JPH1063009A - Burning pretreating solution for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a planographic printing plate not causing surface stain and excellent in sensitivity of the image area by using a burning pretreating soln. contg. an anionic surfactant and a fluorine-contg. surfactant which is a polymer contg. an acrylate or methacrylate having an aliphatic fluoro group as constituent units. SOLUTION: This burning pretreating soln. applied to a planographic printing plate before burning contains an anionic surfactant and a fluorine-contg. surfactant which is a polymer contg. an acrylate or methacrylate having an aliphatic fluoro group as constituent units. The fluorine-contg. surfactant may be a copolymer of an acrylate or methacrylate having an aliphatic fluoro group with poly(oxyalkylene) acrylate or poly(oxyalkylene) methacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment solution for burning which is used after exposing and developing a photosensitive lithographic printing plate and before performing a burning process.

[0002]

2. Description of the Related Art Lithographic printing is a printing method that skillfully utilizes the property that water and oil are not essentially mixed. The printing plate surface receives water and repels oil-based ink and water. The former is a non-image area and the latter is an image area. Therefore, the photosensitive composition used for preparing a lithographic printing plate is required to have a property of repelling water and receiving oily ink after image formation. A photosensitive composition used for preparing a lithographic printing plate includes a positive type and a negative type, and the positive type photosensitive composition generally comprises an o-quinonediazide compound. The positive-type photosensitive lithographic printing plate is an o-quinonediazide compound alone or mixed with an alkali-soluble resin such as a novolak-type phenolic resin or cresol resin and coated on a suitable support such as metal or plastic, and is transparent. When exposed to actinic rays through a positive image, the exposed portion of the o-quinonediazide compound decomposes and changes to alkali-soluble, and is easily removed by an aqueous alkali solution to give a positive image. Therefore, when a support having a hydrophilic surface is used, the portion removed with the aqueous alkali solution exposes the hydrophilic surface of the support, and this portion receives water and repels the ink. On the other hand, the portion remaining as an image is lipophilic and accepts ink. On the other hand, negative photosensitive compositions often use a diazonium salt, an azide compound or a photopolymerizable compound, and such a photosensitive material is used alone or mixed with an additive such as a suitable resin, and is coated on a support. Is painted on. When a support having a hydrophilic surface is used, the unexposed portion is removed with a developer to expose the hydrophilic surface of the support, and this portion accepts water and repels the ink. On the other hand, the portion that is cured by exposure and remains as an image during development is lipophilic and accepts ink.

When the lithographic printing plate thus prepared is printed by an offset printing machine, a beautiful printed matter can be obtained. A lithographic printing plate prepared from such a photosensitive lithographic printing plate can provide tens of thousands of beautiful printed matter by appropriately selecting the composition of a support and a photosensitive layer applied thereon. In particular, by using a grained and anodized aluminum plate as a support, it is possible to obtain up to 100,000 beautiful printed matters. However, there is also a demand for obtaining a larger number of printed materials from one printing plate. In such a case, a photosensitive lithographic printing plate using a metal plate such as aluminum or zinc as a support is exposed and developed by a usual method, and then heated at a high temperature (so-called burning treatment) to strengthen the image area. Is valid. That is, by performing the burning process, the number of prints obtained from one lithographic printing plate can be increased several times as compared with the case where the burning process is not performed. Furthermore, when printing with a special printing ink that contains many components that dissolve the image on the printing plate, such as UV-curable ink or low-temperature drying ink, the image portion is eluted in the printing plate made by the usual method without burning treatment. Although the number of printings is significantly lower than when ordinary inks are used, the burning resistance greatly improves the solvent resistance of the image area. A sufficient number of prints can be obtained.

However, the non-image area of the printing plate which was hydrophilic before the processing (that is, the area where the surface of the hydrophilic support was exposed by development) is subjected to the burning treatment so that the hydrophilic property is lost. Since the ink is accepted, a stain (so-called background stain) occurs on the background of the printed matter. If the heating is performed to such an extent that the background stain does not occur, the burning effect cannot be obtained, and the image cannot be reinforced. Therefore, it is necessary to always perform surface adjustment processing to prevent the non-image portion from being stained due to the burning processing. Conventionally, various proposals have been made as surface conditioning treatments used before and / or after the burning treatment step. Prior to the burning treatment, Japanese Patent Application Laid-Open No. 51-34001 discloses a treatment method for preventing the hydrophilicity of the non-image portion from being reduced.
For example, it is disclosed that the treatment is carried out before burning with an aqueous solution of sodium alkylnaphthalenesulfonate, sodium alkyldiphenylethersulfonate and lithium nitrate. Of these, when an aqueous solution of an organic sulfonic acid salt such as sodium alkylnaphthalenesulfonate or sodium alkyldiphenylethersulfonate is used, the foaming properties are remarkably high, so that it can be used in a spray circulation type processing machine that is currently widely used. Was inadequate and could not automate the plate making operation. In addition, when treated with a solution containing lithium nitrate and burned, prevention of background fouling was not sufficient.

Further, DE 2530422 C2 and JP-A-64-4
No. 9687 discloses a perfluoroalkyl sulfonate, a perfluoroalkyl carboxylate, a perfluoroalkyl phosphate, a perfluoroalkyltrimethylammonium chloro compound, a perfluoroalkyl alcohol, a perfluoroalkylpolyoxyethylene oxide adduct and the like. Is described. However, these compounds are disadvantageous in that when they are subjected to the burning treatment, their ability to prevent the non-image area from becoming dirty and the halftone dot shadow area from becoming desensitized are poor, so that stains and ink blemishes tend to occur. Also, when applying using an automatic applicator, a large amount of an antifoaming agent is required because the foam easily forms and overflows from the tank. In addition, the foam of the foamed fine particles collects on the image area, and when dried and subjected to a burning treatment, fine ring-shaped marks become uneven in ink, so-called poor ink deposition, and 500 or more sheets must be printed to obtain normal printing. There is a problem that a normal printed matter cannot be obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an improved burning pretreatment solution which does not have the above-mentioned disadvantages. More specifically, it is an object of the present invention to provide a pretreatment solution for burning, which does not generate background contamination and can provide a lithographic printing plate having excellent oil sensitivity in an image area. Another object of the present invention is to provide a burning pretreatment liquid that can be applied to a lithographic printing plate using a spray circulation type processing machine or the like.

[0007]

Means for Solving the Problems The present inventors have proposed a treatment liquid applied to a lithographic printing plate before performing a burning treatment (hereinafter referred to as a burning pretreatment liquid) containing an acrylate having a fluoroaliphatic group or an acrylate having a fluoroaliphatic group. The inventors have found that the above objects can be achieved by adding a fluorine-based surfactant and a polymer having a methacrylate as a constitutional unit, thereby completing the present invention. Accordingly, the present invention relates to a lithographic printing plate burning pretreatment solution containing a fluorosurfactant, which is a polymer having acrylate or methacrylate having a fluoroaliphatic group as a constituent unit, and an anionic surfactant.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a fluorine-based surfactant which is a polymer having an acrylate or methacrylate having a fluoroaliphatic group as a constituent unit used in the present invention, specifically, an acrylate or a fluorocarbon having a fluoroaliphatic group is used. Copolymers of a methacrylate having an aliphatic group with poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate are exemplified.
In the copolymer, the monomer unit of acrylate or methacrylate having a fluoroaliphatic group is preferably 7 to 60% by weight based on the weight of the copolymer,
The molecular weight of the copolymer is suitably from 3000 to 100,000.

The fluoroaliphatic group has 3 to 20 carbon atoms, may be linear or branched, contains 40% by weight or more of fluorine, and has at least 3 terminal carbon atoms. Is preferably a fully fluorinated fluoroaliphatic group. Specific examples of the acrylate or methacrylate having a fluoroaliphatic group include N-butylperfluorooctanesulfonamidoethyl acrylate, N-propylperfluorooctanesulfonamidoethyl acrylate, and methyl perfluorooctanesulfonamidoethyl acrylate. The molecular weight of the polyoxyalkylene group in poly (oxyalkylene) acrylate or methacrylate is 200 to 3000
It is preferred that As the oxyalkylene group,
Oxyethylene, oxypropylene and oxybutylene groups are exemplified, and oxyethylene and oxypropylene groups are preferred. For example, acrylate or methacrylate to which 8 to 15 mol of oxyethylene groups are added is used. If necessary, a foaming property can be suppressed by adding a dimethylsiloxane group or the like to the terminal of the polyoxyalkylene group. The fluorosurfactant which is a copolymer as described above is generally available on the market, and a commercially available product can be used in the present invention. Two or more fluorine-based surfactants can be used in combination. In the burning pretreatment liquid of the present invention, the content of the fluorine-based surfactant is suitably 0.0001 to 5% by weight, and preferably 0.001% by weight, based on the total weight of the burning pretreatment liquid.
001 to 3% by weight.

[0010] The burning pretreatment liquid of the present invention also contains an anionic surfactant. Such a surfactant assists in evenly applying the burning pretreatment liquid to the surface of the lithographic printing plate, and also has a part of an effect of suppressing the generation of stains in a non-image area due to the burning treatment. Examples of the anionic surfactant used in the present invention include alkyl benzene sulfonate, alkyl diphenyl ether disulfonate, alkyl naphthalene sulfonate, aldehyde condensate of alkyl naphthalene sulfonate,
α-olefin sulfonate, sulfonic acid group-containing surfactant such as alkyl sulfonate, lauryl sulfate, polyoxyethylene alkyl ether sulfate,
Sulfate surfactants such as polyoxyethylene alkylphenyl ether sulfate are particularly preferred. Two or more anionic surfactants may be used in combination. The anionic surfactant is suitably contained in the range of 0.05 to 30% by weight, and preferably in the range of 0.1 to 20% by weight, based on the total weight of the burning pretreatment liquid.

The burning pretreatment liquid of the present invention may further contain various acids, alkalis and salts for adjusting pH. Mineral acids and organic acids can be used as the acid. For example, nitric acid, sulfuric acid, mineral acids such as phosphoric acid, citric acid, succinic acid, oxalic acid, tartaric acid, acetic acid, malic acid, phytic acid, organic phosphonic acid, p-toluenesulfonic acid, organic acids such as xylenesulfonic acid, Potassium, lithium, sodium or ammonium salts of these acids;
Alternatively, hydroxides, carbonates, hydrogencarbonates and the like of alkali metals may be mentioned. These acids, salts and alkalis adjust the pH of the burning pretreatment solution of the present invention to 2 to 10, preferably 3 to 10.
-8 can be contained.

Further, the burning pretreatment liquid of the present invention includes:
A polymer compound having a film forming property can also be added. For example, gum arabic, starch derivatives (eg, dextrin, enzymatically decomposed dextrin, hydroxypropylated enzymatically degraded starch, carboxymethylated starch, phosphorylated starch, etc.), alginates, and fibrin derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose) Natural products such as methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and their modified glyoxals) and their modified products, polyethylene glycol and its copolymers, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polyacrylamined and its copolymers. Polymer, polyacrylic acid and its copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer It compounds such as polystyrene sulfonic acid and copolymers thereof. These polymer compounds may be used alone or in combination of two or more. The range of use is suitably from 0.0001 to 3% by weight based on the total weight of the burning pretreatment liquid.

The pretreatment solution for burning of the present invention may further contain a preservative, an antifoaming agent, a coloring agent and the like. Preferable preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives,
Benztriazole derivatives, amidizing anidine derivatives, quaternary ammonium salts, derivatives such as pyridine, quinoline, guanidine, etc., thiocarbamic acid derivatives, diazines, triazole derivatives, oxazoles, oxazine derivatives, 2-bromo-2-nitropropane-1,3- Diols and the like. The preferable addition amount is an amount that exerts a stable effect on bacteria, mold, yeast and the like, and varies depending on the kind of bacteria, mold and yeast, but is 0.001 to 3.0 with respect to the burning pretreatment liquid. It is preferably in the range of% by weight, and it is preferable to use two or more kinds in combination so as to exert effects on various molds and bacteria. In addition, a silicone antifoaming agent is preferable as the antifoaming agent. Specifically, any of an emulsified dispersion type and a solubilized type can be used. The amount used is 0.001 to 0.001% of the total weight of the burning pretreatment liquid.
0.1% by weight is suitable. The colorant is used to impart a desired color tone to the burning pretreatment liquid of the present invention and to give visual contrast, and can be selected from a wide range of dyes. Particularly preferred dyes are blue,
Indicator dyes having dyeings such as purple, red, and yellow exhibit excellent effects. For example, dyes such as crystal violet, safranin, brilliant blue, malachite green, and acid rhodamine B can be suitably used.

The burning pretreatment liquid of the present invention is obtained by subjecting a photosensitive lithographic printing plate to image exposure, development and, if necessary, washing with water.
Unnecessary parts for printing are removed with a correction agent, and a printing plate with no room for further correction is created.
Apply before burning. As a method, a sponge or absorbent cotton impregnated with a burning pretreatment liquid is applied on a lithographic printing plate, or a printing plate is immersed in a vat filled with a treatment liquid, or is applied automatically. Coating with a coater or the like is applied. Further, making the amount of the coating uniform with a squeegee or a squeegee roller after the coating gives more preferable results. The lithographic printing plate coated with the burning pretreatment liquid is dried, if necessary, and then burned (for example, a burning processor 13 sold by Fuji Photo Film Co., Ltd.).
00). The heating temperature and time in this case depend on the type of the component forming the image,
The temperature is preferably in the range of 180 to 300 ° C. for 1 to 20 minutes. The lithographic printing plate subjected to the burning treatment can be subjected to a conventional treatment such as washing with water or gumming as needed.

The burning pretreatment solution of the present invention can be applied to various lithographic printing plates. In particular, a photosensitive lithographic printing plate using an aluminum plate as a support (a printing plate to which photosensitivity has been previously applied, and a PS plate, ). A preferred PS plate is a photosensitive layer comprising a mixture of a diazo resin (a salt of a condensate of p-diazodiphenylamine and paraformaldehyde) and shellac as described in, for example, British Patent No. 1,350,521. On an aluminum plate, a diazo resin and a polymer having a hydroxyethyl methacrylate unit or a hydroxyethyl acrylate unit as a main repeating unit as described in UK Patent Nos. 1,460,978 and 1,505,739. Negative PS plates such as those having a photosensitive layer comprising a mixture of
No. 806 discloses a positive PS plate in which a photosensitive layer comprising a mixture of an o-quinonediazide photosensitive material and a novolak-type phenol resin is provided on an aluminum plate. Further, a PS plate in which a photosensitive layer of a photocrosslinkable photopolymer is provided on an aluminum plate, as specifically shown in U.S. Pat. No. 3,860,426, U.S. Pat.
PS plate in which a photosensitive layer of a photopolymerizable photopolymer composition as described in the specifications of 4,072,528 and 4,072,527 is provided on an aluminum plate, UK Patent No. 1,235,
Also preferred are PS plates having a photosensitive layer comprising a mixture of azide and a water-soluble polymer provided on an aluminum plate as described in the specifications of JP-A-281 and JP-A-1,495,861. Among these PS plates, a particularly preferred PS plate is a positive PS plate having a photosensitive layer composed of an o-naphthoquinonediazide compound and a novolak resin, and is disclosed in U.S. Pat.
No. 434, from column 3 bottom line to column 6 line 14 is described in detail.

[0016]

The use of the pre-burning treatment liquid of the present invention eliminates the need for surface conditioning after the burning treatment. Nevertheless, a lithographic printing plate having no stain on the non-image area, high oil sensitivity in the image area, and excellent printing durability can be obtained. In addition, since the burning pretreatment liquid of the present invention has a low foaming property, it can be applied to a lithographic printing plate using a spray circulation type processing machine, and there is a great advantage that the plate making operation can be automated.

[0017]

The present invention will be described in more detail with reference to the following examples.

Example 1 100 parts by weight of naphthoquinone- (1,2) -diazide (2) -5-sulfonic acid ester of 1,5-dihydroxynaphthalene and 4 parts by weight of a novolak-type cresol-formaldehyde resin in 100 parts by weight of ethylene Dissolved in glycol monomethyl ether. Next, 0.24 thickness
This solution was applied on a grained aluminum plate having a thickness of 2.5 mm to a dry weight of 2.5 g / m ² . The positive photosensitive lithographic printing plate thus prepared was brought into close contact with the transparent positive and exposed for 30 seconds with a 3 KW metal halide lamp from a distance of 1 m, followed by sodium silicate 5% by weight.
It was immersed in an aqueous solution for about 1 minute and developed. Then after washing with water,
A burning pretreatment liquid having the following composition was applied by a coater and dried. Pure water 954.6 g Phytic acid (50%) 5.0 g Sodium dodecylbenzenesulfonate (60% aqueous solution) 35.0 g 4-isothiazolin-3-one derivative 0.1 g 2-bromo-2-nitropropanediol 0.1 g Sodium hydroxide 5.0 g N-butyl perfluorooctanesulfonamidoethyl acrylate [CH ₂ = CHCOOCH ₂ CH ₂ (C ₄ H ₉ ) NSO ₂ C ₈ F ₁₇ monomer ratio 40% by weight] and poly (oxyethylene) acrylate [CH ₂ = CHCOO- (C ₂ H ₄ O) _n -H monomer ratio 60% by weight] (molecular weight 15,000) 0.2 g

The printing plate thus treated was heated in a commercial burning processor at a temperature of 260 ° C. for 6 minutes. After cooling, the surface of the plate was observed. As a result, there were almost no thick coating portions unique to the coater on the left and right sides of the plate, and a good surface quality burning treatment was performed. Then, GU-7
(Gum solution manufactured by Fuji Photo Film Co., Ltd.) was applied, and this printing plate was attached to an offset printing machine, Heidelberg SOR-M, and printing was performed. 200,000 sheets were printed.

[0019]

Comparative Example 1 A lithographic printing plate treated under exactly the same conditions as in Example 1 was subjected to sodium perfluoroalkyl sulfonate in a 4% by weight aqueous solution of ammonium borate instead of the burnin pretreatment liquid used in Example 1. It was treated with a solution in which 0.05% by weight was dissolved. Thereafter, the same burning treatment as in Example 1 was performed, and after cooling, the plate surface was observed.
As a result, line-like unevenness was found on the left and right sides of the plate at about 10 to 20 cm from the end. Thereafter, GU-7 (a gum solution manufactured by Fuji Photo Film Co., Ltd.) was applied and printing was performed in the same manner as in Example 1. As a result, ink bleeding was generated in the halftone dot image from the beginning of printing, and streak-like portions were formed. The quality of the surface is 1
Even after printing 00 sheets, the ink did not adhere normally, and after processing with a plate cleaner to prevent the ink blemishes and the poorly adhered ink from being treated with a plate, a normal printed matter could be obtained.

[0020]

EXAMPLE 2 Example 1 on a 0.3 mm thick aluminum plate which was grained and anodized (anodized in 15% by weight sulfuric acid at a current density of 1.6 amps / dm ² for 2 minutes).
A positive photosensitive lithographic printing plate was prepared by applying the same photosensitive liquid as described above. A transparent positive image is adhered to this, and from a distance of 1 m 3
After exposing for 40 seconds with KW's metal halide lamp,
It was immersed in a 7% by weight aqueous solution of sodium silicate for about 1 minute for development. This lithographic printing plate is subjected to continuous application of a pretreatment solution for burning, burning and gumming by an automatic integrated burning processor [Process Materials Co., Ltd.]. ] Was continuously processed. Here, the burning temperature is set to 150
℃, post-heating 240 ℃, the passage time of the furnace is about 3 minutes,
The burning pretreatment liquid used had the following composition.

Pure water 954.4 g Ammonium citrate 5.0 g Sodium alkyl diphenyl ether sulfonate (50% aqueous solution) 40.0 g 4-isothiazolin-3-one derivative 0.2 g Benzoic acid methyl ester 0.2 g N-propyl Perfluorooctanesulfonamidoethyl acrylate [CH ₂ = CHCOOCH ₂ CH ₂ (C ₃ H ₇ ) NSO ₂ C ₈ F ₁₇ monomer ratio 30% by weight] and poly (oxyethylene) acrylate [CH ₂ = CHCOO- (C ₂ H ₄ O) A compound obtained by adding dimethylsiloxane (monomer ratio 10% by weight) to the terminal of the copolymer having an _n- H monomer ratio of 60% by weight] (molecular weight: 18,000) 0.2 g After burning as in Example 1, As a result of observing the coated surface quality, good surface quality without coating unevenness was obtained. When the printing plate was directly attached to a printing machine Heidelberg SOR-M and printed, a beautiful printed matter was obtained on several sheets from the start of printing, and 300,000 sheets of printed matter could be continuously obtained.

[0022]

Comparative Example 2 The same steps as in Example 2 were performed up to the development step.
The processing was performed in the same manner as in Example 2. However, the burning pretreatment liquid used had the following composition. Pure water 954.4 g Ammonium citrate 5.0 g Sodium alkyl diphenyl ether sulfonate (50% aqueous solution) 40.0 g 4-isothiazolin-3-one derivative 0.2 g Benzoic acid methyl ester 0.2 g Sodium perfluoroalkyl sulfonate 0.2 g As a result, the foam was remarkably foamed from the spray pipe and the tank portion in the treatment liquid application section, and the liquid overflowed from the tank, and the operation of the automatic processing machine had to be stopped. Further, the coating surface quality of the plate was in a state of poor quality with many small streaks.

[0023]

Example 3 Example 1 of US Pat. No. 3,635,709
Polyhydroxyphenyl and naphthoquinone obtained by condensation polymerization of acetone and pyrogallol
4 parts by weight of 1,2-diazide (2) -5-sulfonic acid ester and novolak-type cresol formaldehyde resin 4
Parts by weight of ethylene glycol monomethyl ether 10
0 parts by weight, and the dry weight was 2.5 g / m ^{2 on} the grained and anodized aluminum plate used in Example ^2.
And a positive photosensitive lithographic printing plate was prepared. This positive photosensitive lithographic printing plate was exposed, developed and washed with water under the same conditions as in Example 1, then a burning pretreatment liquid having the following composition was applied, and then subjected to a burning treatment at 260 ° C. for 5 minutes.

Pure water 949.5 g 2-phosphonobutane-1,2,4-tricarboxylic acid (50%) 5.0 g Sodium isopropylnaphthalenesulfonate 30.0 g Sodium meta-xylene sulfonate 10.0 g Sodium hydroxide 5.0 g N -Butyl perfluorooctanesulfonamidoethyl acrylate [CH ₂ = CHCOOCH ₂ CH ₂ (C ₄ H ₉ ) NSO ₂ C ₈ F ₁₇ monomer ratio 50% by weight] and poly (oxyethylene) acrylate [CH ₂ = CHCOO- (C ₂ H ₄ O) _n -H monomer ratio of 50 wt% of the copolymer (molecular weight 22,000) 0.5 g

The lithographic printing plate obtained had a uniform and good coating surface quality. When printing was performed by attaching it to a printing machine Heidelberg SOR-M without gumming, beautiful prints were obtained on several sheets from the start of printing, and 200,000 sheets of prints could be continuously obtained.

[0026]

Example 4 A solution was prepared by dissolving 20 parts by weight of shellac and 3 parts by weight of a diazo resin obtained by condensing p-toluenesulfonic acid salt of p-diazodiphenylamine with formaldehyde in 80 parts by weight of dimethylformamide. On the other hand, the grained aluminum plate is immersed in a 0.2% aqueous solution of potassium zirconium fluoride at 80 ° C. for 3 minutes, subjected to a hydrophilization treatment, washed with water, and dried. It was applied so as to be 2.0 g / m ² . The negative photosensitive lithographic printing plate thus obtained was exposed through a transparent negative with a 3 KW metal halide lamp from a distance of 1 m for 30 seconds, immersed in an aqueous solution of isopropyl alcohol 20% by weight for about 1 minute, and then washed with cotton wool. When the surface was rubbed lightly, only the unexposed portions were peeled off and removed, and the surface of the support was exposed. After washing with water, the burning pretreatment liquid used in Example 1 was applied and dried. After performing the burning treatment under the same conditions as in Example 1, the printing was performed by attaching to an offset printing machine. A beautiful printed matter was obtained, and when printing was continued as it was, 150,000 sheets of printed matter having almost the same condition as the printing start could be obtained.

[0027]

Example 5 Sand graining with a pumice / water slurry and a nylon brush, and anodizing treatment (2 A / dm in 20% sulfuric acid)
Anodized at ² for 2 minutes. ) And then treated with a 2.5% by weight aqueous solution of sodium silicate at 70 ° C for 1 minute to a thickness of 0.3.
mm aluminum plate was prepared. A photosensitive solution having the following composition was applied to the aluminum plate so that the weight after drying was 2.0 g / m ² . Copolymer of 2-hydroxyethyl methacrylate / acrylonitrile / ethyl methacrylate / methacrylic acid = 37/34/22/7 (weight ratio) 5.0 g diazo resin obtained by condensing p-toluenesulfonic acid salt of p-diazodiphenylamine with formaldehyde 0.5g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.1g Methyl cellosolve 95ml Water 5ml

The negative-working photosensitive lithographic printing plate thus obtained was exposed through a transparent negative with a 3 KW metal halide lamp from a distance of 1 m for 30 seconds and developed using the following developer. Benzyl alcohol 30 ml Diethanolamine 10 g Sodium sulfite 5 g Sodium isopropylnaphthalenesulfonate 10 g Water 1 L After washing with water, the burning pretreatment liquid used in Example 2 was applied.
After drying and performing a burning treatment under the same conditions as in Example 2, when the printing was performed by attaching to an offset printing machine, a beautiful printed matter was obtained with a few sheets of the printing start. It was possible to obtain 200,000 copies of the printed matter without change in tone.

[0029]

Example 6 An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then washed thoroughly with water.
After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, washing with running water and neutralizing and washing with 20% HNO ₃ ,
Washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an electric quantity of 160 coulomb / dm ² using a sine wave alternating current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μ (Ra indication). Subsequently, it is immersed in a 30% aqueous solution of H ₂ SO ₄ ,
After desmutting for 20 minutes, the resultant was subjected to anodizing treatment in a 20% H ₃ PO ₄ aqueous solution for 5 minutes at a current density of 2 A / dm ^{2 so} that the amount of anodized film becomes 1.2 g / m ² . Thereafter, it was immersed in a 2.5% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water, and dried. The aluminum plate was coated with a photosensitive solution having the following composition so that the weight after drying was 1.3 g / m ² .

Methyl methacrylate / N- [6- (methacryloyloxy) hexyl) -2,3-dimethylmaleimide / methacrylic acid = 10/60/30 (molar ratio) Copolymer ( _MW = 8.0 × 10 ⁴⁾ ) 5g sensitizer

[0031]

Embedded image

0.5 g 4-diazodiphenylamine PF ₆ salt (diazo monomer) 0.03 g FC-430 (fluorinated surfactant manufactured by 3M USA) 0.05 g 1-methoxy-2-propanol 100 g

The negative photosensitive lithographic printing plate thus obtained was exposed through a transparent negative with a 3 kW metal halide lamp from a distance of 1 m for 30 seconds, and was exposed to No. 3 sodium silicate 2
After immersion for 1 minute in an aqueous solution containing 1% by weight of sodium metasilicate and 1% by weight of sodium metasilicate, when the surface was lightly rubbed with absorbent cotton, only the unexposed portion was peeled off and the surface of the support was exposed. After washing with water, the pretreatment solution for burning used in Example 2 was applied and dried, and after performing a burning treatment under the same conditions as in Example 2, the printing was performed by attaching to a printing machine (Heidelberg SOR-M) and printing. From this, a beautiful printed matter was obtained on dozens of sheets, and printing was continued as it was. As a result, 150,000 printed matters having almost the same condition as the printed state could be obtained.

Claims (1)

[Claims] 1. A lithographic printing plate burning pretreatment solution containing a fluorosurfactant, which is a polymer having an acrylate or methacrylate having a fluoroaliphatic group as a constitutional unit, and an anionic surfactant.