JP2684253B2 - Plate making method of lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to the development of a positive-working photosensitive lithographic printing plate having an intermediate layer and a positive-working photosensitive layer containing an o-quinonediazide compound on a hydrophilized aluminum support. It relates to a processing method.

[0002]

2. Description of the Related Art Recently, an aqueous solution of sodium silicate or an aqueous solution of potassium silicate is relatively advantageously used as a developer for a positive PS plate having a photosensitive layer containing an o-quinonediazide compound as a photosensitive substance on an aluminum support. ing. This is because developability and stability are easily adjusted by the content ratio and concentration of silicon oxide and sodium oxide (or potassium) as components of sodium silicate (or potassium). However, in this type of developing solution, when the automatic developing process is repeated, water-insoluble dust and sludge due to silicon oxide is generated at the bottom of the developing tank.
There were problems such as clogging of the spray pipe and nozzle.
Also, due to drying and liquid splash when the automatic processor is stopped,
It was also a cause of various problems because it was precipitated as water-insoluble silica around the developing bath. Further, when this type of developer is used as a waste liquid, if neutralization treatment is performed, silicon oxide precipitates in a gel state, which causes environmental pollution.

Therefore, a developer containing no silicon oxide has been studied several times. However, with a developer without silicon oxide, the hydrophilicity of the non-image area of the printing plate is not sufficient, and the substrate is stained during printing, or due to the absence of silicon oxide, the support is etched by the alkaline component in the developer. However, there is a problem in that the aluminum component of the support is eluted in a large amount and the developability is significantly impaired.

In order to improve this, conventionally, the surface of an aluminum support is treated with an alkali metal silicate as disclosed in US Pat. No. 3,181,461, or disclosed in Japanese Patent Publication No. 36-22063. A method of hydrophilizing such as fluorozirconic acid treatment as described above or polyvinylphosphonic acid treatment as disclosed in US Pat. No. 3,276,868 has been used. However, in these methods, the hydrophilicity of the non-image area of the printing plate becomes sufficient, and the etching of the support by alkali is also eliminated, but the adhesion between the photosensitive composition and the hydrophilized support becomes insufficient, The number of prints was only about several thousand.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to prevent problems such as clogging of the spray nozzle due to accumulation of dust and sludge without deposition of silicic acid even when a long-term development process is carried out by an automatic processor. It is to provide a development processing method which does not exist. Another object of the present invention is to provide a development processing method in which the load at the time of waste liquid neutralization processing is reduced and environmental pollution is reduced. A further object of the present invention is to provide a developing method suitable for producing a lithographic printing plate having strong adhesion between the image area and the aluminum support and excellent printing durability. Further, the object of the present invention is developability,
It is an object of the present invention to provide a developing method suitable for producing a lithographic printing plate excellent in stain resistance during printing.

[0006]

The present inventors have completed the present invention as a result of extensive studies to achieve the above object. The present invention provides a hydrophilically-treated aluminum support with R ¹ (PO (OH) ₂ ) _n or R ^1- (PO
A substituted or unsubstituted aliphatic compound or aromatic compound represented by (OH) (R ² )) _n (n is 1 or 2, and when n is 1, R ¹ and R ² are substituted or unsubstituted) Represents an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an acyl group or an acyloxy group, and when n is 2, R ¹
Represents a substituted or unsubstituted alkylene group or arylene group, R ² is as defined above), and an organic layer containing at least one compound selected from the group consisting of compounds consisting of A photosensitive lithographic printing plate provided with a positive photosensitive layer containing a quinonediazide compound, after image exposure, an alkali metal salt or ammonium salt of an inorganic acid other than silicic acid, an alkali metal hydroxide, ammonium hydroxide and a water-soluble organic A plate-making method for a lithographic printing plate, which comprises developing with an aqueous solution containing at least one compound selected from the group consisting of amine compounds.

The present invention will be described in detail below. The aluminum support used in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and a trace amount of a foreign element. The foreign elements include silicon, iron, manganese, copper, magnesium, chromium,
Examples include zinc, bismuth, nickel and titanium. The content of the foreign element in the alloy is at most 10% by weight or less. The aluminum suitable for the present invention is pure aluminum, but completely pure aluminum is difficult to produce due to refining technology, and therefore, it is preferable that the content of the foreign element is as low as possible.
In addition, 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 thus roughened aluminum plate is subjected to alkali etching treatment and neutralization treatment, if necessary. 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.

[0010] The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but in general, the electrolyte concentration is 1 to 80% by weight in solution, and the liquid 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 1.0 g / m ² or more, more preferably 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 hydrophilic treatment used after the above-mentioned treatment, a conventionally known hydrophilic treatment is used. As such a hydrophilic treatment, US 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 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-
A substituted or unsubstituted aliphatic compound or aromatic compound represented by (PO (OH) ₂ ) _n (n is 1 or 2),
(II) a substituted or unsubstituted aliphatic compound or aromatic compound (n is 1 or 2) represented by R ^1- (PO (OH) (R ² )) _n , (when n is 1, R ¹ , R ² is a substituted or unsubstituted alkyl group (preferably having 1 to 1 carbon atoms).
4), an alkoxy group (preferably having 1 to 14 carbon atoms)
), An aryloxy group (preferably having 6 to 10 carbon atoms).
Group), an aryl group (preferably having 6 to 10 carbon atoms), an acyl group (preferably having 1 to 14 carbon atoms),
It is an acyloxy group (preferably having 1 to 14 carbon atoms), and when n is 2, R ¹ is an alkylene group (preferably having 1 to 14 carbon atoms) or an arylene group (preferably having 6 to 10 carbon atoms). R ² is as defined above, and the substituent is an alkyl group (provided that it is a substituent for an aryl residue), an aryl group (however, a substituent for an alkyl residue), an alkoxy group , An acyl group, an acyloxy group, an aryloxy group, a vinyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and a halogen). Is a compound of.

The aryloxy group is 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 salts. 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.

The following is a specific example. 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) are phenylphosphinic acid, naphthylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, p-nitrophenylphosphinic acid, p-methoxyphenylphosphinic acid, p
-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.

Two or more of these compounds may be used in combination. 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 from 2 mg / m ² to
200 mg / m ² is suitable, preferably 5 mg / m ² to
It is 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. Also, 200mg
Even if it is more than / m ² , sufficient printing durability cannot be obtained. The solution used when providing the organic layer of the present invention is adjusted to pH 1 by adjusting the pH with a basic substance such as ammonia, triethylamine, potassium hydroxide, etc., or an acidic substance such as hydrochloric acid, phosphoric acid, etc.
It can also be used in the range of -12. 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 phosphonic acids having an amino group such as carboxymethyl cellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, amino acids such as glycine and β-alanine, triethanolamine. Hydrochlorides of amines having a hydroxy group such as the hydrochlorides of the above can be mixed.
The organic layer of the present invention preferably contains at least 30% by weight of the compound of the formula (I) and / or (II), more preferably 80% by weight or more, and most preferably 100% by weight.

On the aluminum support coated with the organic layer thus obtained, a photosensitive layer containing a positive photosensitive composition having a known o-quinonediazide compound is provided to provide a photosensitive lithographic printing plate. 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,
48-63803, 48-96575, 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.

In the present invention, particularly preferred o-naphthoquinonediazide compound 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 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 obtained o-naphthoquinonediazide compound is a mixture of 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduction amounts, but all of the hydroxyl groups are 1,2-diazonaphthoquinonesulfonic acid ester. The ratio of the compound converted in (3) 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-working photosensitive compounds (including the above-mentioned combinations) in the photosensitive composition of the present invention is suitably 10 to 50% by weight, more preferably 15 to 50% by weight. It is 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 novolac resin having this property, such as phenol formaldehyde resin, m
-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, acrylic esters, methacrylic esters and hydroxystyrenes having an aromatic hydroxyl group, such as N-
(4-hydroxyphenyl) acrylamide or N-
(4-hydroxyphenyl) methacrylamide, o-,
m-, p-hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or methacrylate,
(2) Acrylic acid esters having an aliphatic hydroxyl group,
And methacrylic acid esters such as 2-hydroxyethyl methacrylate or 2-hydroxyethyl methacrylate, (3) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid, (4)
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, -2-acrylic acid
(Substituted) alkyl acrylates such as chloroethyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N -(Substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate, (6)
Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N
-Ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-
Acrylamide or methacrylamide such as N-phenylacrylamide, (7) vinyl ether such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) vinyl acetate, Vinyl esters such as bityl chloroacetate, vinyl butyrate and vinyl benzoate, (9) Styrenes such as styrene, α-methylstyrene and chloromethylstyrene, (10) Methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone , Vinyl ketones such as phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (12) N-vinyl Pyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile,
(13) N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-
Amino) sulfonylphenyl methacrylamide, N-
Methacrylamides such as (1- (3-aminosulfonyl) naphthyl) methacrylamide and N- (2-aminosulfonylethyl) methacrylamide, and acrylamides having the same substituents as described above, and o-aminosulfonylphenyl. Unsaturation of methacrylic acid esters such as methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylnaphthyl) methacrylate, and acrylic acid esters having the same substituents as above. Sulfonamide.

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 above copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the preferable carboxylic acid value of the copolymer is 0 to 4 meq / g, and more preferably 0.5 to 2. 5me
q / g.

The preferred molecular weight of the above copolymer is 1-10.
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, it has an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin. It is preferable to use a condensate of phenol and formaldehyde together in order to improve the oil sensitivity of the image.

Cyclic acid anhydrides, phenols and organic acids are preferably added to the photosensitive composition of the present invention in order to enhance 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.

Examples of phenols include 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, there is disclosed in 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 ratio of the above 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. Further, in order to increase the development latitude in the photosensitive composition of the present invention, 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 Kasei Co., Ltd., alkylimidazoline type), etc. Is mentioned.

The proportion of the above 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.

As the image colorant, other dyes can be used in addition to the above salt-forming organic dyes. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 3
12, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (C142535), Ethyl Violet, Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (CI5201).
5) etc. can be mentioned. Further, Japanese Patent Application Laid-Open No.
The dyes described in Japanese Patent No. 93247 are particularly preferable.

The photosensitive composition according to the present invention is dissolved in a solvent which dissolves the above-mentioned components and applied 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,
There are dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents may be used alone or as a mixture. 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 the coatability, such as JP-A-62-1 is used.
Fluorine-based surfactants such as those described in JP 70950 can be added. , A preferable addition amount is
0.01 to 1% by weight of the total photosensitive composition, more preferably
It is 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.

As salts of inorganic acids other than silicic acid contained in the developer of the present invention, sodium triphosphate, potassium triphosphate, ammonium triphosphate, sodium diphosphate, potassium diphosphate, Dibasic ammonium phosphate, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate,
Examples thereof include ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonium borate. Examples of the alkali metal hydroxide include potassium hydroxide, sodium hydroxide, lithium hydroxide and ammonium hydroxide. Particularly preferred are carbonates and hydrogen carbonates. These may be used alone or as a mixture.

The water-soluble organic amine compound used in the developing solution of the present invention includes monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, Examples include compounds such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and the like. Among them, monoethanolamine, diethanolamine, triethanolamine and the like are particularly preferable, and may be used in combination with an inorganic alkali metal salt or the like.

The concentration of these basic compounds in the aqueous solution is preferably 0.05% by weight to 10% by weight. They are,
More preferably, if it is less than pH 11, it is easy to handle during plate-making work, and the neutralization treatment is also easy. If necessary, an anionic surfactant may be added to the developer. Further, an organic solvent can be added. Examples of the anionic surfactant include sodium salts of lauryl alcohol sulfate, sodium salts of octyl alcohol sulfate, ammonium salts of lauryl alcohol sulfate, salts of higher alcohol sulfates having 8 to 22 carbon atoms such as secondary sodium alkyl sulfate, such as cetyl. Aliphatic alcohol phosphate salts such as sodium salt of alcohol phosphate ester, for example, alkylaryl sulfonate salts such as sodium salt of dodecylbenzenesulfonic acid, sodium salt of isopropylnaphthalenesulfonic acid, sodium salt of metanitrobenzenesulfonic acid, etc. , For example C ₁₇ H
₃₃ CON (CH ₃ ) CH ₂ CH ₂ SO ₃ Na and other sulfonates of alkylamides, such as dibasic fatty acid ester sulfonates such as sodium sulfosuccinate dioctyl ester and sodium sulfosuccinate dihexyl ester Is 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.

As the organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and those having a solubility of 5% by weight or less are preferable. 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 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, additives such as an antifoaming agent and a water softener can be contained. Examples of the water softener include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ ,
Polyphosphates such as Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ and Calgon (sodium polymetaphosphate), eg ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt Triethylenetetramine hexaacetic acid, its potassium salt, its sodium salt; hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt;
Examples thereof include aminopolycarboxylic acids such as 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its potassium salt, its sodium salt, and the like. The optimum amount of such a water softener varies depending on the hardness of the hard water used and the amount used. However, if a general amount is used, 0.01 to 5% by weight in the developer at the time of use is used. , More preferably 0.01 to 0.5% by weight.

Light sources used for exposing the photosensitive lithographic printing plate of the present invention include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps and metal halide lamps. The plate-making method of the photosensitive lithographic printing plate of the present invention is described in JP-A-54-8002 and JP-A-55-1150.
It goes without saying that the methods described in JP-B No. 45 and JP-A-59-58431 can also be used. That is, after the development processing, it may be subjected to a desensitization treatment after washing with water, a desensitization treatment as it is, a treatment with an aqueous solution containing an acid, or a desensitization treatment after treating with an aqueous solution containing an acid. Furthermore, in the developing process of this type of photosensitive lithographic printing plate, the developing solution becomes tired depending on the processing amount,
Replenisher or fresh developer may be used to restore throughput. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246.

In addition, the plate making process as described above is described in JP-A-2
It is preferably carried out using an automatic developing machine as described in JP-A-7054 and JP-A-2-32357. Further, in the present invention, when the photosensitive lithographic printing plate is imagewise exposed, developed, washed with water or rinsed, 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 desensitizing gum which is optionally applied in the final step of the plate making process, Japanese Patent Publication Nos. 62-16834 and 62-25118 are available.
No. 63-52600, JP-A-62-7595,
Those described in JP-A-62-11693 and JP-A-62-83194 are preferable.

Further, in the present invention, when the photosensitive lithographic printing plate is imagewise exposed, developed, washed with water or rinsed, erased if desired, and burned after washing with water, it is preferable to remove the impurities from the light of the prior art. 61-2518, 55
-28062, JP-A-62-31859, 61-
It is preferable to treat with a leveling solution as disclosed in each publication of No. 159655.

[0047]

According to the present invention, there is no generation of precipitates and sludge even when the development processing is carried out for a long time with an automatic processor, and the neutralization of the fatigue solution is easy. In addition, the developability is good, and the lithographic printing plate obtained has excellent printing durability and stain resistance of non-image areas.

[0048]

EXAMPLES The present invention will be described more specifically below with reference to examples.
explain. In addition, "%" in the examples is not particularly specified
Only "% by weight" shall be indicated. <Examples 1-3, ratio
Comparative Examples 1 to 3> 8 pieces of 2S aluminum plate having a thickness of 0.15 mm
To a 10% aqueous solution of sodium triphosphate kept at 0 ° C
Soak for 30 seconds to degrease, and use the pumice slurry as an aluminum foil.
Grain it with a nylon brush while pouring it on the plate, then 6
Etch for 10 seconds in 0 ℃ sodium aluminate solution
And then washed with a 3% aqueous solution of sodium hydrogensulfate.
Was. This aluminum plate is subjected to a current density of 2 A in 20% sulfuric acid.
/ Dm^TwoAnodize for 2 minutes at 70 ° C, then 2.
Treat with 5% sodium silicate aqueous solution for 1 minute,
A um plate support A was prepared. Substrates treated in this way
Undercoat liquid (I) having the following composition is applied to the surface of A, and the temperature is 90 ° C.
Dry for 1 minute. The coating amount after drying is 20 mg / m^TwoSo
Was. (I) Phenylphosphoric acid 0.1 g ... Example 1 Methanol 95 g Water 5 g In the same manner, instead of phenylphosphoric acid in the undercoating liquid (I),
Phenylphosphonic acid (Example 2), phenylphosphine
20 mg / m of an undercoat liquid using an acid (Example 3) ^TwoBoard A
A support coated on the above was prepared.

On the other hand, for comparison, a support (Support B) which had been anodized in the examples was used without applying the undercoating liquid (Comparative Examples 1 and 3). For further comparison, Support A was used without applying the undercoat liquid (Comparative Example 2). The following photosensitive solution was applied to the substrate thus produced. Esterification product of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride (esterification rate: 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 Part Victoria Pure Blue BOH (dye from Hodogaya Chemical Co., Ltd.) 0.016 parts by weight Megafac F-176 (fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.004 parts by weight Methyl ethyl ketone 12 parts by weight Parts ethanol 4 parts by weight ethylene dichloride 4 parts by weight The coating dry weight was 2 g / m ² .

This photosensitive lithographic printing plate was imagewise exposed to a carbon arc lamp of 30 amps from a distance of 70 cm for 45 seconds, and a developer A or B having the following composition was used for 30 seconds at 25 ° C. in an automatic processor. Developed. Developer A Undiluted solution (diluted with water 1: 4) Water 75 parts by weight Potassium hydrogen carbonate 3.5 parts by weight Potassium carbonate 7 parts by weight Perex NBL (manufactured by Kao Atlas Co., Ltd.) 15 parts by weight Phenoxyethanol 2 parts by weight Part Developer B Potassium silicate 2% by weight aqueous solution 100 parts by weight (SiO ₂ / K ₂ O molar ratio 0.75) C ₁₀ H ₇ -O- (C ₂ H ₄ O) ₇ -SO ₃ K 5 parts by weight Results Is shown in Table 1. The stain resistance indicates the print stain on the non-image portion of the printing plate after development, and the printing durability indicates the number of printed sheets in practical printing. Further, the presence or absence of sludge was also shown when 25% of the water of the fatigue liquid was forcibly evaporated at the place where each development treatment was carried out at 10 m ² / l.

Table 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ No. Support undercoat Developer Stain resistance Number of prints Presence of sludge ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Actual 1 A Phenylphosphoric acid A A 100,000 None Fruit 1 A Phenylphosphonic acid A A 100,000 None Fruit 1 A phenylphosphinic acid A B 90,000 None ───────────────────────────── ────── Ratio 1 B None A D 100,000 None Ratio 2 A None A C 050,000 None Ratio 3 B None BB B 100,000 Yes ━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━ Stainability: A = none, B = nearly no, C = somewhat, D = many In Examples 1 to 3, long-term For automatic processing Showed no occurrence of scum-sludge Te, waste neutralization process was easy. Further, it was found that the developability was good, stains did not occur during printing, and the plate had sufficient printing durability. On the other hand, in Comparative Example 1, generation of dust and sludge was not observed, but stains occurred during printing because the support was not subjected to the hydrophilic treatment. Further, in Comparative Example 2, the stain resistance during printing was improved, but the number of printed sheets was not sufficient. Further, in Comparative Example 3, although the stain resistance during printing and the printing durability were sufficient, dust and sludge were generated in the long-term processing, and the spray nozzle of the automatic developing machine was clogged.

As described above, the present invention is an excellent plate-making method which is sufficiently satisfactory in stain resistance and printing durability and free from the problem of waste liquid sludge and sludge. It turns out to be preferable. <Examples 4 to 6 and Comparative Examples 4 to 6> An aluminum plate having a thickness of 0.30 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. After dipping in 10% sodium hydroxide at 70 ° C for 60 seconds for etching, and then rinsing with running water, 20% HN
It was neutralized with O ₃ and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. The surface roughness was measured and found to be 0.6μ.
(Ra display). Continued 30% H ₂ SO
_{4 After} dipping in aqueous solution and desmutting at 55 ℃ for 2 minutes,
Anodizing in a 20% H ₂ SO ₄ aqueous solution at a current density of 2 A / dm ^{2 to} a thickness of 2.7 g / m ² , then treating with a 2% sodium silicate aqueous solution at 70 ° C. for 20 seconds, Support C was prepared.

An undercoat liquid having the following composition was applied to the surface of the support C thus treated and dried at 80 ° C. for 30 seconds. The coating amount after drying was 10 mg / m ² . On the other hand, for comparison, the support (Support D) which had been anodized in the example was used without coating the undercoating liquid (Comparative Examples 4 and 6).

For comparison, Support C was used without applying the undercoat liquid (Comparative Example 5). The following photosensitive solution was applied to the substrate thus manufactured. The dry coating weight was 2.5 g / m ² . Photosensitive solution 0.8 parts by weight of polyhydroxyphenyl obtained by condensation of acetone and pyrogallol Naphthoquinone-1,2-diazide-5-sulfonic acid ester phenol formaldehyde resin 2.2 parts by weight (weight average molecular weight 1500) novolak type octylphenol 0.02 parts by weight formaldehyde resin phthalic anhydride 0.08 parts by weight 2-trichloromethyl-5- (p-meth 0.04 parts by weight xystyryl) -1,3,4-oxadiazole crystal violet paratoluene 0.03 parts by weight Parts by weight Sulfonate Methyl cellosolve acetate 20 parts by weight Methyl ethyl ketone 8 parts by weight This photosensitive lithographic printing plate was manufactured by Fuji Photo Film Co., Ltd.
It was exposed using an S light (2 kw metal halide lamp), and developed with developer C or D shown below at 25 ° C. for 30 seconds.

Developer C Undiluted solution (diluted with water 1: 1 for use) Water 1000 parts by weight Triethanolamine 20 parts by weight Monoethanolamine 5 parts by weight Perex NBL 30 parts by weight Developer D Sodium silicate 2.5 wt% aqueous solution of 100 parts by weight of (SiO ₂ / Na ₂ O molar ratio _{0.65) C 10 H 7 -O- (} C 2 H 4 O) 4 -SO 3 Na 8 parts by weight results shown in table 2. The stain resistance indicates the print stain on the non-image area of the printing plate after development, and the printing durability indicates the number of printed sheets in practical printing. Further, it was also shown whether or not sludge was generated when 25% of the water of the fatigue liquid was forcibly evaporated at the place where each development treatment was carried out at 10 m ² / l. ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ No. Support base coat Developer Stain stains Number of printable sheets Sludge presence ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Actual 4 C Naphthylphosphoric acid C A 90,000 None Actual 5 C Diphenylphosphinic acid C B 80,000 None 6C naphthylphosphonic acid CA 90,000 None ──────────────────────────────────── Ratio 4 D No C D 90,000 No Ratio 5 C No C C 030,000 No Ratio 6 D No D B 90,000 Yes ━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━ In each of Examples 4 to 6, generation of dust and sludge was not observed in the long-term automatic processing, and the waste liquid neutralization processing was easy. It was also found that the developability was good, stains did not occur during printing, and the plate had sufficient printing durability. On the other hand, in Comparative Example 4, no generation of shavings was observed, but
Staining occurred during printing because the support was not hydrophilized. In Comparative Example 5, the stain resistance during printing was improved, but the number of printed sheets was not sufficient. Further, in Comparative Example 6, although stain resistance during printing and printing durability were sufficient, dust and sludge were generated during long-term processing.

As described above, the present invention is an excellent plate-making method which is sufficiently satisfactory in stain resistance and printing durability and free from the problem of waste liquid sludge and sludge. It turns out that is also preferable.

Claims (1)

(57) [Claims] 1. A hydrophilized aluminum support.
And R¹(PO (OH)_Two )_nOr R¹-(PO (O
H) (R^Two))_nA substituted or unsubstituted aliphatic represented by
Compound or aromatic compound (n is 1 or 2, n
When is 1, R ¹, R^TwoIs a substituted or unsubstituted alkyl
Group, alkoxy group, aryloxy group, aryl group, acyl group
Represents an alkyl group or an acyloxy group, and when n is 2, R¹Is replaced
Or represents an unsubstituted alkylene group or arylene group,
R^TwoIs as defined above)
Provide an organic layer containing at least one selected compound,
Positively containing an o-quinonediazide compound thereon.
After exposing the photosensitive lithographic printing plate provided with the mold type photosensitive layer to an image,
Alkali metal salts or ammonium salts of inorganic acids other than acids,
Alkali metal hydroxide, ammonium hydroxide and water soluble
At least one selected from the group consisting of organic amine compounds
Characterized by being developed with an aqueous solution containing various compounds.
Method for making lithographic printing plates.