JP2000089469A - Photosensitive lithographic printing plate, its supporting body, their production, developing method of the photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent remaining of films after development, to prevent production of printing contamination caused by remaining films, and to obtain good printing durability. SOLUTION: (1) This supporting body has a nonionic surfactant layer on an aluminum plate subjected to roughening treatment and anodic oxidation, and is further heated to a temp. higher than the clouding point of the nonionic surfactant. (2) The printing plate is produced by applying a photosensitive layer on the nonionic surfactant layer of the supporting body described in (1). (3) The clouding point in (1) and (2) is specified to >35 deg.C. (4) As for the treating method, the photosensitive lithographic printing plate described in (2) is developed with an aq. developer. Or, (5) the developing temp. is controlled to lower than the clouding point of the nonionic surfactant.

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, a support thereof, a method for producing the same, and a method for developing the photosensitive lithographic printing plate. The present invention relates to a technique for treating the surface of a roughened and anodized aluminum plate on which the photosensitive layer is to be provided (improvement of residual film after development, printing durability and stain).

[0002]

2. Description of the Related Art A lithographic printing plate is obtained by developing a photosensitive lithographic printing plate obtained by coating a photosensitive composition in a thin layer on an aluminum plate after image exposure. The aluminum plate is usually subjected to a surface roughening treatment such as a mechanical method such as a brush grain method or a ball grain method, an electrochemical method such as an electrolytic grain method, or a method combining the both. After a further anodic oxidation treatment, if desired, a hydrophilic treatment is performed to form a lithographic printing plate support, on which a photosensitive layer is provided to form a photosensitive lithographic printing plate (so-called PS plate). Is done. This photosensitive lithographic printing plate is usually subjected to image exposure, development, correction, gumming steps and the like to form a lithographic printing plate, which is attached to a printing machine for printing.

[0003] In such a photosensitive lithographic printing plate, a phenomenon occurs in which a part of the components of the photosensitive layer remains on the grain (roughened surface) during development, and is called "residual film". There was a problem of generating stains in printing.

Several techniques for improving the residual film have been disclosed so far. However, in practice, all of them have improved the residual film but deteriorated the printing durability.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems, and there is no residual film.
It is an object of the present invention to provide a photosensitive lithographic printing plate which does not generate stains due to it and has good printing durability, a support used therefor, a method for producing the same, and a method for developing the photosensitive lithographic printing plate. .

[0006]

As a result of the study, the present inventor has found that by using an aluminum support in which a nonionic surfactant solution is reacted with a grain, the photosensitive layer components can be transferred to the grain during development. It has been found that adsorption can be prevented, and the present invention has been accomplished.

Further, according to the present invention, by applying heat to a temperature higher than the cloud point of the nonionic surfactant, the hydration bond of the nonionic surfactant is broken, and the normally hydrophilic grain surface can be made lipophilic. As a result, the adhesive strength with the photosensitive layer was increased, and the printing durability was also increased.

Further, according to the present invention, a hydrated bond is restored in a developed portion by performing development processing at a temperature below the cloud point with an aqueous developer, and a hydrophilic surface is obtained.
The present inventors have found that a good photosensitive lithographic printing plate free from stains can be obtained, and have accomplished the present invention.

The constitution of the present invention which achieves the above object of the present invention is the following (1) to (8).

(1) A layer of a nonionic surfactant is provided on the surface of an aluminum plate which has been subjected to a roughening treatment and an anodic oxidation treatment, and the layer is heated to a temperature higher than the cloud point of the nonionic surfactant. And a photosensitive lithographic printing plate comprising a photosensitive layer coated on the layer.

(2) A nonionic surfactant layer having a cloud point of 35 ° C. or more is provided on the surface of the aluminum plate which has been subjected to the surface roughening treatment and the anodic oxidation, and the layer is heated to a temperature not lower than the cloud point. A photosensitive lithographic printing plate comprising a photosensitive layer coated on said layer after heating.

(3) A nonionic surfactant layer is provided on the surface of the roughened and anodized aluminum plate, and the layer is heated to a temperature higher than the cloud point of the nonionic surfactant. A support for a photosensitive lithographic printing plate, characterized in that the support has a curved surface.

(4) A layer of a nonionic surfactant having a cloud point of 35 ° C. or more on the surface of the aluminum plate which has been subjected to the surface roughening treatment and the anodic oxidation treatment, and the layer is heated to a temperature higher than the cloud point. A support for a photosensitive lithographic printing plate having a heated surface.

(5) At least one surface of the aluminum plate is subjected to a roughening treatment and an anodic oxidation treatment, and a nonionic surfactant layer as described in the above (1) or (2) is provided on this surface, and A method for producing a photosensitive lithographic printing plate, comprising heating the layer to a temperature above the cloud point of the nonionic surfactant and then applying the photosensitive layer.

(6) At least one surface of the aluminum plate is subjected to a roughening treatment and an anodic oxidation treatment, and a nonionic surfactant layer as described in the above (3) or (4) is provided on this surface, and A method for producing a support for a photosensitive lithographic printing plate, comprising a step of heating the layer to a temperature above the cloud point of the surfactant.

(7) A method for developing a photosensitive lithographic printing plate according to (1) or (2), wherein the lithographic printing plate is developed with an aqueous developer.

(8) The method for developing a photosensitive lithographic printing plate as described in (7) above, wherein the developing temperature is lower than the cloud point of the nonionic surfactant in the nonionic surfactant layer.

Hereinafter, the present invention will be described in detail.

In the invention according to claims 1 to 8, the aluminum plate is a plate made of pure aluminum or an aluminum alloy. The aluminum alloy includes various things, for example, silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium,
Includes alloys of aluminum with metals such as sodium and iron.

Prior to the surface roughening treatment, the aluminum plate is preferably subjected to a degreasing treatment in order to remove oils, fats, rust, dust and the like on the surface of the aluminum plate. As the degreasing treatment, solvent degreasing using trichlene, thinner, or the like, emulsion degreasing treatment using an emulsion of kerosene, triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used to remove stains and natural oxide films that cannot be removed only by the above degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, and chromic acid,
Alternatively, it is preferable to perform a neutralization treatment by dipping in a mixed acid thereof. When electrochemical surface roughening is performed after this neutralization treatment, it is particularly preferable to match the acid used for the neutralization treatment with the acid used for the electrochemical surface roughening.

The surface roughening treatment can be performed by mechanical surface roughening treatment, electrolytic surface roughening treatment or the like. The mechanical surface roughening method is not particularly limited, but brush polishing and honing polishing are preferable. In brush polishing, for example, the bristle diameter is 0.2 to 1 mm.
The cylindrical brush on which the brush bristles are implanted is rotated and pressed against the surface of the support while supplying a slurry in which the abrasive is dispersed in water to the contact surface to roughen the surface. In honing polishing,
A slurry in which an abrasive is dispersed in water is ejected under pressure from a nozzle and collides obliquely with the support surface to roughen the surface. Further, mechanical roughening can also be performed by pasting a previously roughened sheet to the surface of the support and applying pressure to transfer the roughened surface pattern. Prior to the degreasing treatment, a mechanical roughening treatment may be performed.

In the electrolytic surface roughening treatment, the surface of the aluminum plate is roughened in an acidic electrolytic solution by using an alternating current. As the electrolytic solution at this time, hydrochloric acid, nitric acid, or the like is used, and hydrochloric acid is more preferable. Nitrate, if necessary,
Chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like can be added, but acetic acid is particularly preferred.

The voltage applied in the electrolytic surface roughening treatment is preferably from 1 to 50 V, more preferably from 5 to 30 V. The current density (peak value) is 10 to 200 A / dm ²
Is preferably 20 to 150 A / dm ² .
The amount of electricity is 100 to 2000 C /
dm ² is preferable, and 200 to 1000 C / dm ² is more preferable. The temperature is preferably from 10 to 50 ° C, preferably from 15 to 45 ° C.
C is more preferred. The hydrochloric acid concentration is preferably 0.1 to 5% by weight. The current waveform used for the electrolysis is appropriately selected depending on the roughened shape to be obtained, such as a sine wave, a rectangular wave, a trapezoidal wave, and a sawtooth wave, and a sine wave is particularly preferable.

The aluminum plate which has been subjected to electrolytic surface roughening is
It is preferable to etch the surface by immersing it in an aqueous solution of acid or alkali to remove smut and the like on the surface and control the pit shape of the rough surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and examples of the alkaline agent include sodium hydroxide, potassium hydroxide, and the like. Among these, it is preferable to use an aqueous solution of an alkali. The treatment is carried out at a solution temperature of 20 to 90 ° C. for 5 seconds to 5 minutes using a 0.05 to 40% aqueous solution of the above alkali. After etching the surface with an aqueous alkali solution, the surface is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof to perform a neutralization treatment. When anodizing is performed after the neutralization, it is particularly preferable that the acid used for the neutralization is matched with the acid used for the anodization.

As the electrolytic solution used for the anodic oxidation treatment, any electrolyte can be used as long as it forms a porous oxide film. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, sulfamic acid, benzenesulfonic acid, etc. 2
A mixed acid of a combination of two or more types is used. Anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be specified unconditionally. In general, however, the concentration of the electrolytic solution is 1 to 8
0% by weight, temperature 5 to 70 ° C, current density 1 to 60 A / dm
^2. Appropriate voltage ranges from 1 to 100 V and electrolysis time from 10 seconds to 5 minutes. Preferred is a sulfuric acid method, which is usually treated with a direct current, but an alternating current can also be used. Sulfuric acid concentration is 10-50% by weight, temperature 20-50 ° C, current density 1
It is preferable that the electrolytic treatment is performed at ２０20 A / dm ² for 10 seconds to 5 minutes. Preferably, the electrolyte contains aluminum ions.

The anodized aluminum plate may be subjected to a sealing treatment as required before providing the nonionic surfactant layer according to the first to eighth aspects of the present invention. The sealing treatment can be performed using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

A hydrophilic layer may be provided on an aluminum plate which has been subjected to anodizing treatment or sealing treatment subsequent to the anodizing treatment. U.S. Pat.
181,461, an alkali metal silicate described in the specification,
The hydrophilic cellulose described in U.S. Patent No. 1,860,426, JP-B-6-94234, JP-B-6-94234.
No. 2436, amino acids and salts thereof, hydroxyl-containing amines and salts thereof described in Japanese Examined Patent Publication No. 5-32238, phosphates described in JP-A-62-19494, JP-A-59-101651. For example, a polymer compound containing a monomer unit having a sulfo group described in Japanese Patent Application Laid-Open No. H10-260, etc. can be used.

Further, in order to prevent abrasion on the photosensitive layer when the photosensitive lithographic printing plates are superposed, and to prevent elution of the aluminum component into the developing solution during development, see Japanese Patent Application Laid-open No.
JP-A-151136, JP-A-57-63293, JP-A-60-73538, JP-A-61-67863, JP-A-6-35174, and the like. Provided processing can be performed.

The nonionic surfactant on the anodized surface of the roughened and anodized aluminum plate includes:
For example, polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene polyoxypropylene cetyl ether, Polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearamide, polyoxyethylene oleamide, polyoxy Ethylene castor oil, polyoxyethylene abiethyl ether, polyoxyethylene Down lanolin ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene glyceryl monooleate, polyoxyethylene glyceryl monostearate,
Polyoxyethylene propylene glycol monostearate, oxyethylene oxypropylene block polymer, distyrenated phenol polyethylene oxide adduct, tribenzyl phenol polyethylene oxide adduct, octylphenol polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolau And polyoxyethylene sorbitan monolaurate.

In the present invention, among the nonionic surfactants, a nonionic surfactant having a cloud point of 35 ° C. or higher is preferable. As a nonionic surfactant whose cloud point is 35 ° C or higher,
Emulgen 910, Emulgen 911, Emulgen 95
0, Emulgen 1-9P, Emulgen PP-150, Emulgen 99-290 (all manufactured by Kao Corporation) and the like.

As a method of providing a layer of a nonionic surfactant on the anodized surface of the roughened and anodized aluminum plate, an aqueous solution of a nonionic surfactant is applied on the surface, or a nonionic surfactant is coated on the surface. A method of immersing the surface in an aqueous solution of an activator is preferred. As the application method,
Conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used. The concentration of the nonionic surfactant in the coating solution is suitably in the range of 0.01 to 20% by weight, preferably 0.1 to 5% by weight.
It is. The coating amount is usually 0.01 to 2 g as a solid content.
/ M ² is appropriate. In the case of the immersion treatment, the concentration of the nonionic surfactant is preferably 0.01 to 20% by weight, more preferably 0.1 to 5% by weight, and the treatment temperature is preferably 1 second to 5 minutes, more preferably 1 to 40%. Seconds. After coating or dipping, the nonionic surfactant solution film present on the anodized surface is dried to form a nonionic surfactant layer.

In order to heat the nonionic surfactant layer formed on the anodized surface to a temperature higher than the cloud point of the nonionic surfactant, a method of supplying hot air is used. A known heating means such as a heating method or a method of heating with infrared rays can be used. A preferred heating means is a method of heating by passing through a constant temperature zone maintained at a constant temperature.

In the invention according to the first to eighth aspects, the photosensitive layer provided on the support of the photosensitive lithographic printing plate includes those in which the photosensitive layer is eluted and removed imagewise by development. The photosensitive layer may be a negative type or a positive type.

Examples of the photosensitive material contained in the negative photosensitive layer include photosensitive materials of photopolymerization type, photocrosslinking type, and diazo type.

The photopolymerizable photosensitive material is not particularly limited.
Any known photopolymerizable photosensitive material can be applied,
Examples of preferred photosensitive materials include (a) at least 2
And a photosensitive material containing a vinyl monomer having two terminal vinyl groups, (b) a photopolymerization initiator, and (c) a polymer compound as a binder. (A) above,
(B) and (c) are (a) 20 to 80% by weight, (b) 0.1 to 20% by weight, and (c) 20 to 80% by weight in the solid content of the photopolymerizable photosensitive material. %.

The photosensitive layer using a photopolymerizable photosensitive material may contain a diazo compound, a thermal polymerization inhibitor, a plasticizer, a dye, a pigment and the like.

The photo-crosslinkable photosensitive material is not particularly limited.
Any known photocrosslinkable photosensitive material can be applied,
As an example of a preferable photosensitive material, a photosensitive material containing a compound having a group capable of photodimerization can be given. The compounds having a group capable of photodimerization can be used alone or as a mixture of two or more compounds.

The photocrosslinkable photosensitive material preferably contains a sensitizer in addition to the compound having a photodimerizable group. In addition, the photosensitive layer using the photocrosslinkable photosensitive material may be mixed with an inorganic powder or a polymer, if necessary, for the purpose of imparting shape retention.

The diazo photosensitive material is not particularly limited, either.
Any of known diazo type photosensitive materials can be applied. As a diazo compound used as a diazo type photosensitive material, a diazo resin which is a condensate of p-diazodiphenylamine and formaldehyde is a typical one, and a water-insoluble and organic solvent-soluble one is preferable. Japanese Patent Publication No. 47-1167, 57-4
Water-insoluble and ordinary organic solvent-soluble compounds described in 3890 and the like can be used. Diazo resin is
It is appropriate that the content is usually 1 to 20% by weight, preferably 2 to 10% by weight based on the solid content of the photosensitive layer.

Examples of the positive photosensitive layer include a photosensitive layer containing an orthoquinonediazide compound as a photosensitive material. As the orthoquinone diazide compound, for example,
An ester compound of o-naphthoquinonediazidosulfonic acid with a polycondensation resin of phenols and aldehydes or ketones may be mentioned, and the following compounds described in JP-A-58-43451 may also be mentioned. That is, for example, 1,2-benzoquinonediazidosulfonic acid ester, 1,2-naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide,
Known 1,2-quinonediazide compounds such as 1,2-naphthoquinonediazidesulfonic acid amide, and more specifically, "Light-Sensitive Systems" by J. Kosar (Light-Sensiti).
ve Systems), pages 339-352 (1965).
Year), John Willie and Sons (John
Wiley & Sons, Inc. (New York) and WSDS For (WS De For)
est) "Photoresist" (Photoresis)
t) Volume 50, (1975), McGraw-Hill (McG
1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl described in Raw-Hill, Inc., New York. 1,2-benzoquinonediazide-4- (N-ethyl-N-β-naphthyl) -sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-5) -Sulfonyl) -3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfonic acid-4 ″ -hydroxydiphenyl-4 ″ -azo-β-naphthol ester,
N, N-di- (1,2-naphthoquinonediazido-5-sulfonyl) -aniline, 2- (1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide- 5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-
2,3,4-trihydroxybenzophenone ester,
Condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone, 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy- 1,1 '
Condensate of 1 mol of diphenylsulfone, 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of purprogalin, 1,2-naphthoquinonediazide-5- (N-dihydroabiethyl) -sulfonamide And 1,2-quinonediazide compounds. In addition, Japanese Patent Publication No. 37-1953 and 37-362
No. 7, No. 37-13109, No. 40-26126,
No. 40-3801, No. 45-5604, No. 45-2
Nos. 7345 and 51-13013, JP-A-48-96
No. 575, No. 48-63802, No. 48-63803
And the 1,2-quinonediazide compounds described in the above publications. The o-quinonediazide compound is
Each of the above compounds may be used alone, or two or more of them may be used in combination.

The photosensitive layer containing an orthoquinonediazide compound as a photosensitive material preferably contains an alkali-soluble resin. Examples of the alkali-soluble resin include a novolak resin, a vinyl polymer having a phenolic hydroxyl group, and a condensation resin of a polyhydric phenol and an aldehyde or ketone described in JP-A-55-57841.

Examples of the novolak resin include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolycondensation resin described in JP-A-55-57841, and And a copolycondensation resin of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-127553. The novolak resin preferably has a molecular weight (polystyrene standard) having a number average molecular weight Mn of 3.00 × 10 ^{2 to} 7.50 × 10 ³ and a weight average molecular weight M.
w is 1.00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.00 × 10 ^{3 to} 2.00 × 10 ^4. It is. The novolak resins may be used alone or in combination of two or more. The proportion of the novolak resin in the photosensitive layer is preferably from 5 to 95% by weight.

The proportion of the orthoquinonediazide compound in the photosensitive layer is preferably from 6 to 60% by weight, particularly preferably from 10 to 50% by weight. If necessary, a plasticizer, a surfactant, an organic acid, an acid anhydride and the like can be added to the photosensitive layer containing an orthoquinonediazide compound as a photosensitive material. Further, a photosensitive layer containing an orthoquinonediazide compound as a photosensitive material may be provided with, for example, p-tert in order to improve the oil sensitivity of the photosensitive layer.
An oil-sensitizing agent such as -butylphenol formaldehyde resin, pn-octylphenol formaldehyde resin, or a resin in which these resins are partially esterified with an o-quinonediazide compound can also be contained.

A printout material for forming a visible image by exposure is added to the photosensitive layer containing a photopolymerizable or photocrosslinkable photosensitive material and the photosensitive layer containing an orthoquinonediazide compound as a photosensitive material. be able to. The printout material is used with a compound that produces an acid or free radical upon exposure to light and changes its color by interaction with an acid or free radical generated from the compound upon exposure to form a color image. As the printout material, a dye that changes its color tone by interacting with an acid or a free radical generated by exposure is used.

As the above dyes, those which change color tone by reacting with free radicals or acids can be preferably used. Here, “changing the color tone” includes any of a change from a colorless color tone to a color tone, and a color tone from a colorless color tone to a different color tone. Preferred dyes are those that form a salt with an acid to change the color tone.

In the invention according to claims 1 to 8, various additives can be further added to the photosensitive layer of the photosensitive lithographic printing plate. For example, alkyl ethers (for example, ethylcellulose and methylcellulose) for improving coating properties, fluorine-based surfactants, and nonionic surfactants [for example, Pluronic L-64 (Asahi Denka Co., Ltd.)
Plasticizer (for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid), and a sensitizing agent for improving the lipophilicity of the image area (for example, JP-A-55 / 55) No.-527, a half-esterified product of a styrene-maleic anhydride copolymer with an alcohol),
Stabilizers [for example, phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-
5-sulfonic acid, tartaric acid, etc.)], a development accelerator (for example,
Higher alcohols, acid anhydrides, etc.). The amount of these additives varies depending on the intended use, but is generally 0.01 to 0.01% based on the total solid content of the photosensitive composition.
３０30% by weight. In the invention according to claims 1 to 8, a photosensitive layer containing a photosensitive material such as a photopolymerization type, a photocrosslinking type, and a diazo type, and a photosensitive layer containing an orthoquinonediazide compound as a photosensitive material are each of the above-described necessary components. It is manufactured by applying a coating solution obtained by dissolving components in a solvent to the surface of a support and drying to form a photosensitive layer.

As a coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, and the like can be used. The concentration of the coating solution is 1 to 50
A weight percent range is appropriate. The coating amount of the coating liquid is usually
A solid content of about 0.2 to 10 g / m ² is appropriate.

The photosensitive lithographic printing plate according to the first or second aspect of the present invention is subjected to image exposure and development processing to form an image, thereby obtaining a lithographic printing plate. Conventional methods can be applied to image exposure and development processing.

In the photosensitive lithographic printing plate according to the first or second aspect of the present invention, when an aqueous developing solution is used as a developing solution used for development, a higher effect can be obtained in preventing the generation of stains. it can. Here, the aqueous developer means a developer in which at least 70% by weight, preferably at least 80% by weight of the solvent of the developer is water. As the aqueous developer, a developer containing an alkali metal silicate can be used. The object of the present invention is that the temperature of the developing treatment with the developer is lower than the cloud point of the nonionic surfactant used for the nonionic surfactant layer of the support of the photosensitive lithographic printing plate to be developed. It is preferable from the point of achieving a high degree.

In the aqueous developer, it is preferable that potassium accounts for at least 20% by weight based on the total gram atoms of the alkali metal. The preferred content of potassium is 20 to 100% by weight, most preferably 30 to 100% by weight. The developer can contain another alkaline agent. Examples of the alkaline agent include potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium tertiary phosphate, sodium dibasic phosphate, tertiary sodium phosphate.
Inorganic alkaline agents such as ammonium phosphate, diammonium phosphate, sodium metasilicate, sodium bicarbonate, sodium borate, ammonium borate, ammonia, etc., and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine , Diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, organic amine compounds such as pyridine, and the like. The above can be used in combination.

The aqueous developer includes an anion, a nonion,
It may contain a cationic or amphoteric surfactant and an organic solvent.

Examples of the anionic surfactant include higher alcohol sulfates having 8 to 22 carbon atoms, such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate and secondary sodium alkyl sulfate. Salts, for example, aliphatic alcohol sulfates such as sodium salt of acetyl alcohol sulfate, for example, alkylaryl sulfonates such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, and sodium metanitrobenzene sulfonic acid; For example, C ₁₇ H ₃₃ CON (CH ₃ )
Examples include sulfonic acids of alkylamides such as CH ₂ CH ₂ SO ₃ Na, and sulfonates of dibasic fatty acid esters such as dioctyl sodium sulfosuccinate and sodium sulfosuccidihexyl ester.

As the nonionic surfactant, Japanese Patent Application Laid-Open No.
Nos. -84241, 62-168160 and 62-
No. 175758, cationic surfactants disclosed in JP-A-62-175775, and amphoteric surfactants include, for example, alkyl carboxy betaine type, alkyl amino carboxylic acid type and alkyl imidazoline type compounds. Alternatively, an organic boron compound disclosed in Japanese Patent Publication No. 1-57895 can be used. The surfactant is suitably contained in the range of 0.1 to 5% by weight based on the total weight of the developing solution at the time of use.

Suitable organic solvents are those having a solubility in water of about 10% by weight or less, and preferably those having a solubility in water of 2% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 1,4-phenylbutanol, 2,2-phenylbutanol, 1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m- Examples thereof include methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, and 3-methylcyclohexanol. The content of the organic solvent is preferably from 1 to 5% by weight based on the total weight of the developing solution at the time of use.

The aqueous developer may further contain, if necessary, additives such as an alkali-soluble mercapto compound and / or thioether compound, a water-soluble reducing agent, an antifoaming agent and a water softener.

As the water softener, for example, Na ₂ P ₂ O ₇ ,
Polyphosphates such as Na ₃ P ₁ O ₉ , Na ₂ O ₁ (NaO ₃ P) PO ₃ Na ₂ , and cargon (sodium polymetaphosphate), for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt: diethylenetriaminepentaacetic acid; Potassium salt, sodium salt thereof; triethylenetetramine hexaacetic acid, potassium salt, sodium salt thereof; hydroxyethylethylenediamine triacetic acid, potassium salt, sodium salt thereof; nitrilotriacetic acid, potassium salt, sodium salt thereof; Diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt;
Aminopolycarboxylates such as 1,3-diamino-2-propanoltetraacetic acid, its potassium salt and its sodium salt, and organic sulfones such as ethylenediaminetetra (methylenephosphonic acid) and its potassium and sodium salts Acid salts and the like can be mentioned. The optimum amount of such a water softener varies depending on the hardness of the hard water used and the amount used. However, if a general amount is used, 0.01 to 5% by weight in the developer at the time of use is used. , More preferably 0.01
It is contained in the range of 0.5% by weight.

Examples of the water-soluble reducing agent include phenolic compounds such as hydroquinone and methoxyquinone; amine compounds such as phenyleneamine and phenylhydrazine; sulfites such as sodium sulfite, potassium sulfite and sodium hydrogen sulfite; Examples include phosphites such as potassium and potassium hydrogen phosphite, sodium thiosulfate, sodium dithionite and the like. The content is preferably from 0.01 to 10% by weight based on the total weight of the developing replenisher.

As the alkali-soluble mercapto compound and / or thioether compound, a compound having at least one mercapto group and / or thioether group in the molecule and having at least one or more acid group is preferable. Compounds having at least one mercapto group and a carboxyl group are preferred. For example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid,
4-mercaptobutanoic acid, 2,4-dimercaptobutanoic acid, 2-mercaptotetradecanoic acid, 2-mercaptomyristic acid, mercaptosuccinic acid, 2,3-dimercaptosuccinic acid, cysteine, N-acetylcysteine, N-
(2-mercaptopropionyl) glycine, N- (2-
Mercapto-2-methylpropionyl) glycine, N-
(3-mercaptopropionyl) glycine, N- (2-
Mercapto-2-methylpropionyl) cysteine, penicillamine, N-acetylpenicillamine, glycine-cysteine-glutamine condensate, N- (2,3-dimercaptopropionyl) glycine, 2-mercaptonicotinic acid, thiosalicylic acid, 3-mercaptobenzoic Acid, 4-mercaptobenzoic acid, 3-carboxy-2-mercaptopyridine, 2-mercaptobenzothiazole-5-carboxylic acid, 2-carcapto-3-phenylpropenoic acid, 2-
Mercapto-5-carboxyethylimidazole, 5-
Mercapto-1- (4-carboxyphenyl) tetrazole, N- (3,5-dicarboxyphenyl) -2-mercaptotetrazole, 2- (1,2-dicarboxyethylthio) -5-mercapto-1,3,3 4-thiadiazole, 2- (5-mercapto-1,3,4-thiadiazolylthio) hexanoic acid, 2-mercaptoethanesulfonic acid, 2,3-dimercapto-1-propanesulfonic acid,
2-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid, 3-mercapto-4- (2-sulfophenyl) -1,2,4-triazole, 2-mercaptobenzothiazole-5-sulfonic acid, 2-mercaptobenzoic acid Imidazole-6-sulfonic acid, mercaptosuccinimide, 4-mercaptobenzenesulfonamide, 2
-Mercaptobenzimidazole-5-sulfonamide, 3-mercapto-4- (2- (methylaminosulfonyl) ethoxy) toluene, 3-mercapto-4- (2
-(Methylaminosulfonylamino) ethoxy) toluene, 4-mercapto-N- (p-methylphenylsulfonyl) benzamide, 4-mercaptophenol, 3-
Mercaptophenol, 3-mercaptophenol,
3,4-dimercaptotoluene, 2-mercaptohydroquinone, 2-thiouracil, 3-hydroxy-2-mercaptopyridine, 4-hydroxythiophenol, 4-
Hydroxy-2-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 2,3-dihydroxypropylmercaptan, tetraethylene glycol, 2-mercapto-4-octylphenyl ether methyl ether, 2-mercapto-4-octylphenol methane Sulfonylaminoethyl ether, 2-mercapto-4-octylphenol methylaminosulfonylbutyl ether thiodiglycolic acid, thiodiphenol, 6,8-dithiooctanoic acid or an alkali metal thereof,
Examples thereof include salts with alkaline earth metals and organic amines.
The content of the above compound in the developer is suitably from 0.01 to 5% by weight.

Known lithographic printing plates can be used with known gum solutions and rinsing solutions.

[0060]

EXAMPLE A JIS 1050 aluminum plate having a thickness of 0.24 mm was immersed in a 1% aqueous solution of sodium hydroxide kept at 50 ° C., subjected to a dissolution treatment so that the dissolution amount was 2 g / m ² , and washed with water. Thereafter, the substrate was immersed in a 1% aqueous hydrochloric acid solution for 10 seconds, neutralized, and then washed with water. Then, the aluminum plate was subjected to electrolytic surface roughening treatment under the conditions shown in Table 1 using a current density of 50 A / dm ² and a sine wave alternating current. After the electrolytic surface roughening, the substrate was immersed in a 1% aqueous sodium hydroxide solution kept at 50 ° C., etched to a dissolution amount of 2 g / m ² , washed with water, and kept at 25 ° C. It was immersed in a 10% aqueous sulfuric acid solution for 10 seconds, neutralized, and then washed with water.
Then, in a 20% sulfuric acid aqueous solution, using a direct current at a temperature of 25%
℃, current density 5A / dm ² , anodic oxide film weight 2.0
After anodic oxidation treatment to give g / m ² , it was washed with water.

Next, it was immersed in a 2% by weight aqueous solution of a nonionic surfactant shown in Table 1 below at 30 ° C. for 30 seconds, and further dried at a drying temperature shown in Table 1 to form a layer of the nonionic surfactant. The provided supports A to J were obtained.

[0062]

[Table 1]

(Note) In the column of nonionic surfactant solution,
"None" means that the immersion treatment with the nonionic surfactant solution was not performed.

Next, a coating solution 1 or 2 for a photosensitive layer having the following composition is applied to each of the supports A to J using a wire bar, and dried at 100 ° C. for 1 minute to form a positive photosensitive lithographic printing plate. Plates 1 to 10 and negative photosensitive lithographic printing plates 11 to 20 were obtained. The coated amount after drying was about 1.8 g / m ² .

Coating solution for photosensitive layer 1 Esterification reaction product of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 2,3,4-trihydroxybenzophenone 0.5 g Phenol formaldehyde resin (weight average molecular weight: 2300) 2 0.0g 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 0.02g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.03g crystal violet 0.01g oil blue # 603 (manufactured by Orient Chemical Industries, Ltd.) 0.015 g ethylene dichloride 18 g 2-methoxyethyl acetate 12g photosensitive layer coating solution 2 4-diazo diphenyl amine and a polycondensate of formaldehyde (PF ₆ ^- salt) 1.0 g binder resin ( N- (4-hydroxy Phenyl) methacrylamide / methacrylic acid / ethyl acrylate / acrylonitrile 10/8/62/20 molar ratio copolymer (weight average molecular weight: 50,000, acid value: 180) 10.0 g polyacrylic acid (40% aqueous solution) 6 g Victoria Pure Blue BOH 0.2 g Ethylene glycol monomethyl ether 200 ml The photosensitive lithographic printing plate thus obtained was placed in a vacuum oven, Samples 1 to 10 were transparent positive films, Sample 1
1 to 20 are exposed through a transparent negative film from a distance of 1 m using a 3 kW metal halide lamp for 50 seconds, and are shown in FIG. 1 with a combination of a support and a developing solution as shown in Table 2 below. The film was developed with an automatic developing machine, and the residual film, printing durability and stain were evaluated by the following methods. The results shown in Table 2 were obtained.

In the automatic developing machine shown in FIG. 1, the photosensitive lithographic printing plate is transported horizontally from left to right in the figure with the photosensitive layer on the transport path P, and the developer in the developer tank 1 is discharged. After being supplied from the developing shower 2 onto the photosensitive layer and developed, and squeezed by the developing diaphragm roller 3, the first washing tank 4 and the second
Rinse water in each of the tank 5 and the third tank 6 is supplied from the water shower 7 and washed, and then the finisher liquid in the finisher tank 8 is applied from the finisher supply shower 9. Reference numeral 10 denotes a flush inlet blade. Each of the washing tanks replenishes the third tank with fresh water, the overflow of which is supplied to the second tank, the overflow of the second tank is supplied to the first tank, and only the overflow from the first tank is drained.

Developing solution 1: KD-6 (a positive developing solution manufactured by Konica Corporation) 5 times diluted working solution, developed at 35 ° C. for 10 seconds Developing solution 2: KD-53 (a negative developing solution common to Konica Corporation) Double-dilution working solution, development at 30 ° C for 12 seconds Evaluation method Residual film: The ultraviolet reflection intensity of the non-image area of the printing plate after development is S
Spectrophotometer U-3210 (manufactured by Hitachi, Ltd.) was used. The positive photosensitive lithographic printing plate was measured at 280 nm, the negative photosensitive lithographic printing plate was measured at 375 nm (abs), and the measured value on the support not coated with the photosensitive layer coating solution was also determined. Type Δabs = [measured value at 280 nm] −
[Measured value of support not coated with photosensitive solution at 280 nm] Negative Δabs = [Measured value at 375 nm] −
[Measured value of the support not coated with the photosensitive solution at 375 nm] was calculated, and the obtained value (Δabs) was used as an index of the degree of the remaining film. The smaller this value is, the smaller the remaining film is, and if it is 0.05 or less, there is no practical problem.

Printing durability: The obtained lithographic printing plate was set on a printing machine GTO manufactured by Heidelberg, and coated paper, printing ink (Hi-Echo Red manufactured by Toyo Ink) and fountain solution (SEU-3: 2 manufactured by Konica). .5%), and printing is continued until an inking failure appears in the solid portion of the image portion of the printed matter or ink is deposited in the non-image portion, and the number of printed sheets at that time is counted. The printing durability was evaluated based on the number of sheets.

Soil: The obtained lithographic printing plate was set on a printing machine GTO manufactured by Heidelberg Co., Ltd., and coated paper, printing ink (Hi-Echo Red manufactured by Toyo Ink Co., Ltd.), and dampening solution (SG-51 manufactured by Tokyo Ink Co., Ltd .: 1. 5%) and print
The stain on the non-image area of the printed matter when the dampening water amount was reduced was visually evaluated.

[0070]

[Table 2]

The meanings of the symbols in the stain column in Table 2 are as follows.

：: Stain does not occur even if the dampening solution amount is greatly reduced. △: Stain does not occur even if the dampening solution amount is slightly reduced. Δ: Stain occurs even when the dampening solution amount is extremely small. Dirt occurs even with normal dampening water volume

[0073]

According to the present invention, there is provided a photosensitive lithographic printing plate having no residual film, no resulting stain, and having good printing durability, a support used therefor, a method for producing the same, and a method for producing the same. A method for developing a lithographic printing plate is provided.

[Brief description of the drawings]

FIG. 1 is a view showing a schematic configuration of an automatic developing machine used in an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Developer tank 2 Developing shower 3 Developing squeeze roller 4 Rinse 1st tank 5 Rinse 2nd tank 6 Rinse 3rd tank 7 Rinse shower 8 Finisher tank 9 Finisher supply shower 10 Rinse inlet blade

Claims (8)

[Claims] 1. A nonionic surfactant layer is provided on a surface of a roughened and anodized aluminum plate, and the layer is heated to a temperature equal to or higher than the cloud point of the nonionic surfactant. A photosensitive lithographic printing plate characterized by having a photosensitive layer coated on said layer. 2. A layer of a nonionic surfactant having a cloud point of 35 ° C. or higher on a surface of an aluminum plate which has been subjected to surface roughening and anodizing, and heating the layer to a temperature higher than the cloud point. And a photosensitive lithographic printing plate having a photosensitive layer coated on the layer. 3. A nonionic surfactant layer is provided on the surface of the roughened and anodized aluminum plate, and the layer is heated to a temperature higher than the cloud point of the nonionic surfactant. A support for a photosensitive lithographic printing plate having a surface. 4. A layer of a nonionic surfactant having a cloud point of 35 ° C. or higher on a surface of an aluminum plate which has been subjected to a surface roughening treatment and anodizing, and the layer is heated to a temperature higher than the cloud point. A support for a photosensitive lithographic printing plate, characterized by having a patterned surface. 5. An aluminum plate having at least one surface subjected to a roughening treatment and an anodic oxidation treatment, on which a layer of the nonionic surfactant according to claim 1 or 2 is provided, and wherein said layer is formed of said nonionic surfactant. A method for producing a photosensitive lithographic printing plate, comprising applying a photosensitive layer after heating to a temperature higher than the cloud point of the activator. 6. An aluminum plate having at least one surface subjected to a surface roughening treatment and an anodic oxidation treatment, a nonionic surfactant layer according to claim 3 or 4 provided on this surface, and said layer being treated with said surface active agent. A method for producing a support for a photosensitive lithographic printing plate, comprising a step of heating to a temperature higher than the cloud point of the agent. 7. A method for developing a photosensitive lithographic printing plate, comprising developing the photosensitive lithographic printing plate according to claim 1 with an aqueous developer. 8. The method for developing a photosensitive lithographic printing plate according to claim 7, wherein the developing temperature is lower than the cloud point of the nonionic surfactant in the nonionic surfactant layer.