a cleaner. The cleaner uses Hoechst plate cleaner RC-95, 500
The operation of infiltrating the above-mentioned cleaner into the waste cloth every time printing zero sheets, wiping the image portion of the printing plate 10 times, and then leaving it for 3 minutes was repeated. (The same cleaner was used under the same conditions in the following Examples and Comparative Examples.)

Example 2 The substrate (I) was treated with a 0.5% aqueous solution of polyvinylphosphonic acid at 40 ° C. for 5 seconds, washed with water, treated with a 2.5% aqueous solution of sodium silicate at 70 ° C. for 12 seconds, and washed with water. . The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Table 3 shows the cleaning stains and the printing durability when the cleaner was used.

Example 3 The substrate (I) was treated with a 2.0% aqueous solution of polyvinylphosphonic acid at 60 ° C. for 5 seconds, washed with water, treated with a 25% aqueous solution of sodium silicate at 70 ° C. for 12 seconds, and washed with water. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Dirt at this time,
Table 3 shows the printing durability when the cleaner was used.

Example 4 The substrate (I) was treated with a 0.5% aqueous solution of polyvinylphosphonic acid at 60 ° C. for 5 seconds, washed with water, treated with a 10% aqueous solution of sodium silicate at 70 ° C. for 12 seconds, and washed with water. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Dirt at this time,
Table 3 shows the printing durability when the cleaner was used.

Example 5 The substrate (I) was treated with a 0.5% aqueous solution of polyvinylphosphonic acid at 60 ° C. for 5 seconds, washed with water, treated with a 2.5% aqueous solution of sodium silicate at 70 ° C. for 12 seconds, and washed with water. . Thereafter, a hydrophilic undercoat liquid shown in Table 2 was applied. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Table 3 shows the cleaning stains and the printing durability when the cleaner was used.

Table 2 Undercoat liquid ・ Methyl methacrylate / ethyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (60/25/15 molar ratio) 0.02 g ・ Methanol 100 g

Comparative Example 1 The substrate (I) was treated with a 2.5% aqueous solution of sodium silicate at 70 ° C. for 12 seconds and washed with water. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Table 3 shows the cleaning stains and the printing durability when the cleaner was used.

Comparative Example 2 The substrate (I) was treated with a 2.0% aqueous solution of polyvinylphosphonic acid at 60 ° C. for 5 seconds and washed with water. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Table 3 shows the cleaning stains and the printing durability when the cleaner was used.

COMPARATIVE EXAMPLE 3 The substrate (I) was treated with a 2.5% aqueous solution of sodium silicate at 70 ° C. for 12 seconds, washed with water, and washed with 0.5% aqueous solution.
% Polyvinylphosphonic acid aqueous solution at 60 ° C for 5 seconds,
Washed with water. The composition shown in Table 1 was applied to the substrate thus prepared so that the coating weight after drying was 2.5 [g / m ² ], and dried to form a photosensitive layer. Table 3 shows the cleaning stains and the printing durability when the cleaner was used.

[0041]

[Table 1]

From Table 3, it can be seen that the photosensitive lithographic printing plate according to the present invention is excellent in both wiping stains and printing durability when using a cleaner.

[0043]

According to the photosensitive lithographic printing plate of the present invention, it is possible to provide a photosensitive lithographic printing plate which has improved printing durability when a cleaner is used, without deteriorating stains during printing. .

Claims (1)

[Claims] 1. A photosensitive lithographic printing plate having an aluminum support which has been anodized, treated with an aqueous solution of polyvinylphosphonic acid, and treated with an aqueous solution of an alkali metal silicate.