JPH06234285A - Production of photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To obtain a photosensitive lithographic plate improved in water retentivity, hard to contaminate, and enhanced in adhesion between a photosensitive layer and a substrate by a method wherein a surface of an aluminum alloy plate or the like is electrolytically roughened and anodized, and thereon the photosensitive layer is applied by a specific coating weight. CONSTITUTION:In the production of a photosensitive lithographic plate, a surface of an aluminum plate or an aluminum allay plate is electrolytically roughened and anodized, and thereon a photosensitive layer is applied. At this time, the electrolytically roughening treatment is carried out using an alternating current in an electrolyte containing chlorine ion under conditions that an on-anode current density is 20-30A/dm<2> and an on-anode quantity of electricity is 300 coulomb/dm<2> or more. The coating weight of the photosensitive layer is set within the range of 0.5-2.0g/m<2>. In this manner, the obtained photosensitive lithographic plate is so improved in water retentivity that a shadow part cannot collapse even with a small amount of dampening water, hard to contaminate, and enhanced in adhesion between the photosensitive layer and the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate having a photosensitive layer on a support obtained by electrolytically roughening and anodizing an aluminum plate or an alloy plate thereof. The present invention relates to a method for producing a photosensitive lithographic printing plate having excellent performance in preventing the halftone portion (shadow portion) from becoming dirty.

[0002]

2. Description of the Related Art The lithographic printing method is a printing method utilizing the fact that water and oil are essentially immiscible. An area that repels ink (hereinafter, this area is referred to as "non-image area") and an area that repels water and receives oil-based ink (hereinafter, this area is referred to as "image area") are formed. The aluminum support used for the lithographic printing plate has excellent hydrophilicity and water retention because the surface is used so as to bear the non-image area, and further, the adhesion to the photosensitive layer provided thereon. It is required to have various conflicting performances such as excellent properties. When the support has a low hydrophilicity, ink adheres to the non-image area during printing, causing so-called background stain. When the water retention of the support is low,
If the amount of dampening water is not increased during printing, the shadow area will be clogged. Therefore, the so-called water width becomes narrow.

In order to obtain an aluminum support having good performance, it is customary to grain the surface of an aluminum plate to give fine irregularities. This graining includes mechanical graining methods such as ball graining, brush graining, wire graining, blast graining, and electrolytic graining for electrolytically etching an aluminum plate in an electrolytic solution containing hydrochloric acid and / or nitric acid. A roughening method and a composite roughening method in which a mechanical roughening method and an electrolytic roughening method described in US Pat. No. 4,476,006 are combined are known. However, the support roughened by these conventional methods is still insufficient in hydrophilicity, water retention and adhesion. That is, in order to improve the hydrophilicity to a desirable level, it is necessary to make the irregularities on the rough surface shallow and smooth to a certain extent, but this will reduce the water retention capacity of the support and worsen the adhesion to the photosensitive layer. On the contrary, if the unevenness of the rough surface is deepened, the water retention property, that is, the water width is widened, and the adhesiveness with the photosensitive layer is improved, but scumming occurs. In recent years, the lithographic printing industry has been rapidly increasing in speed and automation, and in the present situation where skilled workers are lacking, it is easy for even non-skilled workers to print, and lithographic printing plates with higher quality and more stable than ever. That is, a lithographic printing plate having a wide water width and being resistant to stains has long been desired.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to have a high water-retaining property, the shadow portion will not be crushed even if the amount of dampening water is reduced, and stains will not easily occur. Another object of the present invention is to provide a method for producing a photosensitive lithographic printing plate which gives a lithographic printing plate having good adhesion.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that
It was found that it is important to form a deep and uniform electrolytic roughening pit (EG pit) shape on the surface of an aluminum support, and to control the amount of a photosensitive layer coated on the surface, and complete the present invention. Came to. That is, according to the present invention, an aluminum or aluminum alloy plate is subjected to an alternating current in an electrolytic solution containing chloride ions to produce an anode current density of 20 to 30 A / dm.
^2. Electrolytic surface roughening treatment is performed under the condition of an electric quantity of 300 coulombs / dm ² or more at the time of anode, and then anodization is performed, and then a photosensitive layer is applied in an amount of 0.5 to 2.0 g / m ^2. And a method for producing a photosensitive lithographic printing plate.

The method for producing the photosensitive lithographic printing plate of the present invention will be described in detail below. The aluminum plate used in the present invention is selected from a pure aluminum plate, an alloy plate containing aluminum as a main component and a slight amount of a foreign element, or a plastic film laminated or vapor-deposited with aluminum. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of foreign elements in the alloy is 10% by weight or less. Aluminum suitable for the present invention is pure aluminum, but completely pure aluminum is difficult to produce due to refining technology, and thus may contain slightly different elements. Thus, the aluminum plate applied to the present invention, the composition of which is not specified, conventionally publicly known material, for example JIS A 1050, JIS A 1100, JIS A 3103, JI
SA 3005 etc. can be used appropriately. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6.
It is about mm. Then, the surface of the aluminum plate is subjected to electrolytic graining treatment.

In a preferred embodiment of the present invention, a surface treatment for removing the rolling oil adhering to the aluminum surface and cleaning the surface is performed prior to the electrolytic surface roughening treatment. Generally, in order to remove rolling oil, a method of cleaning the surface with a solvent such as trichlene or a surfactant is used. Further, the aluminum alloy plate is immersed in an aqueous solution of 1 to 30% sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, etc. at a temperature of 20 to 80 ° C. for 5 seconds to
A method of immersing for 250 seconds and then immersing in a 10-30% nitric acid or sulfuric acid aqueous solution at a temperature of 20-70 ° C. for 5 seconds-250 seconds to perform neutralization and smut removal after alkali etching is also commonly used. . After surface cleaning of this aluminum alloy plate, electrolytic surface roughening treatment is performed. The electrolytic solution used for electrolytic graining treatment in the present invention is an electrolytic solution containing chlorine ions. The concentration is preferably used in the range of 0.01 to 3%, more preferably 0.05 to 2.5%. This chlorine ion can be provided by adding hydrochloric acid or the like. Further, a corrosion inhibitor, a stabilizer, a grain leveling agent and the like can be added to the electrolytic solution. Typical examples of these additives are as follows. For example, chlorides such as sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, amines such as trimethylamine, diethanolamine, ethylenediamine, hexamethylenediamine, aldehydes such as formaldehyde, phosphoric acid, citric acid, sulfosalicylic acid, citric acid, apple Organic and inorganic acids such as acids can be contained in an amount of 0.05 to 3%.

The temperature of the electrolytic solution is usually 10 to 60 ° C. As the alternating current used at this time, any one of a rectangular wave, a trapezoidal wave, and a sine wave can be used as long as positive and negative polarities are alternately converted. Phase alternating current can be used. The current density at the time of the anode is 20 to 30 A / dm ² . If it is less than 20 A / dm ² , EG pits are not formed, and if it exceeds 30 A / dm ² , large shallow EG pits are formed and the dampening water on the printing plate cannot be controlled, so that the shadow part is easily soiled. And a good printed matter cannot be obtained. The amount of electricity at the anode is 300 coulomb / dm ² or more, preferably 300 to 200.
It is 0 coulomb / dm ² . If it is less than 300 coulombs / dm ² , shallow EG pits are formed, so that the fountain solution on the printing plate is insufficient and the shadow portion is easily soiled. On the other hand, if it exceeds 2000 coulombs / dm ² , large and deep EG pits are unevenly formed, and scumming is likely to occur. The aluminum plate surface-roughened in this manner may have a thickness of 10-5 if necessary.
It is preferable to remove smut adhering to the surface with 0% hot sulfuric acid (40 to 60 ° C.) or a dilute alkali (sodium hydroxide or the like). When removed with alkali, it is subsequently immersed in acid (nitric acid or sulfuric acid) for neutralization for cleaning.

Further, if desired, an anodizing treatment is performed in order to improve the water retention and abrasion resistance of the surface. As the electrolyte used for anodizing the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because it varies depending on the electrolyte used, but generally the concentration of the electrolyte is 1 to 80% by weight solution, the liquid temperature is 5 to 70 ° C, and the current density is 1 to 60 A / dm.
² , a voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are suitable. In the sulfuric acid method, the treatment is usually performed with a direct current, but it is also possible to use an alternating current. Sulfuric acid is used at a concentration of 5 to 30%, and is used in a temperature range of 20 to 60 ° C.
It is electrolyzed for 250 seconds. The electrolytic solution preferably contains aluminum ions. Further, the current density at this time is preferably 1 to 20 A / dm ² . In the case of the phosphoric acid method, the treatment is performed at a concentration of 5 to 50%, a temperature of 30 to 60 ° C., and a current density of 1 to 15 A / dm ² for 10 to 300 seconds. The amount of the anodized film is suitably 1.0 g / m ² or more, but 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 / m ² , printing durability is insufficient, or the non-image area of the planographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. Scratch stains are likely to occur.

After the anodizing treatment, the aluminum surface is optionally hydrophilized. As the hydrophilic treatment used in the present invention, US Patent No. 2,714,066,
There are alkali metal silicate (eg aqueous sodium silicate) processes such as those disclosed in Nos. 3,181,461, 3,280,734 and 3,902,734. In this method, the support is immersed or electrolyzed in an aqueous sodium silicate solution. In addition, Japanese Patent Publication Sho 36-22
For example, the method of treatment with potassium fluorozirconate disclosed in Japanese Patent Application No. 063 and polyvinyl phosphonic acid as disclosed in US Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 may be used. It is also preferable that after the graining treatment and the anodic oxidation, the sealing treatment is performed. Such sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

If necessary, an organic undercoat layer is provided on the aluminum plate before the photosensitive layer is coated. Examples of the organic compound used in this organic undercoat layer include phosphonic acids having an amino group such as carboxymethyl cellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, and naphthyl. Organic phosphonic acids such as phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and triethanolamine hydrochloride The hydroxy Although selected from such as hydrochloric acid salt of an amine having a group,
You may use it in mixture of 2 or more types.

This organic undercoat layer can be provided by the following method. That is, water or a solvent in which the above organic compound is dissolved in an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof is applied on an aluminum plate and dried to provide a method, and water or methanol, ethanol, methyl ethyl ketone, etc. In a solution prepared by dissolving the above organic compound in the organic solvent or a mixed solvent thereof, the aluminum plate is immersed to adsorb the above organic compound, and then washed with water or the like and dried to form an organic undercoat layer. Is the way. In the former method, a solution having a concentration of 0.005 to 10% by weight of the above organic compound can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, or curtain coating may be used. Also, in the latter method, 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 to 90 ° C, preferably 25.
Is about 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The pH of the solution used for this is adjusted with basic substances such as ammonia, triethylamine and potassium hydroxide, and acidic substances such as hydrochloric acid and phosphoric acid.
It can also be used in the range of pH 1-12. Further, a yellow dye may be added to improve the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is 2
~ 200 mg / m ² is suitable, preferably 5-100 mg
/ M ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same applies when the amount is larger than 200 mg / m ² .

On the back surface of the support of the photosensitive lithographic printing plate (PS plate) using the support thus obtained, a coating layer made of an organic polymer compound (for preventing scratching of the photosensitive layer when it is overlaid ( Hereinafter, this coating layer is referred to as a back coat layer), if necessary. At least one resin selected from the group consisting of a saturated copolymerized polyester resin, a phenoxy resin, a polyvinyl acetal resin, and a vinylidene chloride copolymerized resin having a glass transition point of 20 ° C. or higher is used as the main component of the back coat layer. The saturated copolyester resin is composed of a dicarboxylic acid unit and a diol unit. Examples of the dicarboxylic acid unit of the polyester used in the present invention include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid and tetrachlorophthalic acid; adipic acid, azelaic acid, succinic acid, oxalic acid and suberic acid. , Sebacic acid, malonic acid, saturated aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and the like.

The back coat layer further includes dyes and pigments for coloring, silane coupling agents for improving adhesion to an aluminum support, diazo resins containing diazonium salts, organic phosphonic acids, organic phosphoric acids and cations. Waxes, higher fatty acids, higher fatty acid amides, silicone compounds composed of dimethylsiloxane, modified dimethylsiloxane, polyethylene powder and the like, which are usually used as a slip agent, are appropriately added. The thickness of the back coat layer is basically sufficient as long as it does not damage the photosensitive layer even if there is no interleaving paper, and the range of 0.01 to 8 μm is preferable. If the thickness is less than 0.01 μm, it is not possible to prevent scratches on the photosensitive layer when the PS plates are stacked and handled. If the thickness exceeds 8 μm, the back coat layer may swell due to the chemicals used around the printing plate during printing, the thickness may change, and the printing pressure may change to deteriorate the printing characteristics. Various methods can be applied to coat the back coat layer on the back surface of the aluminum support. For example, make a solution in a suitable solvent,
Alternatively, a method of forming an emulsified dispersion and coating and drying, for example, a method of laminating a film-shaped product in advance with an adhesive or heat to an aluminum support, and a method of forming a molten film with a melt extruder and laminating to a support Etc., but the most preferable method for ensuring the above-mentioned coating amount is a method of forming a solution and coating and drying. As the solvent used here, the organic solvents described in JP-A-62-251739 are used alone or in combination.

On the aluminum plate having a hydrophilic surface thus obtained, a photosensitive layer made of a known photosensitive composition is provided to obtain a photosensitive lithographic printing plate. As the photosensitive composition, a positive type composition containing an o-quinonediazide compound as a main component, a diazonium salt, an alkali-soluble diazonium salt, a photopolymerizable compound containing an unsaturated double bond-containing monomer as a main component, and cinnamic acid or dimethyl A negative type having a photocrosslinkable compound containing a maleimide group as a photosensitive material is used. In addition, Japanese Examined Patent Publication Nos. 37-17172 and 38-6
961, JP-A-56-107246, 60-25.
No. 4142, Japanese Patent Publication Nos. 59-36259, 59-25.
217, JP-A-56-146145 and JP-A-62-19.
No. 4257, No. 57-147656, No. 58-100.
The electrophotographic photosensitive layers described in 862 and 57-161863 can also be used. Among the above photosensitive materials, examples of the photopolymerizable compound containing an unsaturated double bond-containing monomer as a main component include U.S. Pat. Nos. 2,760,863 and 3,060,02.
A composition comprising a photopolymerization initiator and an addition-polymerizable unsaturated compound having two or more terminal ethylene groups described in Japanese Patent No. 3 and JP-A-59-53836 can be used. Further, as a negative type photosensitive material containing a photocrosslinkable compound containing a dimethylmaleimide group, for example, JP-A-52-98 is disclosed.
No. 8, European Patent No. 0410654, JP-A-3-2888.
Examples thereof include the photosensitive materials described in JP-A No. 53-53 and JP-A-4-25845.

Among these, as the o-naphthoquinonediazide compound used as a positive photosensitive composition, the 1,2-diazonaphthoquinonesulfonic acid and pyrogallol-acetone resin described in JP-B-43-28403 are used. Esters are preferred. Other suitable orthoquinonediazide compounds include, for example, U.S. Pat.
There are esters of 1,2-diazonaphthoquinone-5-sulfonic acid and phenol-formaldehyde resin described in JP-A No. 120 and No. 3,188,210, and JP-A-2-96163 and JP-A-2-96165. There is an ester of 1,2-diazonaphthoquinone-1-sulfonic acid and a phenol-formaldehyde resin described in JP-A-2-967671 and JP-A-2-96761. Other useful o-naphthoquinonediazide compounds include:
Those known in numerous patents can be mentioned. For example, JP-A Nos. 47-5303, 48-63802 and 48
-63803, 48-96575, 49-38.
No. 701, No. 48-13854, Japanese Patent Publication No. 37-180
No. 15, No. 41-11222, No. 45-9610,
No. 49-17481, U.S. Pat. No. 2,797,213,
No. 3,453,400, No. 3,544,323, No. 3,573,917
No. 3,674,495, No. 3,785,825, British Patent No.
1,227,602, 1,251,345, 1,267,005,
1,329,888, 1,330,932, German Patent 854,
Mention may be made of those described in each specification such as No. 890.

A 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. Specific examples of such compounds are described in JP-A Nos. 51-139402 and 58-15094.
No. 8, No. 58-203434, No. 59-165053.
No. 60, No. 12-14445, No. 60-134235.
Issue No. 60-163043, Issue No. 61-118744
No. 6, No. 62-10645, No. 62-10646, No. 62-153950, No. 62-178562, No. 6
4-76047, U.S. Pat. Nos. 3,102,809 and 3,12.
No. 6,281, No. 3,130,047, No. 3,148,983, No.
Examples thereof include those described in respective publications or specifications such as 3,184,310, 3,188,210, and 4,639,406. When synthesizing these o-naphthoquinone diacid compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinone sulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound.
It is more preferable to react 3 to 1.0 equivalent. 1,2-
As the cyazonaphthoquinone sulfonic acid chloride, 1,
2-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.
The proportion of the diazonaphthoquinonesulfonic acid esterified compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%. is there. The amount of these positive-working photosensitive compounds (including the above-mentioned combinations) in the photosensitive composition is suitably 10 to 50% by weight, more preferably 15 to 40% by weight.

The o-quinonediazide compound alone can form the photosensitive layer, but it is preferable to use a resin soluble in alkaline water together as a binder. As such a resin soluble in alkaline water, there are novolac type resins such as phenol formaldehyde resin, o-, m- and p-cresol formaldehyde resin, m / p-mixed cresol formaldehyde resin, phenol / cresol ( o-, m-, p-, m /
mixed formaldehyde resin and the like may be used. Further, 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 monomers (1) to (13) as constituent units and having a molecular weight of usually 10,000 to 200,000. (1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having aromatic hydroxyl groups, such as N- (4
-Hydroxyphenyl) acrylamide or N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
And p-hydroxystyrene, o-, m- and p-
Hydroxyphenyl acrylate or methacrylate, (2) acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid, methacrylic acid, maleic anhydride. Unsaturated carboxylic acids such as, methaconic acid,

(4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylate-2 -(Substituted) acrylic acid esters such as -chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, (Substituted) methacrylic acid esters such as glycidyl methacrylate and N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N- Hexyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N
-Phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide. Or methacrylamide,

(7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as octyl vinyl ether and phenyl vinyl ether, (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, (9) styrenes such as styrene, methylstyrene and chloromethylstyrene, ( 1
0) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (1)
2) N-vinylpyrrolidone, N-vinylcarbazole,
(13) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N-, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. [1- (3-Aminosulfonyl) naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacryl Methacrylamides such as amide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o Aminosulfonylphenyl acrylate, m- aminosulfonylphenyl acrylate,
p-aminosulfonylphenyl acrylate, 1- (3
-Aminosulfonylphenylnaphthyl) acrylates and other unsaturated sulfonamides such as acrylic acid esters, o-aminosulfonylphenyl methacrylate, m
-Unsaturated sulfonamides such as methacrylic acid esters such as aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate.

Further, a monomer copolymerizable with the above-mentioned monomer may be copolymerized. Further, a copolymer obtained by copolymerizing the above-mentioned monomers is also modified, for example, with glycidyl acrylate, glycidyl methacrylate, etc., but is not limited thereto. The above copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the preferable acid value of the copolymer is 0.
-10 meq / g, more preferably 0.2-5.0 meq / g. The preferred molecular weight of the above copolymer is 10,000 to 100,000. Further, polyvinyl butyral resin, polyurethane resin, polyamide resin and epoxy resin may be added to the above-mentioned copolymer, if necessary. Such alkali-soluble polymer compounds may be used alone or in combination of two or more, and 80% by weight of the total photosensitive composition
It is used in the following addition amounts. Further, U.S. Pat.
As described in No. 9, it is not possible to use a condensate of phenol and formaldehyde, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, having a C3-8 alkyl group as a substituent in combination. It is preferable for improving the oil sensitivity. 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 anhydrides include US Pat. No. 4,115,12
No. 8 phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-
Endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,
4 ', 4 "-trihydroxy-triphenylmethane,
4,4 ', 3 ", 4" -tetrahydroxy-3,5
3 ', 5'-tetramethyltriphenylmethane and the like can be mentioned. Further, as organic acids, JP-A-60-88 is used.
There are sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters, carboxylic acids and the like described in JP-A No. 942, JP-A-2-96755 and the like, and specifically, p-toluene sulfone. acid,
Dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfate, 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-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. The ratio of the cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is 0.
05 to 15% by weight is preferable, more preferably 0.1 to 5
% By weight.

Further, in the photosensitive composition of the present invention, in order to broaden the stability of processing (so-called development latitude) under developing conditions, a nonionic interface as described in JP-A-62-251740 is used. Activators, amphoteric surfactants such as those described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include:
Sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate,
Examples thereof include polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N.
-Tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and alkyl imidazoline series (for example, trade name Levon 15, manufactured by Sanyo Kasei Co., Ltd.) and the like. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.05% by weight.
It is 1 to 5% by weight.

In the photosensitive composition of the present invention, a printout agent for obtaining a visible image immediately after exposure and a dye or pigment as an image colorant can be added. Typical examples of the printout agent include a combination of a compound that releases an acid upon exposure (photoacid releasing agent) and an organic dye capable of forming a salt. Specifically, JP-A-50-3620
No. 9 and 53-8128
-A combination of naphthoquinone diazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-36223.
No. 54, No. 54-74728, No. 60-3626, No. 6
Examples include combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 1-143748, 61-151644 and 63-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give a clear printout image.

As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, 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 (CI42535), Ethyl Violet, Rhodamine. B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI5201)
5) etc. can be mentioned. In addition, JP-A-62-2
The dyes described in Japanese Patent No. 93247 are particularly preferable.

The photosensitive composition is dissolved in a solvent that dissolves each of the above components and applied onto the aluminum plate of the support.
The solvent used here is, for example, JP-A-62-2517.
Organic solvents as described in JP-A-39 are used alone or in combination. The photosensitive composition is dissolved and dispersed at a solid content concentration of 2 to 50% by weight and applied on a support.
To be dried. The coating amount of the layer of the photosensitive composition (photosensitive layer) coated on the support varies depending on the use, but generally, the weight after drying is preferably 0.3 to 4.0 g / m ^2. .
The smaller the coating amount, the smaller the exposure amount for obtaining an image, but the film strength decreases. As the coating amount increases, the exposure amount is required but the photosensitive film becomes stronger. For example, when used as a printing plate, a printing plate having a high printable number (high printing durability) can be obtained. In the photosensitive composition,
A surfactant for improving the quality of the coated surface, for example, a fluorinated surfactant as described in JP-A-62-170950 can be added. The preferred addition amount is 0.001 to 1.0% by weight of the total photosensitive composition,
More preferably, it is 0.005-0.5% by weight.

Next, examples of the negative PS plate photosensitive composition include those having a photosensitive layer containing a photosensitive diazo compound, a photopolymerizable photosensitive layer, a photocrosslinkable photosensitive layer, and the like.
Of these, the photocurable photosensitive copying material comprising a photosensitive diazo compound will be described in detail with reference to examples. As the photosensitive diazo compound, a diazo resin obtained by condensing an aromatic diazonium salt and a reactive carbonyl group-containing organic condensing agent, particularly aldehydes such as formaldehyde and acetaldehyde or acetals in an acidic medium is preferably used. The most typical one is a condensate of P-diazodiphenylamine and formaldehyde. Methods for synthesizing these diazo resins are described, for example, in U.S. Patent No. 2,678,498,
No. 3,050,502, No. 3,311,605 and No. 3,277,
No. 074. Further, as the photosensitive diazo compound, a co-condensation diazo compound of an aromatic diazonium salt described in JP-B-49-48,001 and a substituted aromatic compound containing no diazonium group is preferably used. A co-condensed diazo compound with an aromatic compound substituted with an alkali-soluble group such as a hydroxyl group is preferable. Furthermore, JP-A-4-18559, JP-A-4-190361 and JP-A-4-172353.
A photosensitive diazo compound obtained by condensing an aromatic diazonium salt with a reactive carbonyl compound having an alkali-soluble group as described in JP-A No. 1993-154 is also preferably used. There are diazo resins using inorganic anions such as mineral acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid or double salts with zinc chloride as counter anions of these diazonium salts, but they are substantially water-insoluble and organic. Solvent-soluble diazo resins are particularly preferred. Such preferred diazo resins are described in detail in JP-B-47-1167 and U.S. Pat. No. 3,300,309.

Further, JP-A-54-98613 and 56-56
A diazo resin having a counter anion of halogenated Lewis acid such as tetrafluoroboric acid and hexafluorophosphoric acid and perhalogen acid such as perchloric acid and periodic acid as described in JP-A-121031 is preferably used. To be
Also, JP-A-58-209733 and JP-A-62-1757.
The diazo resins having a long-chain alkyl group-containing sulfonic acid as a counter anion, which are described in JP-A Nos. 31 and 63-262643, are also preferably used. The photosensitive diazo compound is contained in the photosensitive layer in an amount of 5 to 50% by weight, preferably 8 to 20% by weight. The photosensitive diazo compound is preferably used in combination with a lipophilic polymer compound soluble or swellable in alkaline water as a binder. Examples of such lipophilic polymer compounds include the same compounds (1) to (1) as those used in the positive-type photosensitive composition described above.
A copolymer having a molecular weight of 10,000 to 200,000, which has the monomer shown in (13) as its constitutional unit, can be mentioned. Further, the monomers shown in (14) and (15) below are used as constitutional units. Polymerized polymer compounds can also be used. (14) Maleimide, N-acryloylacrylamide, N-acetylacrylamide, N-propionylacrylamide, N- (p-chlorobenzoyl) acrylamide, N-acetylacrylamide, N-acryloylmethacrylamide, N-acetylmethacrylamide,
Unsaturated imides such as N-propionyl methacrylamide, N- (p-chlorobenzoyl) methacrylamide,
(15) N- [2- (acryloyloxy) -ethyl]
-2,3-Dimethylmaleimide, N- [6- (methacryloyloxy) -hexyl] -2,3-dimethylmaleimide, unsaturated monomers having a crosslinkable group in the side chain such as vinylcinnamate.

Further, a monomer copolymerizable with the above-mentioned monomer may be copolymerized. Further, a copolymer obtained by copolymerizing the above-mentioned monomers is also modified, for example, with glycidyl acrylate, glycidyl methacrylate, etc., but is not limited thereto. The above copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the preferable acid value of the copolymer is 0.
-10 meq / g, more preferably 0.2-5.0 meq / g. The preferred molecular weight of the above copolymer is 10,000 to 100,000. Further, polyvinyl butyral resin, polyurethane resin, polyamide resin and epoxy resin may be added to the above-mentioned copolymer, if necessary. It is also possible to use a novolac type resin, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, or an alkali-soluble resin containing a phenolic hydroxyl group as disclosed in JP-A-51-43711. it can. Such alkali-soluble polymer compounds can be used alone or in combination of two or more, and usually 40 to 95% by weight in the solid content of the whole photosensitive composition.
It is contained in the range of.

In the photosensitive composition, an oil-sensitizing agent for improving the oil-sensitivity of an image (for example, a half ester of a styrene-maleic anhydride copolymer described in JP-A-55-527) with an alcohol is used. Compound, novolac resin, p-
50% fatty acid ester of hydroxystyrene, etc.) is added. Furthermore, a plasticizer for imparting flexibility and abrasion resistance to the coating film is added. For example, butylphthalyl,
Polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate,
Examples include dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid oligomers and polymers, of which tricresyl phosphate is particularly preferred. Further, in the photosensitive composition, in order to spread stability over time, for example, phosphoric acid, phosphorous acid, citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy- 2-Hydroxybenzophenone-5-sulfonic acid, tartaric acid and the like are added.

Further, in the photosensitive composition, a printout agent for obtaining a visible image immediately after exposure and a dye such as a dye or a pigment as an image colorant can be added. As the dye, those that change color tone by reacting with free radicals or acids are preferably used. For example, Victoria Pure Blue BOH (Hodogaya Chemical), Oil Yellow # 1
01, oil yellow # 103, oil pink # 31
2, oil red, 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.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet (CI42555), Methyl Violet (CI425).
35), ethyl violet, rhodamine B (CI14
5170B), malachite green (CI4200
0), methylene blue (CI52015), brilliant blue, methyl green, erythricin B, basic fuchsin, m-cresol purple, auramine, 4
-P-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide and other triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes are colored or colorless or An example of changing to different color tones is given.

On the other hand, as a discoloring agent that changes from colorless to colored, leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1, 2,
3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p,
p ', p "-tris-dimethylaminotriphenylmethane, p, p'-bis-dimethylaminodiphenylmethylimine, p, p', p" -triamino-o-methyltriphenylmethane, p, p'-bis -Dimethylaminodiphenyl-4-anilinonaphthylmethane, p, p ', p "
-Primary or secondary arylamine dyes represented by triaminotriphenylmethane. Particularly preferred are triphenylmethane dyes and diphenylmethane dyes, more preferably triphenylmethane dyes, and particularly Victoria Pure Blue BOH. The dye is usually contained in the photosensitive composition in an amount of about 0.5 to 10% by weight, more preferably about 1 to 5% by weight.

Cyclic acid anhydrides, phenols, organic acids and higher alcohols can be added to the photosensitive composition in order to enhance the developability. The photosensitive composition is
It is dissolved in a solvent that dissolves each of the above components and coated on an aluminum plate of a support. As the solvent used here, the organic solvents described in JP-A-62-251739 are used alone or in combination. The photosensitive composition is dissolved and dispersed at a solid content concentration of 2 to 50% by weight, coated on a support and dried. The coating amount of the layer (photosensitive layer) of the photosensitive composition coated on the support varies depending on the use, but generally, the weight after drying is 0.3 to 4.
0 g / m ² is preferred. The smaller the coating amount, the smaller the exposure amount for obtaining an image, but the film strength decreases. As the coating amount increases, the exposure amount is required, but the photosensitive film becomes stronger. For example, when used as a printing plate,
A printing plate with a high printable number (high printing durability) can be obtained. A surfactant for improving the coated surface quality can be added to the photosensitive composition as in the case of the positive photosensitive composition described above. In the production of the photosensitive lithographic printing plate, either the back coat layer on the back side or the photosensitive composition layer on the front side may be coated on the support first, or both may be coated simultaneously.

On the surface of the photosensitive layer provided as described above, a matte layer is provided in order to shorten the vacuuming time during contact exposure using a vacuum baking frame and prevent baking blur. Specifically, a method of providing a mat layer as described in JP-A-50-125805, JP-B-57-6582, and JP-A-61-28986, and JP-B-62-62337. Examples of the method include heat fusion of the solid powder as described above. The average diameter of the mat layer used in the present invention is preferably 100 μm or less,
When the average diameter is larger than this, when the PS plates are stored in piles, the contact area between the photosensitive layer and the backcoat layer increases, the slipperiness decreases, and scratches occur on the surfaces of both the photosensitive layer and the backcoat layer. easy. The average height of the mat layer is 10μ
m or less is preferable, and more preferably 2 to 8 μm.
If the average height is higher than this range, it is difficult to attach fine lines and the number of highlight dots decreases, which is not preferable for tone reproduction. When the average height is 2 μm or less, vacuum adhesion is insufficient and burning blur occurs. The coating amount of the mat layer is preferably from 5 to 200 mg / m ^2, more preferably from 20~150mg / m ^2. When the coating amount is larger than this range, the contact area between the photosensitive layer and the back coat layer increases and causes scratches, and when it is smaller than this range, the vacuum adhesion becomes insufficient.

The PS plate thus obtained was passed through a transparent original image through a carbon arc lamp, a mercury lamp, a metal halide lamp,
After being exposed to an actinic ray using a xenon lamp, a tungsten lamp, or the like as a light source, development processing is performed. As a developer and a replenisher for such a PS plate, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, sodium triphosphate, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, Inorganic alkaline agents such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium are mentioned. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkaline agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more. Among these alkaline agents, an aqueous solution of silicate such as sodium silicate or potassium silicate is particularly preferable as the developer for positive PS plate. The reason is that the ratio of silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide M ₂ O (generally [SiO ₂ ] / [M ₂
This is because the developability can be controlled by the concentration and the concentration). For example, JP-A-54-6200
No. 4 as disclosed in Japanese, the molar ratio of SiO ₂ / Na ₂ O 1.0 to 1.5 (that is, [SiO _2] / [Na ₂ O] is 1.0 to 1.5)
And an aqueous solution of sodium silicate having a SiO ₂ content of 1 to 4% by weight, and [SiO ₂ ] / [M] of 0.5 as described in JP-B-57-7427. To 0.75 (that is, [SiO ₂ ] / [M ₂ O] is 1.0 to 1.5), the concentration of SiO ₂ is 1 to 4% by weight, and all alkalis present therein. At least 20% based on gram atom of metal
An aqueous solution of an alkali metal silicate containing potassium is preferably used.

Further, when the PS plate is developed by using an automatic developing machine, an aqueous solution (replenisher) having a higher alkalinity than the developing solution is added to the developing solution, so that the developing solution in the developing tank for a long time is added. It is known that a large number of PS plates can be processed without replacing the plate. Also in the present invention, this replenishment system is preferably applied. For example, the SiO ₂ / Na ₂ O molar ratio of the developer as disclosed in JP-A-54-62004 is 1.0 to 1.5 (that is, [SiO ₂ ] /
[Na ₂ O] is 1.0 to 1.5), and the content of SiO ₂ is 1 to
An aqueous solution of 4% by weight of sodium silicate was used, and the molar ratio of SiO ₂ / Na ₂ O was 0.5 to 1.5 continuously or intermittently depending on the throughput of the positive photosensitive lithographic printing plate. (Ie [Si
A method of adding an aqueous sodium silicate solution (replenisher) having an O ₂ ] / [Na ₂ O] of 0.5 to 1.5) to a developer, and further, JP-B-5.
[SiO ₂ ] /, which is disclosed in JP-A-7-7427.
[M] is 0.5 to 0.75 (that is, [SiO ₂ ] / [M ₂ O] is 1.
0-1.5), using a developer of an alkali metal silicate having a SiO ₂ concentration of 1 to 4% by weight, and [SiO ₂ ] / [M of the alkali metal silicate used as a replenisher. ] Is 0.25
˜0.75 (ie [SiO ₂ ] / [M ₂ O] 0.5-1.5) and both the developer and the replenisher are grams of total alkali metal present therein. A development method consisting of containing at least 20% potassium on an atomic basis is preferably used.

When an alkali metal silicate is used as the replenishing solution, the replenishing solution becomes highly active and the replenishing amount can be reduced by reducing the molar ratio [SiO ₂ ] / [M ₂ O]. However, running costs and the amount of waste liquid are reduced, which is preferable. However, it is known that the support aluminum of the PS plate is dissolved due to high activation to produce an insoluble matter in the developing solution. Such a highly active developer has a SiO ₂ / M ₂ O molar ratio of 0.7 to 1.5 and a S
The concentration of iO ₂ is 1.0 to 4.0% by weight of an aqueous solution of alkali metal silicate, and the replenisher has a SiO ₂ / M ₂ O molar ratio of 0.3 to 1.0. , SiO ₂ concentration is 0.5-4.0% by weight
A system that is an aqueous solution of the alkali metal silicate of is preferably used. The developer and replenisher used for the development of positive and negative PS plates may contain various surface active agents as necessary for the purpose of promoting or suppressing the developability, dispersing development residue and enhancing the ink affinity of the image area of the printing plate. Agents and organic solvents can be added. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial ester. , Sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester , Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide,
Nonionic surfactants such as N, N-bis-2-hydroxyalkylamines, polyoxyethylenealkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietic acid salts,
Hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate ester salts, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxypolyoxyethylenepropyl sulfonates, polyoxy Ethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfate ester salts of fatty acid alkyl esters, alkyl sulfate esters salts,

Polyoxyethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene styryl phenyl ether sulfuric acid ethylene salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphorus Acid ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partial saponification products of styrene / maleic anhydride copolymers, partial saponification products of olefin / maleic anhydride copolymers, naphthalene styrenic acid salt formalin condensates Surfactants such as anionic surfactants, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives and other cationic surfactants Carboxy betaines, aminocarboxylic acids, sulfobetaines, such amino acid esters, amphoteric surfactants such as imidazolines. Among the above-mentioned surfactants, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included.

A more preferred surfactant is a fluorinated surfactant containing a perfluoroalkyl group in the molecule. Such fluorine-based surfactants include perfluoroalkylcarboxylates, perfluoroalkylsulfonates, anionic types such as perfluoroalkyl phosphates, and amphoteric types such as perfluoroalkylbetaines.
Cationic type and perfluoroalkylamine oxide such as perfluoroalkyltrimethylammonium salt, perfluoroalkylethylene oxide adduct, perfluoroalkyl group- and hydrophilic group-containing oligomer,
Nonionic types such as perfluoroalkyl group- and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic group- and lipophilic group-containing oligomers, and perfluoroalkyl group- and lipophilic group-containing urethanes can be mentioned. The above-mentioned surfactants can be used alone or in combination of two or more kinds, and 0.001 to 10% by weight in the developer,
More preferably, it is added in the range of 0.01 to 5% by weight.

Suitable organic solvents are those having a solubility in water of about 10% by weight or less, preferably 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1.
-Butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4 -Methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used liquid. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and it is therefore impossible to expect to secure good developability.

A reducing agent can be further added to the developer and replenisher used for developing the PS plate. This is to prevent stains on the printing plate and is particularly effective when developing a negative PS plate containing a photosensitive diazonium salt compound. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, methole, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. More preferable inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite acid, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionous acid. Examples thereof include salt. Among these reducing agents, sulfite has a particularly excellent antifouling effect. These reducing agents are preferably added to the developer at the time of use in an amount of 0.0
It is contained in the range of 5 to 5% by weight.

An organic carboxylic acid may be further added to the developing solution and the replenishing solution. Preferred organic carboxylic acids are aliphatic carboxylic acids having 6 to 20 carbon atoms and aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a benzene ring, a naphthalene ring, an anthracene ring or the like is substituted with a carboxyl group, and specifically, o-chlorobenzoic acid, p-chlorobenzoic acid,
o-hydroxybenzoic acid, p-hydroxybenzoic acid, o
-Aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid,
2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid,
1-hydroxy-2-naphthoic acid, 3-hydroxy-2
-Naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-
Although there are naphthoic acid and 2-naphthoic acid, hydroxynaphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used in the form of sodium salt, potassium salt or ammonium salt in order to enhance water solubility.
The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is less than 0.1% by weight, the effect is not sufficient, and if it is 10% by weight or more, further improvement of the effect cannot be achieved. Not only that, when other additives are used in combination, dissolution may be hindered. Therefore, the preferable addition amount is 0.1 to 10% by weight with respect to the developing solution at the time of use, and more preferably 0.1.
It is 5 to 4% by weight.

If necessary, the developer and replenisher may further contain defoaming agents, water softeners, and conventionally known compounds such as organic boron compounds described in Japanese Patent Publication No. 1-57895. You can Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid. Acetic acid and aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic salt), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene) Phosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

The optimum value of such a water softener varies depending on its chelating power, the hardness of hard water used, and the amount of hard water. 0.01-5% by weight, more preferably 0.01-
It is in the range of 0.5% by weight. If the addition amount is less than this range, the intended purpose is not sufficiently achieved, and if the addition amount is more than this range, the image area is adversely affected such as color loss. The remaining component of the developing solution and the replenishing solution is water, but if desired, various additives known in the art can be added. It is advantageous in terms of transportation that the developing solution and the replenishing solution are concentrated solutions having a water content smaller than that at the time of use and are diluted with water at the time of use. In this case, the degree of enrichment should be such that each component does not separate or precipitate.

The PS plate thus developed is post-treated with washing water, a rinse solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. Various combinations of these treatments can be used for the post-treatment of the PS plate of the present invention. In recent years, in the plate making / printing industry, automatic developing machines for PS plates have been widely used in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of an apparatus for conveying a PS plate, each processing solution tank and a spraying apparatus, and the exposed PS
While the plate is conveyed horizontally, each processing solution pumped up by a pump is sprayed from a spray nozzle to perform development processing. Further, recently, a method has also been known in which a PS plate is dipped and conveyed by a submerged guide roll or the like in a treatment liquid tank filled with the treatment liquid for treatment. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like.

Examples 1 to 7 and Comparative Examples 1 to 4 JIS A 1050 aluminum plates having a thickness of 0.24 mm were removed with 10% sodium hydroxide to remove the rolling oil adhering to the surface, and then 2
After neutralizing and washing in 0% nitric acid and washing with water, electrolytic surface roughening treatment was performed in a 10% hydrochloric acid electrolyte solution at the current density at the anode and the amount of electricity at the anode shown in Table 1. Then, after dipping in a 1% sodium hydroxide aqueous solution at 40 ° C. for 30 seconds, dipping in a 30% sulfuric acid aqueous solution and desmutting treatment at 60 ° C. for 40 seconds, a current density of 2 A / dm was applied in a 20% sulfuric acid aqueous solution. ^{In 2}
A substrate was prepared by anodizing with direct current so that the weight of the oxide film was 3.0 g / m ² .

An undercoat liquid having the following composition was applied to the surface of the substrate thus treated and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² . Undercoating liquid Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15 g β-alanine 0.10 g Methanol 40 g Pure water 60 g A substrate was prepared in this manner. Next, the following photosensitive solution was applied onto this substrate and dried at 110 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying is shown in Table 1.

[Photosensitive Solution] Esterification product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 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 to 4, weight average molecular weight 3,000, number average molecular weight 1,100, containing 0.7% unreacted cresol) 1.1 g m-cresol-formaldehyde novolac resin (weight average molecular weight 1,700, number average molecular weight 600, containing 1% of unreacted cresol) 0.3 g poly [N- (P-aminosulfonylphenyl) acrylamide-co-normal butyl acrylate-co-diethylene glycol monomethyl ether methacrylate] (As described in Japanese Patent Application No. 3-311241, the molar ratio of each monomer is 40:40:20, weight average molecular weight 40,000, number average molecular weight 20,000) 0.2 g

P-normal octylphenol-formaldehyde resin (as described in US Pat. No. 4,123,279) 0.02 g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydrophthalic anhydride 0.1. 1 g Benzoic acid 0.02 g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -S-triazine 0.01 g 4- [PN- (P -Hydroxybenzoyl) aminophenyl] -2,6-bis (trichloromethyl) -S-triazine 0.02 g 2-trichloromethyl-5- (4-hydroxystyryl) -1,3,4-oxadiazole 0.01 g Victoria Pure Blue BOH Dye with 1-naphthalenesulfonic acid as the counter anion 0.02g

MODIPER F-200 (Nippon Oil and Fats Co., Ltd. Fluorine-based surfactant, 30 wt% methyl ethyl ketone and methyl isobutyl ketone mixed solvent solution) 0.06 g Megafac F177 (Dainippon Ink and Chemicals, Inc. Fluorine -Based surfactant, 20% by weight methyl isobutyl ketone solution) 0.02 g methyl ethyl ketone 15 g 1-methoxy-2-propanol 10 g

On the photosensitive layer thus coated, according to the method described in Example 1 of JP-B-61-28986, (methyl methacrylate / ethyl acrylate / sodium acrylate = 68/20 / A mat layer was provided by electrostatically spraying the aqueous copolymer solution of 12).
The photosensitive lithographic printing plate thus produced was exposed through a transparent positive film through a transparent positive film at a distance of 1 m with a metal halide lamp of 3 kw for 50 seconds, and then SiO ₂ / Na ₂ was used as a developing solution. O molar ratio is 1.74
5.26% aqueous solution of sodium silicate (pH = 12.7)
FR-3 manufactured by Fuji Photo Film Co., Ltd. as a rinse liquid
Processing was carried out through an automatic processor Stablon 900D manufactured by Fuji Photo Film Co., Ltd. charged with (1: 7). After leaving this lithographic printing plate for 1 day, the printing was evaluated. Heidelberg KOR-D was used as the printing machine, Fuji Photo Film Co., Ltd. EU-3 (1: 100) was used as the dampening water, and Toyo Ink Co., Ltd. Mark Five New Ink was used as the ink.

Regarding the stains on the shadow portion after printing, it was judged whether 80% halftone dots of the printed matter were open when the dampening water was squeezed on the printing machine. The degree of stain on the shadow portion is indicated by the following display. A ... fully open B ... almost open
C ... somewhat clogged D ... considerably clogged In addition, it is at the level of B or higher that a preferable printed material having no clogging of the shadow portion can be obtained. As a result, as shown in Table 1, the lithographic printing plate of the present invention did not easily cause background stains, and did not cause stains in the shadow portion even when the dampening water was reduced. Good printed matter was obtained even after printing 70,000 to 100,000 sheets.

[0055]

[Table 1] ─────────────────────────────────── Electrolytic surface roughening conditions Anode in the shadow area of the photosensitive layer Time current Amount of electricity at anode Application amount Soil density (A / dm ² ) (Coulomb / dm ² ) (g / m ² ) ────────────────────── ───────────── Present invention 1 20 400 1.5 A 2 25 300 1.5 B 3 25 400 0.5 A 4 25 400 1.5 A 5 25 400 2.0 B 6 25 500 1.5 A 7 30 30 400 1.5 A ─────────────────────────────────── Comparison Example 1 15 400 1.5 D 2 20 250 1.5 C 3 25 400 2.2 C 4 35 350 350 C ───────────────────── ──────────────

EFFECTS OF THE INVENTION Since the shadow portion of the printing machine is less likely to become dirty, it is easy for an unskilled person to print, and high-quality and stable printed matter can be obtained as compared with the conventional one.

Claims (1)

[Claims] 1. The surface of an aluminum or aluminum alloy plate is subjected to an alternating current in an electrolytic solution containing chlorine ions,
Current density at anode 20 to 30 A / dm ² , electricity at anode 30
After electrolytic graining treatment under conditions of 0 coulomb / dm ² or more and then anodizing, the photosensitive layer is 0.5-2.0 g /
A method for producing a photosensitive lithographic printing plate, which comprises coating with m ² .