JP2709535B2 - Photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive lithographic printing plate and, more particularly, to a positive photosensitive lithographic printing plate comprising an o-quinonediazide compound having an intermediate layer provided on an aluminum plate subjected to a hydrophilic treatment. It relates to a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Heretofore, 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 above 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 has a satin finish. After that, the substrate 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 lithographic printing plate support. A photosensitive layer is provided on the support. To obtain a photosensitive lithographic printing plate (so-called PS plate). 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.

However, in the above lithographic printing plate,
The substance contained in the photosensitive layer is irreversibly adsorbed on the non-image area of the lithographic printing plate obtained by image-exposing and developing the positive working PS plate, and contaminates the non-image area. Problem, or it is difficult to distinguish between the image part and the non-image part in the correction process, and the correction mark remains clearly on the non-uniform plate surface. If the degree of the correction becomes severe, the plate becomes dirty and cannot be used as a printing plate. was there.

In order to improve this, the surface of an aluminum support which has been anodized has conventionally been coated with a material such as that described in US Pat.
Alkali metal silicate treatment (for example, sodium silicate aqueous solution) as disclosed in the specification of Japanese Patent No. 1,461,
Alternatively, a treatment with fluorinated zirconic acid as disclosed in JP-B-36-22063 or the like, or U.S. Pat.
A method of hydrophilizing by polyvinyl phosphonic acid treatment and the like disclosed in 3,276,868 and the like has been used. However, in these methods, although the remaining color of the non-image area or the above-mentioned stainability is improved, the number of printed sheets is only several hundreds because the adhesion between the photosensitive composition and the support is insufficient. .

[0005] In addition, amino acids and salts thereof (alkali metal salts such as Na salt and K salt, ammonium salts, etc.) disclosed in Japanese Patent Application Laid-Open No. Sho 60-1499491 are additionally provided on an anodized aluminum support. Hydrochloride, oxalate, acetate, phosphate, etc.), JP-A-60-232998
Nos. 3,087,067 and 5,887,098. Amines having hydroxyl groups and their salts (hydrochloride, oxalate, phosphate, etc.) disclosed in
A method of undercoating a compound having an amino group and a phosphonic acid group or a salt thereof disclosed in JP-A-165183 is proposed.

However, in these methods, the reduction of the residual color in the non-image area is not always sufficient, and the above-mentioned stains are particularly seriously generated when the developer becomes fatigued. In addition, although not as good as the hydrophilizing treatment of alkali metal silicate or the like, the printing durability deteriorated and was not sufficient as compared with the case without the undercoat.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithographic plate which has less residual color (residual dye components in a photosensitive layer) in a non-image area when developed after imagewise exposure and has less correction stain due to an erasing liquid. The object is to provide a positive photosensitive lithographic printing plate that gives a printing plate. Still another object is to provide a positive photosensitive lithographic printing plate which provides a lithographic printing plate having a high adhesion of an image portion to an aluminum plate and excellent printing durability.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and have completed the present invention. In the present invention, R ¹ (PO (OH) ₂ ) is placed on an aluminum plate that has been subjected to anodizing treatment and then subjected to hydrophilic treatment.
_n or R ^1- (PO (OH) (R ² )) _n where n
Is 1 or 2, and when n is 1, R ¹ and R ² represent a substituted or unsubstituted alkyl group, alkoxy group, aryloxy group, aryl group, acyl group, acyloxy group, and n
Is 2, R ¹ represents a substituted or unsubstituted alkylene group or an arylene group, and R ² is as defined above), the organic layer containing at least one compound selected from the group consisting of And a positive type photosensitive layer containing an o-quinonediazide compound and an organic polymer is provided thereon.

Hereinafter, the present invention will be described in detail. The aluminum plate used in the present invention is a plate-shaped body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of foreign atoms. This foreign atom
There are silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign atoms in the alloy is at most 10% by weight or less. Aluminum which is suitable for the present invention is pure aluminum. However, since pure aluminum is difficult to produce due to refining technology, it is preferable that the content of foreign atoms be as low as possible. or,
Any aluminum alloy having the above-described content can be said to be a material applicable to the present invention. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly available materials can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.5 mm.

Prior to the surface roughening treatment of the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant or an alkaline aqueous solution is performed to remove the rolling oil on the surface. The photosensitive lithographic printing plate of the present invention may be one that can be used on one side only, or one that can be used on both sides by the same treatment. Since the same applies to both surfaces, the case of one surface will be described below. First, the aluminum plate is subjected to a surface roughening treatment. As the surface roughening treatment method, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. There is a way. As a method for mechanically roughening the surface, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. 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 required. As the electrolyte used for the anodizing treatment of the aluminum plate, any electrolyte can be used as long as it forms a porous oxide film.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 the electrolyte.

The anodic oxidation treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, and the solution temperature is 5 to 70 ° C.
It is appropriate that the current density is 5 to 60 A / dm ² , the voltage is 1 to 100 V, and the electrolysis time is 10 seconds to 50 minutes. The amount of the anodic oxide film is preferably at least 1.0 g / m ^2, but is more preferably in the range of 2.0 to 6.0 g / m ² . If the anodic oxide film is less than 1.0 g, the printing durability is insufficient,
The non-image portion of the lithographic printing plate is easily scratched, and so-called "scratch stain" in which ink adheres to the scratched portion during printing.

As the hydrophilization treatment used after the above-mentioned treatment, a conventionally known hydrophilization treatment is used. U.S. Patent No.
No. 2,714,066, No. 3,181,461, No. 3,280,7
No. 34, No. 3,902,734, alkali metal silicates (eg aqueous sodium silicate solution)
There is a law. In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. No. 3,276,86.
No. 8, No. 4,153,461 and No. 4,689,272, for example, a method of treating with polyvinyl phosphonic acid is used. Among these, a particularly preferred hydrophilization treatment is an alkali metal silicate treatment.

After performing these hydrophilic treatments, the following organic layers are provided on the aluminum plate by various methods described below. The compound used in the present invention is (I) R ^1- (PO
(OH) ₂ ) _n or (II) R ^1- (PO (OH) (R
² )) _{n wherein} n is 1 or 2, and when n is 1, R ¹ and R ² are a substituted or unsubstituted alkyl group (preferably having 1 to 14 carbon atoms), alkoxy, Groups (preferably having 1 to 14 carbon atoms), aryloxy groups (preferably having 6 to 10 carbon atoms), aryl groups (preferably having 6 to 10 carbon atoms), acyl groups (preferably having 1 to 14 carbon atoms) 14) and an acyloxy group (preferably having 1 to 14 carbon atoms), and when n is 2, R ¹ is a substituted or unsubstituted alkylene group (preferably having 1 to 14 carbon atoms).
14) or an arylene group (preferably having 6 carbon atoms)
And R ² is as defined above, and the substituent is an alkyl group (limited to a substituent for an aryl residue) or an aryl group (limited to a substituent for an alkyl residue) ), An alkoxy group, an acyl group,
It is at least one selected from an acyloxy group, an aryloxy group, a vinyl group, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, and a halogen. At least one compound selected from the group of compounds represented by the formula:

The aryloxy group includes a phenoxy group,
A p-chlorophenoxy group, a p-methylphenoxy group, a pyridinyl group, and an aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a p-chlorophenyl group, and an acyl group include a formyl group. , Acetyl group,
Examples of the propionyl group, benzoyl group, and acyloxy group include an acetoxy group, a propionyloxy group, and a pivaloyloxy group. The compounds (I) and (II) may be used in the form of a salt. Examples of the salt include salts of calcium, cobalt, iron, nickel, manganese, magnesium, barium, copper, and the like, in addition to alkali metal salts such as potassium, sodium, and lithium.

A specific example will be described below. Examples of the compound of the formula (1) include phenylphosphonic acid, phenylphosphoric acid, naphthylphosphonic acid, naphthylphosphoric acid, glycerophosphonic acid, glycerophosphoric acid, p-nitrophenylphosphonic acid,
p-nitrophenylphosphoric acid, p-methoxyphenylphosphonic acid, p-methoxyphenylphosphonic acid, p-hydroxyphenylphosphonic acid, p-hydroxyphenylphosphoric acid,
p-tolylphosphonic acid, p-tolylphosphoric acid, p-acetylphenylphosphonic acid, p-acetylphenylphosphoric acid,
p-cyanophenylphosphonic acid, p-cyanophenylphosphoric acid, m-chlorophenylphosphonic acid, m-chlorophenylphosphonic acid, methylphosphonic acid, methylenediphosphonic acid, ethylphosphonic acid, ethylenediphosphonic acid, 2-carboxyethylphosphone Acid, phosphonoacetic acid, 2-phenylethylphosphonic acid, 2-hydroxyethylphosphonic acid, 1-hydroxyethane-1,1
-Diphosphonic acid, aminohexyl phosphoric acid, 2-methoxyethyl phosphonic acid, 2-acetylethyl phosphonic acid, glycine-N, N-bis (methylenephosphonic acid), phosphoserine, phosphothreonine, pyridoxal phosphate and the like.

Examples of compounds of formula (II) include phenylphosphinic acid, naphthylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, p-nitrophenylphosphinic acid, p-methoxyphenylphosphinic acid,
-Hydroxyphenylphosphinic acid, p-tolylphosphinic acid, p-acetylphenylphosphinic acid, bisnitrophenylphosphoric acid, dioctyl phosphate, diisopropyl phosphate, dibutyl phosphate, dimethyl phosphate, diethyl phosphate, phosphoric acid Di-2-ethylhexyl ester, phosphoric acid diphenyl ester, methyl phosphinic acid, ethyl phosphinic acid, diethyl phosphinic acid, 2-carboxyethyl phosphinic acid, 2-phenylethyl phosphinic acid, 2-hydroxyethyl phosphinic acid, 2-methoxyethyl phosphine Acid and 2-acetylethylphosphinic acid.

These compounds may be used in combination of two or more. Particularly preferred compounds among these are phenylphosphonic acid, phenylphosphoric acid, naphthylphosphonic acid,
Examples include naphthylphosphoric acid, phenylphosphinic acid, diphenylphosphinic acid, and naphthylphosphinic acid. The organic layer in the present invention can be provided by the following method. That is, a solution in which the above compound is dissolved in water or an organic solvent such as methanol or ethanol or a mixed solvent thereof is applied and dried to form an organic layer,
Water or an organic solvent such as methanol or ethanol, or a mixed solvent thereof, is immersed in a solution in which the above compound is dissolved, and the aluminum plate that has been subjected to the above-mentioned hydrophilization treatment is adsorbed by the compound. And drying to provide an organic layer. In the former method, a coating solution in which the above compound is dissolved at a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the method of washing with water or the like after immersion in a solution in which the compound of the present invention is dissolved, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20%. ° C to 90
° C, preferably 25 ° C to 50 ° C, and the immersion time is
It is 1 second to 20 minutes, preferably 2 seconds to 1 minute.

The coating amount of the organic layer after drying is 2 mg / m ² to
200 mg / m ² is suitable, preferably 5 mg / m ² to
100 mg / m ² , more preferably 10 mg / m ^{2 to} 60
mg / m ² . If the coating amount is less than 2 mg / m ^{2, the} effect of reducing the residual color in the non-image area and the printing durability are not sufficient. On the other hand, when the amount is more than 200 mg / m ^{2, the} effect of reducing the residual color in the non-image area is obtained, but the printing durability is not sufficient.

The pH of the solution used for forming the organic layer of the present invention is adjusted by a basic substance such as ammonia, triethylamine or potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid. Can also be used. Further, a yellow dye may be added for improving the tone reproducibility of the photosensitive lithographic printing plate. In the organic layer of the present invention, known carboxylic acid having an amino group such as carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine can be used. And the like can be mixed with a hydrochloride of an amine having a hydroxy group. The organic layer of the present invention has the above formula (I) and / or
Or it is desirable to contain at least 30% by weight of the compound of (II), more preferably 80% by weight or more, and most preferably 100% by weight.

A photosensitive layer containing a positive photosensitive composition having a known o-quinonediazide compound is provided on the thus obtained aluminum support covered with an organic layer, and a photosensitive lithographic printing plate is prepared. obtain. As the composition for the photosensitive layer, any one 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.

The o-naphthoquinonediazide compound is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403. Other suitable orthoquinonediazide compounds include U.S. Pat. Nos. 3,046,120 and 3,18,120.
No. 8,210, described in JP-A No. 2-9, there is an ester of 1,2-diazonaphthoquinone-5-sulfonic acid chloride and a phenol-formaldehyde resin.
No. 6,163, JP-A-2-96165, JP-A-2-96661, and 1,2-diazonaphthoquinone-4-sulfonic acid chloride and phenol.
There are esters with formaldehyde resins. Other useful o-quinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802,
No. 48-63803, No. 48-96575, No. 49
No. 38701, No. 48-13354, Japanese Patent Publication No. 37-
No. 18015, No. 41-11222, No. 45-961
No. 0, 49-17481, U.S. Pat.
No. 213, No. 3,454,400, No. 3,544,323
No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602, No. 1,251,345, No. 1,267,005, 1,3
No. 29,888, No. 1,330,932, German Patent No. 8
Examples described in each specification such as 54,890 can be mentioned.

The particularly preferred o-naphthoquinonediazide compound in the present invention is a compound obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds are described in JP-A-51-139402,
No. 58-150948, No. 58-203434, No. 59-165053, No. 60-112445, No. 6
0-134235, 60-16043, 61
-118744, 62-10645, 62-1
Nos. 0646, 62-153950, 62-178
No. 562, No. 64-76047, U.S. Pat.
No. 809, No. 3,126,281, No. 3,130,047
No. 3,148,983, No. 3,184,310, No. 3,188,210, No. 4,639,406, etc. Can be mentioned.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. .3 ~
More preferably, the reaction is carried out at 1.0 equivalent. 1,2-diazonaphthoquinonesulfonic acid chloride includes 1,2-diazonaphthoquinonesulfonic acid chloride.
Diazonaphthoquinone-5-sulfonic acid chloride or 1,2-diazonaphthoquinone-4-sulfonic acid chloride can be used.

The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and amounts of introduction, and all the hydroxyl groups are 1,2-diazonaphthoquinonesulfonic acid ester. The ratio of the compound converted in the above to the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

The amount of these positive-acting photosensitive compounds (including the above-mentioned combinations) in the photosensitive composition of the present invention is suitably from 10 to 50% by weight, more preferably from 15 to 50% by weight. 40% by weight. Although the o-quinonediazide compound alone constitutes the photosensitive layer, it is preferable to use a resin soluble in alkaline water as a binder together with this kind of resin. As such a resin soluble in alkaline water, there is a novolak resin having this property.
-Cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o-, or m- / p-, m- / cresol formaldehyde resin such as a mixed formaldehyde resin.

Further, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711 can also be used. Other suitable binders include copolymers having the following (1) to (13) monomers as structural units and usually having a molecular weight of from 100,000 to 200,000. (1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, for example, N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide , O
-, M-, p-hydroxystyrene, o-, m-, p-
Hydroxyphenyl-acrylate or methacrylate, (2) acrylates having an aliphatic hydroxyl group, and methacrylates, for example, 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as maleic anhydride and itaconic acid,
(4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
(Substituted) alkyl acrylates such as hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, Cyclohexyl methacrylate, 4-hydroxybutyl methacrylate,
(Substituted) alkyl methacrylates such as glycidyl methacrylate and N-dimethylaminoethyl methacrylate;
(6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenyl Acrylamide or methacrylamides such as acrylamide and N-ethyl-N-phenylacrylamide; (7) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether; (8) vinyl acetate, bityl chloroacetate, vinyl butyrate, vinyl benzoate, etc. Nylesters, (9) Styrenes such as styrene, α-methylstyrene, chloromethylstyrene, (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (11) ethylene, propylene Olefins such as isobutylene, butadiene and isoprene; (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like; (13) N- (o-aminosulfonylphenyl) methacryl Amide, N- (m-
Aminosulfonylphenyl) methacrylamide, N-
(P-amino) sulfonylphenyl methacrylamide,
Methacrylamides such as N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, acrylamides having the same substituents as described above, and o-amino Methacrylic acid esters such as sulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylnaphthyl) methacrylate,
And unsaturated sulfonamides such as acrylic esters having the same substituents as described above.

Further, a monomer copolymerizable with the above monomer may be copolymerized. In addition, a copolymer obtained by copolymerization of the above-mentioned monomers, for example, modified with glycidyl methacrylate, glycidyl acrylate, or the like is also included, but is not limited thereto. The copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the carboxylic acid value of the copolymer is preferably from 0 to 3 meq / g, more preferably from 0.5 to 2.5 meq / g. 5me
q / g.

The preferred molecular weight of the above copolymer is from 1 to 10
It is ten thousand. If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, or an epoxy resin may be added to the copolymer. Such alkali-soluble polymer compounds can be used alone or in combination of two or more, and are used in an amount of 80% by weight or less of the total composition.

Further, as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms as a substituent such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin is used. It is preferable to use a condensate of phenol and formaldehyde in combination to improve the oil sensitivity of the image.

In the photosensitive composition of the present invention, it is preferable to add a cyclic acid anhydride, a phenol or an organic acid in order to increase the sensitivity. Cyclic acid anhydride include U.S. Pat phthalic anhydride as described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride Examples include phthalic acid, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride.

As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-Tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like described in JP-A No. 2-96755 and JP-A-2-96755. p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid,
Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.

The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is 0.05 to 15%.
% By weight, more preferably 0.1 to 5% by weight. Also, in the photosensitive composition of the present invention, in order to widen the latitude of development, JP-A-62-25174 is used.
0 and non-ionic surfactants described in Japanese Patent Application No. 181248/1990;
An amphoteric surfactant as described in JP-A-21044 and Japanese Patent Application No. 2-115992 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmirate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the activator include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, amogen water (trade name, Daiichi Kogyo Co., Ltd.)
N-tetradecyl-N, N-betaine type), 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, Sanyo Chemical Co., Ltd., alkylimidazoline) Is mentioned.

The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably 0.05% to 15% by weight, more preferably 0.1% to 5% by weight. is there. In the photosensitive composition of the present invention, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, and other fillers can be added. 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. Specifically, JP-A-50-36209 and JP-A-53-81
Combinations of o-naphthoquinonediazide {4} sulfonic acid halogenide and salt-forming organic dyes described in JP-A-28-28, JP-A-53-36223 and JP-A-54-74728.
No. 60-3626, No. 60-138439, No. 61-143748, No. 61-151644, No. 6
Combinations of a trihalomethyl compound and a salt-forming organic dye described in 3-58440 can be mentioned. Such trihalomethyl compounds include oxadiazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give clear print-out images.

The present invention is particularly effective when a photosensitive composition containing such a compound is used, and a lithographic printing plate having almost no residual color can be obtained. 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 # 13
0, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-50
5, Orient Chemical Co., Ltd., Victoria Pure Blue, Crystal Violet (CI425
55), methyl violet (C142535), ethyl violet, rhodamine B (CI45170B),
Malachite green (CI42000) and methylene blue (CI52015). Dyes described in JP-A-62-293247 are particularly preferred.

The photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, 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, and diethylene glycol dimethyl ether. These solvents are used alone or in combination. The concentration (solid content) in the above components is 2 to 50% by weight.
It is. The amount of application varies depending on the application, but generally 0.5 to 3.0 g / m ² as a solid content is preferable. The photosensitivity increases as the coating amount decreases, 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-62-1
A fluorine-based surfactant as described in JP-A-70950 can be added. , A preferable addition amount is
0.01 to 1% by weight of the total photosensitive composition, more preferably
0.05 to 0.5% by weight. The surface of the photosensitive layer provided as described above is preferably matted in order to reduce the time for evacuation during contact exposure using a vacuum printing frame and to prevent printing blur. Specifically, Japanese Patent Application Laid-Open No. Sho 50-12
No. 5805, Japanese Patent Publication No. 57-6582, No. 61-289
No. 86, a method of providing a mat layer, and a method of heat-fusing a solid powder as described in JP-B-62-62337.

The developer for the photosensitive lithographic printing plate of the present invention is specifically sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Potassium tertiary phosphate, potassium diphosphate, ammonium tertiary phosphate,
Aqueous solutions such as ammonium diphosphate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammore water, etc. Are added so that their concentration is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. These are used alone or in combination.

A water-soluble organic amine compound can also be used as a developer component. For example, monomethylamine,
Such as dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneamine, ethylenediamine, pyridine, etc. Compounds. Of these, monoethanolamine, diethanolamine,
Triethanolamine and the like are preferred, and may be used in combination with an inorganic alkali metal salt or the like.

The concentration of these basic compounds in an aqueous solution is preferably 0.05% by weight to 10% by weight. If necessary, an anionic surfactant may be added to the developer. Further, an organic solvent can be added. Examples of the anionic surfactant include higher alcohol sulfates having 8 to 22 carbon atoms, such as sodium salts of lauryl alcohol sulfate, sodium salts of octyl alcohol sulfate, ammonium salts of lauryl alcohol sulfate, and sodium sulphate, such as cetyl. Aliphatic alcohol phosphate salts such as sodium salts of alcohol phosphate esters,
For example, alkylarylsulfonic acid salts such as sodium salt of dodecylbenzenesulfonic acid, sodium salt of isopropylnaphthalenesulfonic acid, and sodium salt of metanitrobenzenesulfonic acid, for example, C ₁₇ H ₃₃ CON (CH
₃ ) Sulfonates of alkylamides such as CH ₂ CH ₂ SO ₃ Na and the like, and sulfonates of dibasic fatty acid esters such as dioctyl sodium sulfosuccinate and dihexyl sodium sulfosuccinate are included.

It is appropriate that the anionic surfactant is contained in the range of 0.1 to 5% by weight based on the total weight of the developing solution at the time of use. When the amount is less than 0.1% by weight, the effect of the use is reduced. When the amount is more than 5% by weight, the dissolution (color loss) of the dye in the image area becomes excessive, There are adverse effects such as deterioration of chemical strength.

Suitable organic solvents are those having a solubility in water of about 10% by weight or less, and preferably those having a solubility in water of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol-1,4-phenylbutanol-1,4-phenylbutanol-2,2-phenylbutanol-1,2-
Fexiethanol, 2-benzyloxyethanol,
o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol and 3
-Methylcyclohexanol and the like.

The content of the organic solvent is preferably from 1 to 5% by weight based on the total weight of the developing solution at the time of use. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the anionic surfactant as the amount of the organic solvent increases. This is because the amount of anionic surfactant is small,
If a large amount of the organic solvent is used, the organic solvent does not dissolve, so that good development property cannot be expected.

Further, if necessary, an antifoaming agent and hard water
Additives such as softeners can also be included. hard water
As a softener, for example, Na_TwoP_TwoO₇, Na_FiveP_ThreeO_Three, Na_ThreeP_ThreeO₉,
Na_TwoO _FourP (NaO_ThreeP) PO_ThreeNa_Two, Calgon (polymetaphosphate sodium
Polyphosphates such as ethylenediaminetetrate
Laacetic acid, its potassium salt, its sodium salt; diethyle
Triaminepentaacetic acid, its potassium salt, sodium
Salt; triethylenetetramine hexaacetic acid, potassium
Salt, its sodium salt; hydroxyethylethylenedia
Mintriacetic acid, its potassium salt, its sodium salt;
Trilotriacetic acid, its potassium salt, its sodium salt;
1,2-diaminocyclohexanetetraacetic acid, its potassium
Salt, sodium salt thereof; 1,3-diamino-2-p
Lopanol tetraacetic acid, its potassium salt, its sodium
List aminopolycarboxylic acids such as salt
Can be. Such a water softener is used to harden the hard water used.
The optimum amount changes according to the degree and amount used,
If the amount of use is shown, 0.01 to 5 times
%, More preferably 0.01 to 0.5% by weight.
Let me do.

The light source used for exposing the photosensitive lithographic printing plate of the present invention includes a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp and the like. 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. Further, in the developing process of this type of photosensitive lithographic printing plate, the developing solution becomes fatigued according to the processing amount, and thus the processing ability may be restored by using a replenisher or a fresh developing solution. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246.

The plate making process described above is disclosed in
It is preferably carried out using an automatic developing machine as described in JP-A-7054 and JP-A-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.

Further, when the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, erasing if desired, and washing after washing with water, burning is performed before burning. -2518, 55-280
No. 62, JP-A-62-131859 and JP-A-61-1596.
It is preferable to carry out treatment with a surface-regulating liquid as disclosed in each publication of No. 55.

[0049]

As described above, the photosensitive lithographic printing plate of the present invention has less residual color in the non-image area after development as compared with the conventional lithographic printing plate, and therefore has excellent plate inspection properties. And a remarkable effect of having higher printing durability.

[0050]

The present invention will be described below more specifically with reference to examples. In the examples, "%" indicates "% by weight" unless otherwise specified.

<Examples 1 to 5 and Comparative Examples 1 to 3> A 0.15 mm thick 2S aluminum plate was immersed in a 10% aqueous solution of tribasic sodium phosphate kept at 80 ° C. for 30 seconds to degrease it. The pumice slurry was grained with a nylon brush while flowing on an aluminum plate, etched in a sodium aluminate aqueous solution at 60 ° C. for 10 seconds, and subsequently washed with a 3% aqueous sodium hydrogen sulfate solution. The aluminum plate was anodized in a 20% sulfuric acid at a current density of 2 A / dm ² for 2 minutes, and then treated with a 2.5% aqueous sodium silicate solution at 70 ° C. for 1 minute to prepare an aluminum plate support A. On the surface of the substrate A thus treated,
The undercoat liquid (I) having the following composition was applied and dried at 90 ° C. for 1 minute. The coating amount after drying was 20 mg / m ² . (I) 0.1 g of phenylphosphoric acid Example 1 95 g of methanol 5 g of water In the same manner, instead of phenylphosphoric acid of the undercoat liquid (I),
An undercoating solution using phenylphosphonic acid (Example 2), naphthylphosphoric acid (Example 3), phenylphosphinic acid (Example 4), and diphenylphosphinic acid (Example 5) was prepared.
A support coated on mg / m ² substrate A was prepared.

On the other hand, for comparison, a support (Comparative Example 1) to which no undercoat liquid was applied was prepared. For further comparison, a support (Comparative Example 2) was prepared by applying the solution (I) to the support A which had been subjected to anodizing treatment. A support to which the solution (I) was not applied was also used (Comparative Example 3). The following photosensitive solution was applied to the substrate thus produced. Esterified product of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride (esterification ratio: 90 mol%) 0.47 parts by weight Phenol formaldehyde resin (weight average molecular weight: 2300) 1.15 parts by weight 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 0.02 parts by weight Naphthoquinone-1,2-diazide-4-sulfonyl chloride 0.01 parts by weight Ethyl violet (dye of Hodogaya Chemical Co., Ltd.) 0.016 parts by weight Megafac F-177 (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.004 parts by weight Methyl ethyl ketone 12 parts by weight Methanol 4 parts by weight Part ethylene dichloride 4 parts by weight The applied dry weight was 2.1 g / m ² .

This photosensitive lithographic printing plate was image-exposed for 45 seconds at a distance of 70 cm from a 30-ampere carbon arc lamp using a developing solution having the following composition.
Developed at 30 ° C for 30 seconds. Stock solution (1: 4 diluted with water) Water 75 parts by weight Potassium bicarbonate 3.5 parts by weight Potassium carbonate 7 parts by weight Perex NBL (manufactured by Kao Atlas Co., Ltd.) 20 parts by weight Phenylcellosolve 2 parts by weight

After development as described above, washing was carried out sufficiently, unnecessary portions were erased with an erasing solution, gummed, and printed by a conventional procedure. Table 1 shows the correction trace stains, the result of the residual color in the non-image portion, and the result of printing durability at this time. From the results shown in Table 1, it can be seen that the photosensitive lithographic printing plate according to the present invention has sufficient performance in all of the remaining colors, stains, and printing durability as compared with Comparative Examples.

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Supporting body When printing Remaining color ^{* 1} Correction of Anode Hydrophilic Undercoat Correction (Number of sheets) Oxidation treatment Trace dirt treatment Example 1 Yes Yes Phenylphosphoric acid None 0.01 100,000 〃 2 Yes Yes Phenylphosphonic acid No 0.02 100,000 ３ 3 Yes Yes Naphthyl phosphoric acid No 0.01 100,000 ４ 4 Yes Yes Phenylphosphinic acid No 0.02 100,000 ５ 5 Yes Yes Diphenylphosphinic acid None 0.01 100,000 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Comparative Example 1 Yes Yes No Fire ants 0.04 10,000 or less 〃 2 Yes No Phenyl phosphate Yes 0.07 80,000 〃 3 Yes No No Ants (ground pollution) 0.15 120,000 ━━━━━━━ * 1) The difference between the density of the non-image area after development and the density of the support before coating (ΔD) displayed.

<Examples 6 to 10, Comparative Examples 4 to 6>
A 30 mm aluminum plate was grained with a nylon brush and a 400 mesh aqueous suspension of pumicestone, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, then neutralized with 20% HNO ₃ , and washed with water. This is V _A
= 12.7 V using a sinusoidal alternating current under the condition of 2.7 V
The electrolytic surface roughening treatment was performed in an aqueous solution of nitric acid at a rate of 160 coulombs / dm ^{2 at} the anode. When the surface roughness was measured, it was 0.6 μ (Ra indication). Continued 30
% H ₂ SO ₄ aqueous solution and desmutted at 55 ° C. for 2 minutes, and then in a 20% H ₂ SO ₄ aqueous solution, current density 2 A
/ Dm ² at 2.7 g / m ² and then anodized at 70 ° C. with 2.5% aqueous potassium silicate solution.
The treatment was performed for 0 second to produce an aluminum support B. The surface of the substrate B thus treated was coated with the same undercoat as in Examples 1 to 5 and Comparative Examples 1 to 3. The following photosensitive solution was applied to the substrate thus produced.

Esters of 1,2-diazonaphthoquinone-5-sulfonyl chloride with pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) 0.45 g cresol-formaldehyde novolak Resin (meta / para ratio, 6: 4, weight average molecular weight 3,000, number average molecular weight 1,100) 1.1 g 4- [PN- (P-hydroxybenzoylaminophenyl) -2,6-bis (trichloromethyl) -S-Triazine 0.02 g Tetrahydrophthalic anhydride 0.05 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.02 g Megafac F-177 (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g methyl ethyl ketone 15 g 1-methoxy-2-propanol 15 g A lithographic printing plate, a vacuum printing frame in by 3kw metal halide lamp from a distance of 1m through the transparent positive film, after performing 50 seconds exposure, the molar ratio of SiO ₂ / K ₂ O is 1.5 Potassium Silicate Development was performed with a 4.5% aqueous solution (pH = 12.9).

After development as described above, washing was performed sufficiently, gumming was performed, and printing was performed in the same procedure as in Examples 1 to 5 and Comparative Examples 1 to 3. Table 2 shows the results. It can be seen that the printing plate according to the present invention is superior to the comparative example.

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Supporting body When printing Remaining color Printing durability Anode Hydrophilic Undercoating modification Oxidation treatment Trace dirt treatment ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 6 Yes Yes Phenyl Phosphoric acid None 0.01 140,000 7 Available Yes Phenylphosphonic acid None 0.02 140,000 8 Available Available Naphthyl phosphoric acid 0.02 140,000 9 Available Available Phenylphosphinic acid None 0.02 140,000 10 Available Available Diphenyl phosphinic acid 0.01 140,000 Available ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Comparative Example 4 Yes Yes No No 0.03 10,000 or less 〃 5 Yes No Phenyl phosphate photon pear 0.04 120,000 〃 6 Yes No ヤ Fire ants 0.05 150,000 ━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

Claims (1)

(57) [Claims] An R ¹ (PO (OH) ₂ ) _n or R ^1- (PO (OH) (R ² )) _n (formula ¹ ) is formed on an aluminum plate that has been subjected to an anodizing treatment and then subjected to a hydrophilic treatment. Where n is 1
Or 2, and when n is 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 is 2, R ¹ is Represents a substituted or unsubstituted alkylene group or an arylene group, wherein R ² is as defined above.
Wherein an organic layer containing at least one compound selected from the group consisting of compounds represented by the formula is provided, and a positive photosensitive layer containing an o-quinonediazide compound and an organic polymer is provided thereon. Sexographic printing plate.