JPH1178280A - Vender part cleaner for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vender part cleaner for planographic printing plate capable of obtaining a planographic printing plate not generating a contaminant on the paper surface corresponding to a vender part. SOLUTION: A vender part cleaner for a planographic printing plate contains at least one compd. selected from a group consisting of a hydrophilic org. polymeric compd., hexametaphosphoric acid and its salt and phytinic acid and its salt. As the hydrophilic org. polymeric compd., there are gum arabic, dextrin, alginate, for example, like sodium alginate, water-soluble cellulose, for example, like carboxymethylcellulose, hydroxyethylcellulose or hydroxypropylmethylcellulose or the like. These hydrophilic polymeric compds. can be used as a combination of two or more kinds of them if necessary and are used in a concn. of about 1-40 wt.%, more pref., 3-30 wt.% with respect to the total wt. of the vender part cleaner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate bender cleaner, and more particularly, to a lithographic printing plate bender capable of obtaining a lithographic printing plate having no stain on the paper surface corresponding to the bender portion. It is related to the part cleaner. A photosensitive lithographic printing plate having an aluminum plate as a support is generally subjected to various surface treatments such as graining, anodic oxidation, and chemical conversion treatment alone or in an appropriate combination on a sheet-like or coil-like aluminum plate. It is obtained by coating, drying and then cutting to a desired size. Such a photosensitive lithographic printing plate is image-exposed and subjected to processing such as development to obtain a lithographic printing plate. When printing such a lithographic printing plate using a rotary press, in order to make it easy to attach the printing plate to the plate body of the rotary printing device, generally, a width of 2 to 3 cm inward from the upper and lower edges of the printing plate. The position is bent by a bender to produce a so-called bender part. At this time, cracks occurred in the anodic oxide film of the bender portion, and the ink attached to the cracks was printed on paper and became soiled, thereby significantly impairing the commercial value of the printed matter. Therefore, a method for preventing such a stain on the bender section of the printing plate has been desired.

[0002]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithographic printing plate bender cleaner capable of obtaining a lithographic printing plate free from contamination on the paper surface corresponding to the bender portion.

[0003]

The object of the present invention is to provide a hydrophilic organic polymer compound, hexametaphosphoric acid and salts thereof,
And a lithographic printing plate bender part cleaner comprising at least one compound selected from the group consisting of phytic acid and salts thereof.

[0004]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail.
Specifically, the coiled aluminum plate is degreased and washed by various methods, grained by various methods, then, if necessary, the residue is removed, and anodizing treatment and hydrophilization treatment are performed.
A photosensitive solution is applied and dried. Thereafter, the plate is slit into a size suitable for a desired printing machine, and after image exposure, development is performed to prepare a lithographic printing plate. A position of about 2 to 3 cm is bent inward from the upper and lower edges of the obtained lithographic printing plate to form a bender portion. Normally, cracks occur in the anodic oxide film at the bent portion, and ink adheres to the cracked portion and stains are generated, but the bender portion cleaner of the present invention is applied around the bender portion, and applied to the plate body of the rotary press. By wrapping and printing, surprisingly, the stain on the paper surface corresponding to the bender section was greatly reduced. As the composition used for the bender part cleaner of the present invention, an aqueous solution containing at least one compound selected from the group consisting of a hydrophilic organic polymer compound, hexametaphosphoric acid and salts thereof, and phytic acid and salts thereof is used. No. The hydrophilic organic polymer compound, hexametaphosphoric acid and its salt, and phytic acid and its salt may be used alone or in combination.

Specific examples of hydrophilic organic high molecular compounds include gum arabic, dextrin, alginate such as sodium alginate, water-soluble cellulose such as carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylmethylcellulose;
Polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, water-soluble copolymer containing acrylamide units, polyacrylic acid, copolymer containing acrylic acid units,
Polyacrylic acid, copolymer containing acrylic acid units, polymethacrylic acid, copolymer containing methacrylic acid units, copolymer of vinyl methyl ether and maleic anhydride, copolymer of vinyl acetate and maleic anhydride And phosphoric acid-modified starch. Among them, it is preferable to contain one kind of hydroxyalkylated starch. These hydrophilic polymer compounds can be used in combination of two or more kinds as necessary, and have a concentration of about 1 to 40% by weight, more preferably 3 to 30% by weight, based on the total weight of the bender cleaner. Used in.

[0006] The hydroxyalkylated starch (ie, hydroxyalkyl etherified starch) used in the present invention has a degree of etherification (ie, the degree of substitution of three hydroxyl groups of a glucose residue) in the range of 0.03 to 0.08. And more preferably in the range of 0.04 to 0.07. Specifically, it is obtained by adding ethylene oxide or propylene oxide to a hydroxyl group in a linear (amylose) or branched (amylopectin) polymer, and is represented by a unit represented by the following general formula I and a unit represented by the following general formula II And a polymer compound containing a unit.

[0007]

Embedded image

(In the general formula [I], R _{1 to} R ₃ may be the same or different, and each represents a hydrogen atom,-(C
_{H 2 CH 2 O) n-} H or _{- (CH 2 CH (CH 3} )
O) n-H, wherein n is an integer of 1 to 3; However,
At least one of R _{1 to} R ₃ represents a group other than a hydrogen atom. )

[0009]

Embedded image

The method for synthesizing the above-mentioned starch derivative is disclosed in US Pat.
It is described in detail in 3067067. The hydroxyalkylated starch can be further enzymatically degraded to make it more soluble in cold water. Such enzymes include α-amylase,
β-amylase, saccharified amylase and the like are used. The hydroxyalkylated starch used in the plate surface protective agent of the present invention is 30% by weight or more, more preferably 40% by weight, in water at 20 ° C.
Those that dissolve in an amount of at least% by weight are preferred. The molecular weight of the starch thus modified is preferably in such a range that the viscosity of the 20% by weight aqueous solution at 20 ° C. becomes 5 to 100 centipoise. The content of the hydroxyalkylated starch in the plate surface protective agent of the present invention is suitably about 5 to 35% by weight, more preferably 10 to 25% by weight. These hydroxyalkylated starches are dissolved in water (usually at 20 to 25 ° C.) and used as a homogeneous aqueous solution.

In the present invention, the hydroxyalkylated starch may be a mixture of other starches such as roasted dextrin. Further, other water-soluble polymer compounds such as gum arabic may be added. Also, Japanese Patent Application Laid-Open No. Sho 62-1169
3, starch modified with phosphoric acid or a derivative thereof, urea-phosphorylated starch described in JP-A-2-113997, carboxyalkylated starch described in JP-A-62-7595, Other starches such as water-soluble soybean polysaccharide described in Kaihei 7-52577 may be further added. In general, when the degree of etherification of hydroxyalkylated starch (that is, the degree of substitution of three hydroxyl groups of glucose residues) is 0.1 or less, the aqueous solution is stored and the starch aging phenomenon (thickening phenomenon) occurs. ) Occurs, but the optimal degree of etherification as the hydroxyalkylated starch of the present invention is
0.03 to 0.08, more preferably 0.04 to 0.08.
0.07. Accordingly, in the present invention, a surfactant may be further contained in order to suppress the aging phenomenon of the hydroxyalkylated starch having the above-mentioned optimum degree of etherification. Surfactants that can be used include anionic surfactants and / or nonionic surfactants.

Specific examples of the hexametaphosphate used in the present invention include alkali metal or ammonium hexametaphosphate. Examples of the alkali metal or ammonium hexametaphosphate include sodium hexametaphosphate, potassium hexametaphosphate, and ammonium hexametaphosphate. Specific salts of phytic acid include alkali metal salts such as sodium salt, potassium salt and lithium salt, ammonium salts, amine salts and the like. Examples of the amine salt include diethylamine, triethylamine, n-propylamine, di-n
-Propylamine, tri-n-propylamine, n-butylamine, n-amylamine, n-hexylamine,
Examples thereof include salts of laurylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ethanolamine, diethanolamine, triethanolamine, allylamine, aniline and the like. The phytate may be a normal salt in which all 12 hydrogens of an acid are substituted, a hydrogen salt in which a part of the acid hydrogen is substituted (an acidic salt), or a simple salt composed of a salt of one kind of base. Any form of double salt containing at least one kind of base as a component can be used. These compounds can be used alone or in combination of two or more.

It is preferable that the bender part cleaner of the present invention further contains a metal salt of a strong acid, whereby the action of preventing adhesion of ink can be enhanced. Specific metal salts of strong acids include sodium, potassium, magnesium, calcium and zinc nitrates, sodium, potassium, magnesium, calcium and zinc salts of sulfuric acid, sodium salts of chromic acid, Potassium, magnesium, calcium and zinc salts, and sodium and potassium fluorides and the like can be mentioned. Two or more of these strong acid metal salts can be used in combination, and the amount thereof is preferably about 0.01 to 5% by weight based on the total weight of the bender cleaner. The pH value of the bender cleaner of the present invention is adjusted to an acidic range, more preferably 1 to 5, and most preferably 1.5 to 4.5. Thus, if the pH of the aqueous phase is not acidic, more acid is added to the aqueous phase. Examples of the acid added as such a pH adjuster include mineral acids such as phosphoric acid, sulfuric acid, and nitric acid, for example, citric acid, tannic acid, malic acid, glacial acetic acid, lactic acid,
Examples include organic acids such as oxalic acid, p-toluenesulfonic acid, and organic phosphonic acid. Of these, phosphoric acid is particularly excellent because it not only functions as a pH adjuster, but also has the effect of enhancing the desensitizing effect, and is preferably 0.01 to 20% by weight based on the total weight of the bender cleaner. Preferably 0.1 to
It is preferable to contain it in the range of 10% by weight.

[0014] The bender cleaner of the present invention preferably contains a wetting agent and / or a surfactant, whereby the coatability of the bender cleaner can be improved. As specific wetting agents, lower polyhydric alcohols are preferable, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentanediol, hexylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, and tripropylene Examples include glycol, glycerin, sorbitol, pentaerythritol and the like, and particularly preferred is glycerin. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl phenyl ether and polyoxyethylene polyoxypropylene block copolymers, such as fatty acid salts, alkyl sulfates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates. Anionic surfactants such as dialkylsulfosuccinate salts, alkylphosphate salts, and naphthalenesulfonic acid formalin condensates, for example, betaine-type, glycine-type, alanine-type, and sulfobetaine-type amphoteric surfactants can be used. These wetting agents and / or surfactants are contained in the range of about 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the bender cleaner. The bender cleaner used in the present invention includes:
2% by weight of filler such as silicon dioxide and talc clay
And dyes and pigments can be contained in an amount of up to 1% by weight.

The bender cleaner of the present invention comprises a hydrophilic aqueous solution as described above. In consideration of the adverse effect on the photosensitive layer of the PS plate, for example, US Pat. No. 4,253,999 and US Pat. No. 4268613, No. 434
Emulsion type bender cleaners such as those described in each specification such as No. 8954 can also be used. In order to treat the lithographic printing plate bender portion with the above-described bender portion cleaner, a method of applying the cleaner of the present invention to the bender portion of the lithographic printing plate using a Molton roll, a sponge, a brush, or the like, and a method of spraying are used. However, a spray method is simple and preferable. The amount of the cleaner applied to the bender was 0.001 to 5 in terms of dry weight.
0 g / m ² , preferably 0.01 to 10 g / m ² , more preferably 0.05 to 5 g / m ² . 0.001 g / m ²
If it is less than 3, the printing paper corresponding to the bender section is stained. Usually, a lithographic printing plate is bent by a bender at a position of 2 to 3 cm inward from the ends of the upper and lower sides, and cracks occur in the anodic oxide film at the bent portion,
The ink adheres to the cracked portion, causing stains. Therefore, the bender cleaner of the present invention is applied around the bent part.

The support of the lithographic printing plate to which the bender cleaner of the present invention is applied is preferably aluminum or an aluminum-coated composite support.
1 to 0.5% by weight, 0.03 to 0.3% by weight of silicon, and 0.3% by weight of copper.
A 1S aluminum plate containing 001 to 0.03% by weight and further 0.002 to 0.1% by weight of titanium is preferable. The surface of the aluminum material is desirably surface-treated for the purpose of increasing water retention and improving adhesion to the photosensitive layer. Alkali, preferably, may be etched by immersing it in an aqueous solution of 1 to 30% by weight of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate or the like at a temperature of 20 to 80 ° C. for 5 to 250 seconds. In the etching bath,
Aluminum ions may be added to about one fifth of the alkali. Then, it is immersed in an aqueous solution of 10 to 30% by weight of nitric acid or sulfuric acid at a temperature of 20 to 70 ° C. for 5 to 25 seconds to neutralize and remove smut after alkali etching. For example, as the surface roughening method, generally known brush polishing method, ball polishing method, electrolytic etching, chemical etching, liquid honing, sand blasting and the like and combinations thereof, and preferably, brush polishing method, electrolytic etching, Chemical etching and liquid honing are mentioned, of which the surface roughening method including the use of electrolytic etching is preferred. Further, JP-A-54-6390
As described in Japanese Patent Publication No. 2 (1994), a method of performing electrolytic polishing after brush polishing is also preferable.

As the electrolytic bath used in the electrolytic etching, an aqueous solution containing an acid, an alkali or a salt thereof or an aqueous solution containing an organic solvent is used. Electrolytes containing salts are preferred. For brush polishing, it is preferable to use a pamistone-water suspension and a nylon brush, and it is preferable that the average surface roughness is 0.25 to 0.9 μm. The electrolytic solution used for the electrolytic etching treatment is an aqueous solution of hydrochloric acid or nitric acid, and the concentration is preferably used in the range of 0.01 to 3% by weight, and more preferably 0.05 to 2.5% by weight. preferable. In addition, a corrosion inhibitor (or stabilizer) such as nitrate, chloride, monoamines, diamines, aldehydes, phosphoric acid, chromic acid, boric acid, ammonium oxalate, etc., if necessary, A graining agent and the like can be added. Also, an appropriate amount (1 to 1)
0 g / liter) of aluminum ions.

The electrolytic etching process is usually performed at 10 to 60 ° C.
At the temperature of the electrolyte. If the alternating current used at this time is one in which the positive and negative polarities are alternately exchanged,
Any of a rectangular wave, a trapezoidal wave, and a sine wave can be used, and normal commercial AC single-phase and three-phase AC currents can be used. The current density is 5 to 100 A / dm ² ,
It is desirable to process for 10 to 300 seconds. The surface roughness of the aluminum alloy support is adjusted by the quantity of electricity,
2 to 0.8 μm.

Further, the surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution as required. The grained aluminum alloy is made of 10 to 50% by weight of hot sulfuric acid (40 to 60% by weight).
℃) or dilute alkali (such as sodium hydroxide)
The smut attached to the surface is preferably removed and etched (preferably in the range of 0.01 to 2.0 g / m ² ). If the smut has been removed and etched with an alkali, it is subsequently neutralized by immersion in an acid (nitric acid or sulfuric acid) for cleaning. After de-smutting the surface, an anodic oxide coating is provided. As the anodic oxidation method, a conventionally well-known method can be used, but sulfuric acid is used as the most useful electrolytic solution. Subsequently, phosphoric acid is also a useful electrolyte. Further, JP-A-55-28400
The mixed acid of sulfuric acid and phosphoric acid disclosed in the publication is also useful.

In the sulfuric acid method, the treatment is usually performed with a direct current, but an alternating current can be used. Sulfuric acid concentration 5-3
Electrolysis treatment is performed at 0% by weight in a temperature range of 20 to 60 ° C. for 5 to 250 seconds, and an oxide film of 1 to 10 g / m ² is provided on the surface. The electrolyte preferably contains aluminum ions. At this time, the current density is 1
~20A / dm ² is preferred. In the case of the phosphoric acid method, 5-
At a phosphoric acid concentration of 50% by weight and a temperature of 30 to 60 ° C., 10
300 seconds, is treated at a current density of 1 through 15A / dm ^2.

Further, if necessary, US Pat. No. 2,71
The silicate (sodium silicate, potassium silicate) treatment described in US Pat. No. 4,066 and US Pat. No. 3,181,461 and the process described in US Pat. No. 2,946,638 are described. Potassium fluoride zirconate treatment, phosphomolybdate treatment described in U.S. Pat. No. 3,201,247, alkyl titanate treatment described in British Patent 1,108,559, German Patent No. 1,
No. 091,433, polyacrylic acid treatment, German Patent 1,134,093 and British Patent No.
1,230,447, polyvinylphosphonic acid treatment described in JP-B-44-6409, and U.S. Pat. No. 3,307,951. Phytic acid treatment, JP-A-58-1
No. 6,893 and JP-A-58-18291, the treatment with a salt of a hydrophilic organic polymer compound with a divalent metal, and the sulfonic acid described in JP-A-59-101651. Having been subjected to a hydrophilic treatment by undercoating of a water-soluble polymer having a group, JP-A-60-6435
Those colored with an acid dye described in JP-A No. 2 are particularly preferable. Other hydrophilic treatment methods include silicate electrodeposition described in U.S. Pat. No. 3,658,662. Further, after graining treatment and anodic oxidation, sealing treatment is preferable. Such a 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.

Further, the aluminum support may be undercoated. Examples of the compound used for the undercoat include carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid optionally having a substituent, naphthylphosphonic acid, and alkylphosphonic acid. Acids, organic phosphonic acids such as glycerophosphonic acid, methylene diphosphonic acid and ethylene diphosphonic acid, organic phosphoric acids such as phenylphosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid which may have a substituent, substituents Having organic groups such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydroxyl groups such as triethanolamine hydrochloride. Water-soluble polymer having hydrochloride Min, a sulfonic acid group as described in JP-A-59-101651, and JP 60-64
Acid dyes and the like described in JP-A-352 are preferably used. This undercoat layer can be provided by dissolving the above compound in water, methanol, ethanol, methyl ethyl ketone, or the like, or a mixed solvent thereof, coating the support on a support, and drying. Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the undercoat layer after drying is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² .

The photosensitive layer of the photosensitive lithographic printing plate according to the present invention includes various types, including a negative photosensitive composition comprising a diazo resin and a hydrophobic resin, and a positive photosensitive composition comprising an o-quinonediazide compound and a novolak resin. A photopolymerizable composition comprising a photosensitive composition, an addition polymerizable unsaturated monomer, a photopolymerization initiator, and an organic polymer compound as a binder, or a photocrosslinking reaction having -CH = CH-CO- bonds in the molecule; And the like provided with a photosensitive resin which causes the following.
A typical negative photosensitive composition includes a composition containing a diazo resin and a binder. The diazo resin is a diazo resin represented by a condensate of an aromatic diazonium salt and a compound containing an active carbonyl group, for example, formaldehyde. Examples of the diazo resin include, for example, p
An organic solvent-soluble inorganic salt of a diazo resin which is a reaction product of a condensate of diazodiphenylamines with an aldehyde such as formaldehyde or acetaldehyde and hexafluorophosphate or tetrafluoroborate;
Sulfonic acid salts with the condensate as described in JP-A-1167, for example, p-toluenesulfonic acid or a salt thereof, propylnaphthalenesulfonic acid or a salt thereof, butylnaphthalenesulfonic acid or a salt thereof, dodecylbenzenesulfonic acid Or a salt thereof, 2-hydroxy-
An organic solvent-soluble diazo resin organic salt which is a reaction product with 4-methoxybenzophenone-5-sulfonic acid or a salt thereof is exemplified. In particular, a high molecular weight diazo compound containing at least 20 mol% of a hexamer or more described in JP-A-59-78340 is preferable.

Further, 3-methoxy-4-diazo-diphenylamine as disclosed in JP-A-58-27141 is condensed with 4,4'-bis-methoxy-methyl-diphenyl ether to form a mesitylene sulfonate. What is done is also suitable. Further, a copolymer containing at least one of a carboxyl group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus, and a hydroxyl group, and a diazonium compound, preferably an aromatic diazonium compound, as structural units. Condensates are preferred. Preferred binders have an acid content of 0.1 to 3.0 m.
eq / g, preferably 0.2 to 2.0 meq / g, which is a substantially water-insoluble (ie, insoluble in a neutral or acidic aqueous solution) and film-forming organic polymer compound, Those which can be dissolved or swelled in an aqueous alkali-based developer and are photo-cured in the presence of the photosensitive diazo resin to make them insoluble or non-swellable in the developer are preferred. When the acid content is less than 0.1 meq / g, development is difficult, and when the acid content exceeds 3.0 meq / g, the image intensity during development is significantly reduced.

Particularly preferred binders include copolymers containing acrylic acid, methacrylic acid, crotonic acid or maleic acid as an essential component, for example, 2-hydroxyethyl as described in JP-A-50-118802. Multi-component copolymers of acrylate or 2-hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile, acrylic acid or methacrylic acid and, if necessary, other copolymerizable monomers, JP-A-53-12090
Acrylic or methacrylic acid, acrylic acid, in which the terminal is a hydroxy group and esterified with a group containing a dicarboxylic acid ester residue as described in JP-A-3
Or a multi-component copolymer of methacrylic acid and, if necessary, another copolymerizable monomer, JP-A-54-98614.
No. 4,086,098, and a monomer having an aromatic hydroxyl group at the terminal thereof (for example, N- (4-hydroxyphenyl) methacrylamide, etc.), acrylic acid or methacrylic acid, and other copolymerizable if necessary. And a multi-component copolymer comprising an alkyl acrylate, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid as described in JP-A-56-4144. In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. Japanese Patent Publication No. 54-19773, in which polyvinyl acetal or polyurethane is alkali-soluble,
Nos. -94747, 60-182437 and 62-5
The binders described in Nos. 8242 and 62-123453 are also useful. Further, a polymer having a maleimide group in the side chain and capable of photoreticulation described in JP-B-5-2227 is also useful. The content of the diazo resin and the binder in the photosensitive layer of the photosensitive lithographic printing plate is 3 to 30% by weight of the diazo resin and the binder is 97 to 7 based on the total amount of both.
0% by weight is suitable. When the content of the diazo resin is small, the sensitivity is high, but when the content is lower than 3% by weight, it is insufficient for photocuring the binder, and the photocured film swells with the developing solution during development, and the film becomes weak. Conversely, if the content of the diazo resin is more than 30% by weight, the sensitivity is lowered and practical difficulties arise. Therefore, a more preferable range is the diazo resin 5
-25% by weight and 95-75% by weight of binder.

The photosensitive compound of the positive photosensitive composition includes an o-quinonediazide compound, and a representative example thereof is an o-naphthoquinonediazide compound. o
-As a naphthoquinonediazide compound, JP-B-43-
Preferred is an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-A-28403. Other suitable orthoquinonediazide compounds include U.S. Pat.
There are esters of 1,2-diazonaphthoquinone-5-sulfonic acid chloride and phenol-formaldehyde resin described in 3,046,120 and 3,188,210. 96163, JP-A-2-96165, and JP-A-2-96661, 1,2-diazonaphthoquinone-4-
There are esters of sulfonic chloride and phenol-formaldehyde resin. Other useful o-naphthoquinonediazide compounds have been reported in numerous patents,
There are known ones. For example,
No.-5303, No.48-63802, No.48-638
No. 03, No. 48-96575, No. 49-38701
No. 48-13354, JP-B-37-18015
No. 41-11222, No. 45-9610, No. 4
No. 9-17481, U.S. Pat. No. 2,797,213,
No. 3,454,400, No. 3,544,323, No. 3,
No. 573,917, No. 3,674,495, No. 3,785,
No. 825, British Patent Nos. 1,227,602 and 1,251,
No. 345, No. 1,267,005, No. 1,329,888
No. 1,330,932, German Patent No. 854,890, and the like.

As a photosensitive compound which acts positively without using an o-naphthoquinonediazide compound, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B-56-2696 is also used in the present invention. can do. Further, a compound generating an acid by photolysis and a -COC group or-dissociated by the acid.
Combinations with compounds having a CO-Si group can also be used in the present invention.

For example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90303), a combination with an orthoester or amide acetal compound (JP-A-51-120)
714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429),
Combination with enol ether compound (JP-A-55-12
No. 995), a combination with an N-acylimino carbon compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-1).
No. 7345), a combination with a silyl ester compound (JP-A-60-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12).
No. 1446).

The photosensitive substance used in the photosensitive lithographic printing plate according to the present invention includes polyesters, polyamides and polycarbonates containing -CH = CH-CO- as a photosensitive group in the polymer main chain or side chain. A polymer containing such a photosensitive polymer as a main component is also suitable. For example, JP-A-55-
Photosensitive polyesters obtained by condensation of phenylenediethyl acrylate with hydrogenated bisphenol A and triethylene glycol, as described in US Pat. No. 40415, such as described in US Pat. No. 2,956,878. Examples thereof include (2-propenylidene) malonic acid compounds such as cinnamylidenemalonic acid and photosensitive polyesters derived from bifunctional glycols.

Further, examples of the photosensitive substance include aromatic azide compounds in which an azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group. For example, polyazide styrene, polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, and JP-B-4 Sho 3, as described in U.S. Pat. No. 3,096,311.
Reaction products of azidoarylsulfanyl chlorides with unsaturated hydrocarbon polymers described in JP-B-5-9613, and JP-B-43-21067, JP-B-44-229, and JP-B-44-229;
And polymers having a sulfonyl azide or a carbonyl azide, as described in JP-A--22954 and JP-A-45-24915. Furthermore, as the photosensitive substance used in the photosensitive composition according to the present invention, a photopolymerizable composition comprising an addition-polymerizable unsaturated compound can also be used. The present invention can also be applied to a photosensitive composition used for an electrophotographic printing plate. For example, JP
JP-A-5-161250 describes a photosensitive composition comprising an electron-donating compound, a phthalocyanine-based pigment, and a phenol resin used for an electrophotographic printing plate.

The photosensitive composition is dissolved in the above-mentioned coating solvent, and is preferably applied to an aluminum support having a hydrophilic surface in a dry coating weight of 0.3 to 5.0 g / m ² , preferably 0.5 to 5.0 g / m ^2. 3.
It is applied to a concentration of 5 g / m ² and dried to obtain a photosensitive lithographic printing plate. The solid content concentration of the photosensitive composition at the time of coating is suitably 1.0 to 50% by weight, preferably
2.0-30% by weight is suitable. As a method for applying the photosensitive composition on the support, a conventionally known method, for example, a method such as roll coating, bar coating, spray coating, curtain coating, and spin coating can be used. The applied photosensitive composition solution is 50
Drying at ~ 150 ° C is preferred. As a drying method, after preliminarily drying at a lower temperature, drying may be performed at a high temperature or directly at a high temperature.

It is preferable to provide a mat layer composed of protrusions provided independently of each other on the photosensitive layer. The purpose of the mat layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate in contact exposure, thereby shortening the vacuuming time and preventing the collapse of minute dots during exposure due to poor adhesion. That is. As a method for applying the mat layer, a method for thermally fusing powdered solid powder described in JP-A-55-12974 and a polymer-containing water described in JP-A-58-182636 are used. And drying. Any of these methods can be used. The mat layer is desirably composed of a substance which is dissolved in an aqueous developer substantially free of an organic solvent or which can be removed thereby. A photosensitive lithographic printing plate having a photosensitive composition layer coated and dried on a roughened aluminum plate can be developed with an aqueous alkali solution-based developer after image exposure to obtain a relief image. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, laser beams and the like.

An alkaline aqueous solution developer used for developing a negative photosensitive lithographic printing plate is disclosed in JP-A-51-774.
No. 01, No. 51-80228, No. 53-44202 and Nos. 55-52054, each having a pH of 8 to 13 and containing 75% by weight or more of water. Are preferred. If necessary, an organic solvent (benzyl alcohol, ethylene glycol monophenyl ether) having a solubility in water of 10% by weight or less at room temperature, an alkali agent (triethanolamine, diethanolamine, monoethanolamine, sodium phosphate, sodium carbonate), anionic surface activity Agents (aromatic sulfonate, dialkyl sulfosuccinate, alkyl naphthalene sulfonate, fatty acid salt, alkyl sulfate salt),
Nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether,
A polyoxyethylene polyoxypropylene block polymer), a stain inhibitor (sodium sulfite, sodium salt of sulfopyrazolone) and a water softener (tetrasodium ethylenediaminetetraacetate, trisodium nitrotriacetate) can be added. However, if organic solvents are contained, toxicity during work, hygiene problems such as odor, fire,
Since there is a problem of safety such as gas explosion, a problem of workability such as generation of bubbles, a problem of pollution by waste liquid, a problem of cost, and the like, those containing substantially no organic solvent are more preferable. Examples of such an aqueous alkaline developer containing substantially no organic solvent include, for example, JP-A-59-84241, JP-A-57-192952 and JP-A-62-22633.
JP-A No. 6-264, etc., a developer composition used when developing a positive-working lithographic printing plate after image exposure to light can be used.

The photosensitive lithographic printing plate according to the present invention is disclosed in JP-A-54-8002, JP-A-55-115045 and JP-A-59-15045.
The plate-making process may be performed by a method described in each publication of JP-A-58431. 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 treatment with an aqueous solution containing an acid, followed by a desensitization treatment. Further, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced. The capacity is reduced.
The processing capacity may be restored using a replenisher as described in JP-A-62004. In this case, U.S. Pat.
It is preferred to replenish by the method described in 2,246. Further, the plate making process as described above is disclosed in Japanese Patent Laid-Open No. 2-70.
It is preferably carried out by an automatic developing machine as described in JP-A Nos. 54 and 2-32357. After the processing with the developing solution, if necessary, unnecessary portions of the image area can be erased with a commercially available negative erasing solution or rubbed with a stone stick.

The developer used for developing the positive photosensitive lithographic printing plate is preferably an alkaline aqueous solution containing substantially no organic solvent, and specifically, sodium silicate, potassium silicate, sodium hydroxide, hydroxide Potassium, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia Aqueous solutions such as are suitable and their concentration is 0.1.
-10% by weight, preferably 0.5-5% by weight. Among these, potassium silicate, lithium silicate, a developer containing an alkali silicate such as sodium silicate is preferable because stains during printing hardly occur,
When the composition of the alkali silicate is [SiO ₂ ] / [M] = 0.
5 to 2.5 (where [SiO ₂ ] and [M] indicate the molar concentration of SiO _{2 and} the molar concentration of the total alkali metal, respectively) and contain 0.8 to 8% by weight of SiO ₂ . Developing solution is preferably used. In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, and magnesium sulfite, resorcin, methylresorcin, hydroquinone, thiosalicylic acid, and the like can be added to the developer. The content of these compounds in the developer is preferably 0.002 to 4% by weight, and more preferably 0.01 to 1% by weight.

Further, in a developing solution, JP-A-50-51324 is used.
JP-A-59-84241 and JP-A-59-84241 and JP-A-59-75255, JP-A-60-111246 and JP-A-60-213943. Or at least one of the nonionic surfactants described in JP-A-55-95946 and JP-A-56-142528. Is preferably used because it can increase the wettability to the photosensitive composition and the development stability (development latitude). The addition amount of such a surfactant is preferably 0.001 to 2% by weight, and particularly preferably 0.003 to 0.5% by weight. Further, as the alkali metal of the alkali silicate, it is preferable that potassium is contained in an amount of 20 mol% or more in all the alkali metals, since the generation of insolubles in the developer is small, and more preferably 9%.
0 mol% or more, most preferably 100 mol% of potassium
Is the case.

Further, the developing solution of the lithographic printing plate to which the bender part cleaner of the present invention is applied may contain a small amount of an organic solvent such as alcohol, a chelating agent described in JP-A-58-190952, An antifoaming agent such as a metal salt or an organic silane compound described in JP-A-30139 can be added. The photosensitive lithographic printing plate according to the present invention is disclosed in JP-A-54-8002 and JP-A-55-1504.
It is needless to say that the plate-making process may be performed by the methods described in JP-A-5-58431 and JP-A-59-58431.
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 development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Although the processing capacity is reduced, in that case, JP-A-54-62004
The processing capacity may be recovered by using a replenisher as described in the above item. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246. Further, the plate making process as described above is described in JP-A-2-7054 and 2-3.
It is preferable to use an automatic developing machine as described in JP-A No. 2357.

In the case where the photosensitive lithographic printing plate according to the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary erasing of an image portion is performed, Japanese Patent Publication No. 2-132
It is preferable to use an erasing liquid as described in JP-A-93-93. Furthermore, when the photosensitive lithographic printing plate is image-exposed, developed, rinsed or rinsed, erased if desired, and washed with water, then burned. -28062
JP-A-62-31859 and JP-A-61-159655.
It is preferable to carry out treatment with a surface conditioning liquid as described in each of the publications.

Synthesis Example 1 4-diazodiphenylamine sulfate (purity 99.5%) 2
9.4 g at 25 ° C. were slowly added to 70 ml of 96% sulfuric acid and stirred for 20 minutes. 3.26 g of paraformaldehyde (purity: 92%) was gradually added over about 10 minutes, and the mixture was stirred at 30 ° C. for 4 hours to allow a condensation reaction to proceed. The condensation molar ratio between the diazo compound and formaldehyde is 1: 1. While stirring the reaction product,
The mixture was poured into 2 liters of ice water and treated with a cold concentrated aqueous solution in which 130 g of sodium chloride was dissolved. The precipitate is filtered off with suction.
The recovered, partially dried solid is dissolved in 1 liter of water, filtered, cooled with ice and washed with potassium hexafluorophosphate 2
The solution was treated with an aqueous solution in which 3 g was dissolved. The precipitate was collected by filtration and air-dried to obtain 30.3 g of the high molecular weight diazo compound (1).
I got The obtained diazo compound (1) was coupled with 1-phenyl-3-methyl-5-pyrazolone in methyl cellosolve to obtain a dye. The weight average molecular weight of the dye (using a low angle light scattering photometer) is 16,500.
Which corresponded to about 45-mers. The molecular weight distribution of this dye was measured by gel permeation chromatography (GPC).
0 mol% was contained.

[0040]

Next, the present invention will be described by way of examples. Example 1 Thickness of a JIS A1050 aluminum material containing 99.5% by weight of aluminum, 0.01% by weight of copper, 0.03% by weight of titanium, 0.3% by weight of iron, and 0.1% by weight of silicon. .3
The surface of a 0 mm rolled plate is grained using a 400 mesh 20% aqueous suspension of pamistone (manufactured by Kyoritsu Ceramics) and a rotating nylon brush (6,10-nylon), and then thoroughly washed with water. did. This was immersed in a 15% by weight aqueous sodium hydroxide solution (containing 4.5% by weight of aluminum), etched so that the amount of aluminum dissolved was 5 g / m ² , and washed with running water. Further, the mixture was neutralized with 1% by weight nitric acid, and then a 0.7% by weight aqueous nitric acid solution (aluminum)
0.5% by weight), a rectangular alternating voltage having a voltage at the anode of 10.5 volts and a voltage at the cathode of 9.3 volts (current ratio r = 0.
90, was subjected to electrolytic surface roughening treatment in an anode electricity quantity of 160 coulomb / dm ² using a current waveform) disclosed in Japanese Example No. Sho 58-5796. After washing with water,
It was immersed in a 0% by weight aqueous sodium hydroxide solution, etched so that the amount of aluminum dissolved was 1 g / m ² , and washed with water. Next, it was immersed in a 50% by weight aqueous solution of 30% by weight sulfuric acid, desmutted, and washed with water.

Further, a porous anodic oxide film forming treatment was carried out in a 20% by weight aqueous sulfuric acid solution (containing 0.8% by weight of aluminum) at 35 ° C. using a direct current. That is, electrolysis was performed at a current density of 13 A / dm ² , and the weight of the anodic oxide film was adjusted to 2.7 g / m ² by adjusting the electrolysis time. To prepare a negative photosensitive lithographic printing plate using a diazo resin and a binder, the support was washed with water, immersed in a 3% by weight aqueous solution of sodium silicate at 70 ° C. for 30 seconds, washed with water and dried.
The aluminum support obtained as described above had a reflection density of 0.30 measured with a Macbeth RD920 reflection densitometer.
And the center line average roughness was 0.58 μm. Next, methyl methacrylate / ethyl acrylate / 2
-Acrylamide-2-methylpropanesulfonic acid sodium copolymer (average molecular weight: about 60,000) (molar ratio: 50/3)
(0/20) was applied by a roll coater such that the coating amount after drying was 0.05 g / m ² . Further, Photosensitive Solution 1 shown below was applied using a bar coater, and dried at 110 ° C. for 45 seconds. The dry coating amount is 2.
It was 0 g / m ² .

Photosensitive solution-1 Diazo resin of Synthesis Example 1 0.50 g Binder-1 5.00 g Stylite HS-2 (manufactured by Daido Kogyo Co., Ltd.) 0.10 g Victoria Pureable-BOH 0.15 g Tricresyl phosphate 0 .50 g Dipicolinic acid 0.20 g FC-430 (surfactant manufactured by 3M) 0.05 g Solvent 1-methoxy-2-propanol 25.00 g Methyl lactate 12.00 g Methanol 30.00 g Methyl ethyl ketone 30.00 g Water 3.00 g

Binder-1 was 2-hydroxyethyl methacrylate / acrylonitrile / methyl methacrylate / methacrylic acid copolymer (weight ratio 50/20/26 /
4. A water-insoluble, alkali-water-soluble film-forming polymer having an average molecular weight of 75,000 and an acid content of 0.4 meq / g). Stylite HS-2 (manufactured by Daido Kogyo Co., Ltd.) is a polymer compound having higher oil sensitivity than a binder, and styrene / mono-4-methyl-2-pentyl maleate = 50/50 (molar ratio). )), And had an average molecular weight of about 100,000. Obtained in this way
A coiled photosensitive lithographic printing plate having a width of 0.3 mm and a width of 800 mm was continuously slit into a width of 796 mm. Plus 560
mm.

The cut sheet-shaped photosensitive lithographic printing plate is image-exposed, and DN-3C (alkaline aqueous solution developer manufactured by Fuji Photo Film Co., Ltd.) is applied with 800H (automatic developing machine manufactured by Fuji Photo Film Co., Ltd.). Development was carried out with a liquid diluted 1: 1 with water, and a solution prepared by diluting FN-2 (a gum solution manufactured by Fuji Photo Film Co., Ltd.) 1: 1 with water was applied to the plate making section and dried. Place the obtained lithographic printing plate 2 cm inward from the upper and lower edges.
It was bent at a position by a bender to produce a bender part. On the upper surface of the bender part, a bender part cleaner of the present invention obtained by mixing 10 g of hydroxypropyl etherified starch (substitution degree 0.05), 1 g of an 85% by weight phosphoric acid aqueous solution and 89 g of pure water is dried with a Molton roll. Weight is 0.
Coating was performed so as to be 1 g / m ² . This printing plate was printed on a rotary offset printing press using newspaper ink from Sakata Ink Co., Ltd. and Toyo Alky fountain solution from Toyo Ink Co., Ltd.
20,000 sheets were printed at a speed of 100,000 sheets / hour. No stain occurred on the printing paper surface corresponding to the bender section of the printing plate.

Examples 2 to 11 The lithographic printing plates obtained in the same manner as in Example 1 were coated with the respective bender cleaners shown in Table 1 in the same manner as in Example 1. Thereafter, printing was performed in the same manner as in Example 1.
No lithographic printing plates using any of the bender cleaners were stained on the paper corresponding to the bender.

[0046]

Example 1 Composition of bender part cleaner 2 Hydroxyethyl etherified starch (degree of substitution 0.08) 10 g Pure water 89 g Phosphoric acid (85 wt% aqueous solution) 1 g 3 Hydroxypropyl etherified starch (degree of substitution 0.05) 5 g Carboxymethyl cellulose 5 g (Cellogen 1A, manufactured by Daiichi Kogyo Yakuhin Co., Ltd.) Pure water 89 g Phosphoric acid (85% by weight aqueous solution) 1 g 4 Hydroxypropyl etherified starch (substitution degree 0.05) 5 g Gum arabic (30% by weight aqueous solution) 5 g Pure water 89 g Phosphorus Acid (85 wt% aqueous solution) 1 g 5 Hydroxypropyl etherified starch (degree of substitution 0.05) 5 g Roasted dextrin 5 g Pure water 89 g Phosphoric acid (85 wt% aqueous solution) 1 g 6 Sodium hexametaphosphate 10 g Pure water 89 g Phosphoric acid (85 wt%) Aqueous solution) 1g 7 Sodium hexametaphosphate 1g Pure 98 g phosphoric acid (85 wt% aqueous solution) 1 g 8 phytic acid (30 wt% aqueous solution) 15 g pure water 85 g 9 phytic acid (30 wt% aqueous solution) 3 g pure water 97 g 10 hydroxypropyl etherified starch (degree of substitution 0.05) 5 g hexametaphosphoric acid Sodium 5g Pure water 89g Phosphoric acid (85% by weight aqueous solution) 1g 11 Hydroxypropyl etherified starch (degree of substitution 0.05) 5g Phytic acid (30% by weight aqueous solution) 3g Pure water 92g

Comparative Example 1 A lithographic printing plate was produced in the same manner as in Example III. afterwards,
A bender portion was prepared in the same manner as in Example 1, and the one without the bender portion cleaner was designated as Comparative Example 1, and printing was performed in the same manner as in Example 1. In the printing paper corresponding to the bender portion of the printing plate of Comparative Example 1, a linear stain was generated.

[0048]

As is clear from the above embodiments, the printing plate coated with the bender cleaner of the present invention does not cause stain on the printing paper surface corresponding to the bender.

Claims (1)

[Claims] 1. A lithographic printing plate bender cleaner comprising at least one compound selected from the group consisting of a hydrophilic organic polymer compound, hexametaphosphoric acid and salts thereof, and phytic acid and salts thereof.