JP2000343849A - Direct drawing type lithographic printing plate and forming method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a direct drawing type lithographic printing plate, in which an image adhesion and a hydrophilicity of non-image area are made compatible which can be used with a favorable workability, and printing apparatus employed therein are made simpler, and its forming method. SOLUTION: This lithographic printing plate has a layer including a hydrophilic organic polymer compound on an anodized aluminum support. All the hydrophilic organic polymer compound in the layer adsorbs onto the support. In order to form this lithographic plate, after a composition including a hydrophilic organic polymer compound is coated on an anodized aluminum support, the excess amount of the above composition is removed by water washing so as to provide a layer including the hydrophilic organic polymer compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct drawing type lithographic printing plate and a method for producing the same. More specifically, a printing image is formed by an ink jet method, and both image adhesion and non-image portion hydrophilicity are achieved. The present invention relates to a method for producing a direct drawing type lithographic printing plate having good workability.

[0002]

2. Description of the Related Art In recent years, in a lithographic printing method, a number of systems for directly drawing digital image information on a printing plate have been proposed due to recent demands for improvement of digital drawing technology and efficiency of processes. This is CTP (Computer
-to-plate) or DDPP (Digital Direct Prin)
ting Plate). As a plate making method, for example, there is a system for recording an image in a light mode or a heat mode using a laser, and a part of the system has begun to be put into practical use. Further, a direct drawing type lithographic printing plate system to which an ink jet method is applied has been attempted because of the advantage of being an inexpensive and compact drawing apparatus.

As one of the direct drawing type lithographic printing plates for drawing a printing image by using the ink jet method as described above, as one of them, an aluminum support is previously subjected to a hydrophilic treatment with a hydrophilic organic polymer compound. Things. However, when the amount of the hydrophilic organic polymer compound treated on the aluminum support is small, there is a problem that stains are generated. In addition, when the amount of the hydrophilic organic polymer compound treated on the aluminum support is large, there have been problems such as the adhesiveness and image precision of the ink jet drawn image being significantly deteriorated.

Therefore, the pre-hydrophilization treatment is performed to such an extent that the image adhesion is not impaired, and after the image writing (or formation),
In some form, it is necessary to further hydrophilize the non-image portion or to remove the lipophilic component from the non-image portion.
For example, washing with a fountain solution, water, an alkaline aqueous solution, an acidic aqueous solution, or the like, or a hydrophilic treatment is performed. However, such processing steps are cumbersome and time-consuming, require special processing equipment or the attachment of processing equipment to a printing press, and the dangers associated with processing (eg, alkaline liquids may be seen). However, there is also a problem that printing errors and time loss may occur due to the presence of incomplete processing.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a direct-drawing type printing apparatus which can achieve both image adhesion and non-image area hydrophilicity in advance, and which can be used with good workability and can be simplified. An object of the present invention is to provide a lithographic printing plate and a method for producing the lithographic printing plate.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have applied a composition containing a hydrophilic organic high molecular compound on an aluminum support and adsorbed the organic high molecular compound on the surface of the aluminum support. After that, it was found that a direct-drawing lithographic printing plate capable of overcoming the above-mentioned drawbacks of the conventional technique can be obtained by washing with water to remove the excess organic polymer compound, and thus completed the present invention. . That is, the present invention is as follows.

(1) A layer containing a hydrophilic organic polymer compound is provided on an anodized aluminum support, and all the hydrophilic organic polymer compounds in the layer are adsorbed on the support. A direct drawing type lithographic printing plate characterized by the following. (2) The direct-drawing type lithographic printing plate as described in (1) above, wherein the printing image is formed by an inkjet method in which an oil-based ink is ejected using an electrostatic field. (3) After coating the composition containing the hydrophilic organic polymer compound on the aluminum support that has been subjected to the anodizing treatment, the layer is washed with water to remove the excess amount of the composition, and the layer containing the hydrophilic organic polymer compound is removed. The method for producing a direct-drawing lithographic printing plate according to the above (1) or (2), wherein

The surface of the anodized aluminum support is usually hydrophilic, but active sites for adsorbing other substances (hereinafter, also simply referred to as active sites) exist on the surface of the aluminum support. it is conceivable that. By providing a hydrophilic organic polymer compound-containing layer on such a support, a direct-drawing lithographic printing plate can be obtained. However, when an excessive amount of a hydrophilic organic polymer compound-containing layer is provided on an aluminum support and an image area is formed on the aluminum support by using an oil-based ink or the like in an inkjet method, an excessive amount of It was considered that the polymer compound-containing layer swelled to deteriorate the image accuracy (a), and the image portion disappeared with elution of the organic polymer compound-containing layer (b). On the other hand, when the number of the hydrophilic organic polymer compound-containing layers provided on the aluminum support is reduced, the active points on the aluminum support cannot be sufficiently covered, and the printing ink is not printed during the printing. There was also a problem that it was adsorbed on the surface, resulting in contamination.

Therefore, in the present invention, after the composition containing a hydrophilic organic polymer compound is applied onto the aluminum support,
A direct-drawing lithographic plate in which all of the hydrophilic organic polymer compound in the layer is adsorbed on the support by providing a layer containing a hydrophilic organic polymer compound by removing the excess amount of the composition by washing with water. Printed version. Here, the expression that all the hydrophilic organic polymer compounds are adsorbed on the support means that when the lithographic printing plate is washed with water at 15 ° C. for 20 seconds, the hydrophilic organic polymer compound on the support is removed. This indicates that the compound does not become less than 90% by weight of the weight initially present, that is, the residual rate is 90% or more and the removal rate is 10% or less.

The direct drawing type lithographic printing plate of the present invention has a hydrophilic property secured by an aluminum support and a hydrophilic organic polymer compound from the beginning, and increases the hydrophilic property during or after image writing. There is no step of changing the hydrophilicity or removing the lipophilic component, and the non-image area is not stained during printing. On the other hand, all the hydrophilic organic polymer compounds provided on the aluminum support of the direct-drawing lithographic printing plate are adsorbed on the support. Thus, it is considered that the adhesive does not fall off due to washing with water, and thus the adhesion between the image portion and the support is sufficiently ensured when the image is written (or formed). Moreover, since the amount of the hydrophilic organic polymer compound is an appropriate amount, it is considered that the hydrophilic organic polymer compound does not swell with dampening water or ink, thereby causing a problem that image accuracy is deteriorated. Absent. Furthermore, since all the hydrophilic organic polymer compound is adsorbed on the support, it is considered that the organic polymer compound will not be eluted into the dampening water during printing, thereby causing printing trouble. Not even.

In the direct drawing type lithographic printing plate of the present invention, the hydrophilic organic polymer compound-containing layer on the aluminum support may be a continuous layer or a discontinuous layer dotted in an island shape. Is also good.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a direct drawing type lithographic printing plate of the present invention will be described in detail. The hydrophilic organic polymer compound contained in the layer of the direct drawing type lithographic printing plate of the invention on the support is not particularly limited, and any of natural polymers and synthetic polymers can be used. .

The following are examples of natural polymers. Gum and modified gums such as gum arabic, karaya gum, qualum gum, tragacan gum, locust bean gum, arabinogalactan, soya gum, sodium alginate gum arabic, starch and starch-acrylonitrile-based graft polymer hydrolyzate, starch-acrylic Acid-based graft polymer hydrolyzate, starch-
Modified starches such as styrenesulfonic acid-based graft polymers, starch-vinylsulfonic acid-based graft polymers, starch-acrylamide-based graft polymers, cellulose, and carboxylated methylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose Cellulose xanthate, cellulose-acrylonitrile-based graft polymer hydrolyzate, cellulose-acrylic acid-based graft polymer hydrolysate, cellulose-styrene sulfonic acid-based graft polymer, cellulose-vinyl sulfonic acid-based graft polymer, cellulose- Modified celluloses such as acrylamide-based graft polymers, casein and acid casein, milk casein, potash casein, rennet case Emissions, ammonia casein, modified casein borax casein, etc., other, agarose, collagen, gluten, gelatin, agar, dextrin, pectin and the like thereof modified compound.

The following are examples of the synthetic polymers. (Meth) acrylate polymers such as polyacrylic acid and polymethacrylic acid, and copolymers containing these monomers as copolymerization components; vinyl polymers such as polyvinyl sulfonic acid, polyvinyl phosphonic acid, polyvinyl pyrrolidone, and polyvinyl alcohol; Examples thereof include a copolymer containing a monomer as a copolymer component, and a homopolymer or a copolymer containing a quaternary onium group-containing monomer such as an ammonium salt, a phosphonium salt, or a sulfonium salt. Among these, a hydrophilic organic polymer compound containing an acid group or an onium group is preferable.
Further, a hydrophilic organic polymer compound containing a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, an active imino group and the like is more preferable.

When a layer containing the above-mentioned hydrophilic organic polymer compound is provided on an aluminum support described below, the composition containing the hydrophilic organic polymer compound is used as an appropriate treatment solution to form a layer on the aluminum support. It is preferably applied to The main component of the treatment liquid containing a hydrophilic organic polymer compound may be water or an organic solvent, and water and the organic solvent may be used as a mixture. Further, the hydrophilic organic polymer compound in the treatment liquid may be used alone or as a mixture of two or more polymer compounds.

Further, the solution may contain basic substances such as ammonia, triethylamine and potassium hydroxide, hydrochloric acid,
Inorganic acids such as phosphoric acid, sulfuric acid and nitric acid; organic sulfonic acids such as nitrobenzenesulfonic acid and naphthalenesulfonic acid;
Organic phosphonic acids such as phenylphosphonic acid, benzoic acid,
Various organic acid substances such as organic carboxylic acids such as coumaric acid and malic acid, and organic chlorides such as naphthalene sulfonyl chloride and benzenesulfonyl chloride
H may be adjusted. Generally, when the main hydrophilic group of the hydrophilic organic polymer compound is an acidic group, the pH is preferably 0 to 7, and when the hydrophilic group is basic, the pH is preferably 7 to 14. is not.

Further, when phosphoric acid or metaphosphoric acid having a P number of 6 or less is added to the solution, the stain performance is further improved. This is because, besides the above-mentioned pH adjusting effect, phosphoric acid or metaphosphoric acid causes a competitive adsorption reaction with the hydrophilic organic polymer compound, thereby increasing the adhesion efficiency of the polymer compound and, at the same time, the phosphoric acid portion is water-insoluble and hydrophilic with aluminum. It is presumed to form a salt.

The above hydrophilic organic polymer compound-containing layer can be provided on an aluminum support described later by the following method. A method of applying the above-mentioned treatment liquid containing a hydrophilic organic polymer compound onto an aluminum support, followed by washing with water and drying, or a method of immersing the aluminum support in the treatment liquid and then washing with water and drying. Can be mentioned.

In the former method, a treatment liquid having a concentration of 0.1 to 10% by weight as a hydrophilic organic polymer compound can be applied by various methods. For example, bar coater coating, spin coating,
Any method such as spray coating, curtain coating, and gheeser coating may be used. In the latter method, the solution concentration is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, and the immersion temperature is 0 ° C to 80 ° C, preferably 10 ° C.
６０60 ° C., and the immersion time is 0.1 seconds to 5 minutes, preferably 0.5 seconds to 120 seconds. Further, the water washing after any of the methods is performed at a water temperature of 5 ° C to 60 ° C, preferably 10 ° C to 5 ° C.
The temperature is 0 ° C., and the washing time is 0.1 second to 5 minutes, preferably 0.5 second to 120 seconds.

In the direct drawing type lithographic printing plate of the present invention, the coating amount after drying of the hydrophilic organic polymer compound-containing composition on the aluminum support described below is 1 μg / m ^{2 in} total.
１００100 mg / m ² or less, more preferably 10 μm
a ^{g / m 2 ~80mg / m 2} . The coating amount is 1 μg /
If it is less than m ² , a sufficient stain prevention effect cannot be obtained.
If it is more than 100 mg / m ² , a sufficient adhesion effect cannot be obtained.

Next, the support used in the direct drawing type lithographic printing plate of the present invention and the processing thereof will be described. The support used in the direct drawing type lithographic printing plate of the present invention is preferably a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a trace amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The alloy composition has a different atomic content of 10% by weight or less. Aluminum that is suitable for the present invention is pure aluminum, but it is preferable that completely pure aluminum contains as little foreign atoms as possible because it is difficult to produce due to refining technology. In addition, any aluminum alloy having the above-described heteroatom content can be said to be a material that can be used in the present invention. As described above, the composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. Preferred materials are JISA 1050 and 1100,
1200, 3003, 3103, and 3005 materials are included. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment for removing a rolling oil on the surface, for example, a treatment with a surfactant or an alkaline aqueous solution is performed as necessary.

(Roughening and Anodizing) The surface of the aluminum plate may be roughened mechanically, electrochemically dissolved and roughened, and chemically. There is a method of selectively dissolving the surface. As a mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1-100V, electrolysis time 10
It is suitable if it is in the range of seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. If the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient,
The non-image portion of the lithographic printing plate is easily scratched, and so-called "scratch stain" in which ink adheres to the scratched portion during printing is likely to occur. In addition, such an anodizing treatment is performed on the surface used for printing on the support of the lithographic printing plate, and an anodized film of 0.01 to 3 g / m ² is also formed on the back surface due to the back of the lines of electric force. It is generally formed.

(Hydrophilization treatment) As the hydrophilization treatment used after the above-mentioned treatment, there is conventionally known:
A hydrophilic treatment is used. Examples of such a hydrophilic treatment include U.S. Pat. Nos. 2,714,066 and 3,181.
No. 461, No. 3,280,734, No. 3,902,7
No. 34 discloses an alkali metal silicate (for example, sodium silicate aqueous solution) method. In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, Japanese Patent Publication No. 36-22
No. 063, and potassium fluoride zirconate disclosed in U.S. Pat. Nos. 3,276,868 and 4,153.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in U.S. Pat. No. 461 and 4,689,272 is used. Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

(Silica treatment) The anodic oxide film of the aluminum plate treated as described above is treated with an alkali metal silicate of 0.001 to 30% by weight, preferably 0.05 to 10% by weight, at 25 ° C. Is immersed in an aqueous solution having a pH of 9 to 13 at, for example, 5 to 80 ° C. for 0.5 to 120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 9, the solution will gel, and if it is higher than 13.0, the oxide film will be dissolved.
As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used to increase the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned processing solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate,
Titanium sulfate, titanium tetraiodide, zirconium chloride oxide,
Zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like can be mentioned. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.10 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight. By the silicate treatment, the hydrophilicity on the aluminum plate surface is further improved, so that during printing, the ink hardly adheres to the non-image area,
The dirt performance is improved.

Next, an ink jet recording method for forming an image on the direct-drawing planographic printing plate of the present invention will be described. The oil-based ink used in the inkjet recording method for forming an image on the direct-lithographic printing plate of the invention is a non-aqueous solvent having an electric resistance of 10 ⁹ Ω · cm or more and a relative dielectric constant of 3.5 or less. It is obtained by dispersing solid and hydrophobic resin particles at normal temperature.

As the non-aqueous solvent having an electric resistance of 10 ⁹ Ω · cm or more and a relative dielectric constant of 3.5 or less, preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, Or, there are aromatic hydrocarbons and halogenated products of these hydrocarbons. For example, hexane, heptane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper C, isoper E, isoper G, isoper H, isoper L (Isoper; trade name of Exxon), Shersol 70,
Shellsol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Co., Ltd.), silicone oil and the like are used alone or in combination. The upper limit of the electric resistance of such a non-aqueous solvent is about 10 ¹⁶ Ω · cm, and the lower limit of the dielectric constant is about 1.9.

The reason why the electric resistance of the non-aqueous solvent used is in the above range is that if the electric resistance is low, the electric resistance of the ink is not appropriate and the ejection of the ink by the electric field is deteriorated. The reason for setting the range is that when the dielectric constant is high, the electric field in the ink is easily relaxed, whereby the ejection of the ink is easily deteriorated.

The resin particles dispersed in the above-mentioned non-aqueous solvent may be hydrophobic resin particles which are solid at a temperature of 35 ° C. or lower and have good affinity for the non-aqueous solvent. Glass transition point is -5 ° C to 110 ° C or softening point 33 ° C
The resin (P) having a glass transition point of 10 to 100 ° C or a softening point of 38 to 1 ° C is more preferable.
20 ° C., more preferably 15 ° C.
80 ° C or a softening point of 38 ° C to 100 ° C.

By using such a resin having a glass transition point or a softening point, the affinity between the surface of the support (hereinafter, plate material) coated with the image receiving layer and the resin particles is increased, and the bonding between the resin particles is improved. Since it becomes stronger, the adhesion between the image portion and the plate material surface is improved, and the printing durability is improved. In contrast,
Regardless of whether the glass transition point or the softening point is low or high, the affinity between the plate material surface and the resin particles is reduced, or the bonding between the resin particles is weakened. The weight average molecular weight (Mw) of the resin (P) is 1 × 10 ³ to 1 × 10 ⁶ , preferably 5 × 10 ³ to 8 × 10 ⁵ , more preferably 1 × 10 ^3.
10 ^{4 to} 5 × 10 ⁵ .

Specific examples of the resin (P) include:
Olefin polymer and copolymer (for example, polyethylene, polypropylene, polyisobutylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer,
Ethylene-methacrylate copolymer, ethylene-methacrylic acid copolymer, etc.), vinyl chloride copolymer (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc.),
Vinylidene chloride copolymer, vinyl alkanoate polymer and copolymer, allyl aronic acid polymer and copolymer,
Polymers and copolymers of styrene and its derivatives (for example, butadienoic acid-styrene copolymer, isoprene-styrene copolymer, styrene-methacrylate copolymer, styrene-acrylate copolymer, etc.), acrylonitrile copolymer, methacrylic acid Lonitrile copolymer, alkyl vinyl ether copolymer, acrylate polymer and copolymer, methacrylate polymer and copolymer, itaconic diester polymer and copolymer,
Maleic anhydride copolymer, acrylamide copolymer, methacrylamide copolymer, phenol resin, alkyd resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, Polyvinyl acetal resin, urethane resin, rosin resin, hydrogenated rosin resin, petroleum resin, hydrogenated petroleum resin, maleic acid resin, terpene resin, hydrogenated terpene resin, chroman-indene resin, cyclized rubber-methacrylic acid ester copolymer Copolymer, cyclized rubber-acrylate copolymer, copolymer containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, Benzo Orchid ring, benzothiophene ring, 1,3-dioxetane ring), and epoxy resins.

The content of the dispersed resin particles in the oil-based ink used for image recording of the direct drawing type lithographic printing plate of the present invention is preferably 0.5 to 20% by weight of the whole ink. If the content is less than 0.5 wt%, it becomes difficult to obtain an affinity between the ink and the surface of the printing original plate, so that problems such as a failure to obtain a good image and a decrease in printing durability are likely to occur. On the other hand, if the content exceeds 20% by weight, it is difficult to obtain a uniform dispersion, the ink tends to be clogged with the discharge head, and it is difficult to obtain stable ink discharge.

The oil-based ink used for image recording of the direct-drawing lithographic printing plate of the present invention contains a coloring material as a coloring component together with the above-mentioned dispersed resin particles as a coloring component for plate inspection of the plate after plate making. Preferably. As the colorant, any pigments and dyes conventionally used in oil-based ink compositions or liquid developers for electrostatography can be used.

As the pigment, those generally used in the technical field of printing can be used irrespective of inorganic pigments and organic pigments. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine Pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, and other conventionally known pigments are particularly limited. It can be used without doing.

As the dyes, azo dyes, metal complex dyes,
Naphthol dye, anthraquinone dye, indigo dye,
Oil-soluble dyes such as carbonium dyes, quinone imine dyes, xanthene dyes, aniline dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes and metal phthalocyanine dyes are preferred.

These facial medicines and dyes may be used alone or in an appropriate combination, but may be contained in an amount of 0.01 to 5% by weight based on the whole ink. Is desirable.

These coloring materials may be dispersed in a non-aqueous solvent as dispersed particles in the non-aqueous solvent separately from the dispersed resin particles, or may be contained in the dispersed resin particles. In the case of containing, pigments and the like are generally coated with the resin material of the dispersed resin particles to obtain resin-coated particles. General.

The average particle size of these particles, including resin particles dispersed in the non-aqueous solvent and further colored particles, is preferably 0.05 μm to 5 μm. More preferably 0.1 μm to 1.0 μm, more preferably 0.1 μm
m to 0.5 μm. This particle size is CAPA-50
0 (trade name of Horiba, Ltd.).

The above non-aqueous dispersion resin particles can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. As the mechanical grinding method, if necessary,
The material to be resin particles is mixed, melted and kneaded, then directly pulverized by a conventionally known pulverizer to obtain fine particles, and a dispersing polymer is used in combination. ), A method of kneading a material to be a resin particle component and a dispersion-assisting polymer (or a backing polymer) in advance to form a kneaded product, pulverizing the mixture, and then dispersing the mixture in the presence of the dispersed polymer. Can be Specifically, a coating method or a method for producing a liquid developer for electrostatography can be used. For example, these are described in Kenji Ueki, “Flow and pigment dispersion in coating”.
Kyoritsu Shuppan (1971), "Solomon, Science of Nurishina",
`` Paint and Surface Coating Theory and Practic
e ”, Yuji Harasaki“ Coating Engineering ”Asakura Shoten (197
1), Yuji Harasaki, "Basic Science of Coatings", Maki Shoten (1977), and the like.

As the polymerization granulation method, a conventionally known non-aqueous dispersing and entrapment method can be mentioned. Specifically, the latest technology of ultrafine polymer supervised by Soichi Muroi, Chapter 2, CMC Publishing (1991) ), Koichi Nakamura, “Development and Practical Use of Recent Electrophotographic Development Systems and Toner Materials”, Chapter 3, (Nippon Scientific Information Co., Ltd., 1985), KEJ Barrett, “Dispersio
n Polymerization in Organic Media ”by John Wiley (1
975).

Usually, a dispersion polymer is used in combination to stabilize the dispersion of the dispersed particles in a non-aqueous solvent. The dispersed polymer contains a repeating unit soluble in a non-aqueous solvent as a main component, and has an average molecular weight of 1 × 10 in weight average molecular weight Mw.
^It is preferably ³ to 1 × 10 ⁶ , more preferably 5 × 10 ³
５5 × 10 ⁵ .

Preferred examples of the soluble repeating unit of the dispersion polymer include a polymerization component represented by the following general formula (1).

[0044]

Embedded image

In the general formula (1), X ₁ is —COO
Represents-, -OCO- or -O-. R represents 10 carbon atoms
Represents an alkyl group or an alkenyl group having from 32 to 32, preferably represents an alkyl group or an alkenyl group having from 10 to 22 carbon atoms, and may be linear or branched. You may have. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group and the like. Can be

A ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, a C 1 -C 1
3 alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), - COO-Z ₁ or -CH ₂ COO-Z ₁
[Z ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (eg, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.)].

Specifically, Z ₁ represents a hydrogen atom or a hydrocarbon group. Preferred examples of the hydrocarbon group include an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group and an ethyl group). Group, propyl group, butyl group, heptyl group,
Hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group,
2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 4 carbon atoms.
18 optionally substituted alkenyl groups (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group , 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group,
An aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, a benzyl group, a phenethyl group,
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), and an optionally substituted aromatic group having 6 to 12 carbon atoms (For example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl) , Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl, etc.) Listed .

In the dispersion polymer, other repeating units may be contained as a copolymer component together with the repeating units represented by the general formula (1). Other copolymer components include:
Any compound may be used as long as it is composed of a monomer copolymerizable with a monomer corresponding to the repeating unit of the general formula (1). The proportion of the polymer component represented by the general formula (1) in the dispersed polymer is preferably at least 50% by weight, more preferably at least 60% by weight.

Specific examples of these dispersion polymers include:
Examples include the dispersion stabilizing resin (Q-1) used in Examples, and a commercially available product (Solprene 1205, manufactured by Asahi Kasei Corporation) can also be used. The dispersion polymer is preferably added in advance during the polymerization when producing the resin (P) particles as an emulsion (latex) or the like. When the dispersing polymer is used, the amount added is about 0.05 to 4% by weight based on the whole ink.

The dispersed resin particles and colored particles (or coloring material particles) in the oil-based ink of the present invention are preferably positively charged or negatively charged electroconductive particles. In order to impart an electric detecting property to these particles, it can be achieved by appropriately utilizing a technique of a wet type electrophotographic developer. Specifically, the above-mentioned “Recent development and commercialization of electrophotographic development systems and toner materials”
139-148, edited by the Society of Electrophotography, "Basics and Application of Electrophotographic Technology", 497-505 (Corona, 1988), Yuji Harasaki "Electrophotography" 16 (No. 2), 44 (1977) And the like, using the electrolysis material described in the above and other additives.

Specifically, for example, British Patent No. 8934
No. 29, No. 934038, U.S. Pat. No. 112239
No. 7, No. 3900412, No. 460989,
JP-A-60-179751, JP-A-60-185963
And JP-A-2-13965.

The charge controlling agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight with respect to 1000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the oil-based ink. That is, if the electric resistance of the ink from which the dispersed particles have been removed is lower than 10 ⁹ Ω · cm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, the amount of each additive must be controlled within this limit. is necessary.

[0053]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. All percentages in the following examples are% by weight unless otherwise specified.

First, the following aluminum supports (substrates) [A] to [E] were prepared. 0.24mm thick
The surface of a JIS A1050 aluminum plate having a thickness of 0.
After graining using a 295 mm nylon brush and a 400 mesh aqueous suspension of pumicestone, it was thoroughly washed with water. After etching by immersing in a 25% aqueous sodium hydroxide solution at 65 ° C. for 20 seconds, the substrate was washed with running water, neutralized with a 20% aqueous nitric acid solution, and washed with water. V _A = 12.7V
Under the conditions described above, an electrolytic surface roughening treatment was performed using a 1% nitric acid aqueous solution at an anode electricity of 260 coulombs / dm ² using a sinusoidal alternating waveform current. When the surface roughness was measured, it was found to be 0.
It was 53 μm (Ra display). This was immersed in a 25% aqueous sodium hydroxide solution at 70 ° C. for 5 seconds for etching, and then washed with running water. Subsequently, it is immersed in a 30% sulfuric acid aqueous solution and desmutted at 70 ° C. for 10 seconds.
The substrate [A] was prepared by anodic oxidation in a 30% aqueous sulfuric acid solution at a current density of 30 A / dm ² and an anodic oxide film equivalent to 2.6 g / m ² , followed by washing with water.

The surface of a JIS A1050 aluminum plate having a thickness of 0.24 mm was made to have a thickness of 0.295 mm and 0.480 mm.
After graining using an aqueous suspension of a nylon brush of 400 mm and a pumicestone of 400 mesh, it was thoroughly washed with water. 2
After etching by dipping in a 5% aqueous sodium hydroxide solution at 70 ° C. for 15 seconds, the resultant was washed with running water, then neutralized with a 20% nitric acid aqueous solution, and washed with water. This was subjected to electrolytic surface roughening treatment with a 0.8% nitric acid aqueous solution at an anode-time electricity quantity of 260 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.5
It was 5 μm (Ra indication). This was etched by immersing it in a 25% aqueous sodium hydroxide solution at 60 ° C. for 5 seconds, and then washed with running water. Subsequently, it is immersed in a 30% sulfuric acid aqueous solution and desmutted at 70 ° C. for 10 seconds.
Anodizing was performed in a sulfuric acid aqueous solution such that the current density was 30 A / dm ² and the amount of the anodic oxide film was equivalent to 2.6 g / m ² , and the substrate was washed with water to prepare a substrate [B].

The surface of a JIS A1050 aluminum plate having a thickness of 0.24 mm is thoroughly washed with water, immersed in a 25% aqueous sodium hydroxide solution at 50 ° C. for 20 seconds, etched, washed with running water, and then washed with a 20% aqueous nitric acid solution. And washed with water. This was converted to 160 coulombs / day with a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with a dm ² anode charge. When its surface roughness was measured, it was 0.49 μm (Ra indication)
Met. This is added to 35% aqueous sodium hydroxide solution
After immersion at 5 ° C. for 5 seconds for etching, the substrate was washed with running water. Subsequently, it is immersed in a 30% sulfuric acid aqueous solution,
After desmutting for 15 seconds in a 10% aqueous sulfuric acid solution, the current density is 15 A / dm ² , and the amount of anodized film is 2.7 g / m ^2.
Substantially anodized and washed with water to form a substrate [C].

The substrate [A] was treated with a 0.15% by weight aqueous solution of sodium silicate at 22 ° C. for 10 seconds and washed with water to prepare a substrate [D]. The substrate [A] was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds and washed with water to prepare a substrate [E].

(Examples 1 to 11, Comparative Examples 1 to 6) The surfaces of the substrates [A] to [E] treated in this manner were immersed in the hydrophilizing treatment solution shown in Table 1 or by a coater bar. After the application, it was dried at 100 ° C. for 10 seconds.

[0059]

[Table 1]

Thereafter, those corresponding to Examples 1 to 11 were washed with running water at 20 ° C. for 30 seconds, and Comparative Examples 1 to 6 were washed.
The direct equivalent lithographic printing plate was obtained without washing with water. The actually prepared substrate and the hydrophilization treatment solution,
Table 2 shows the treatment conditions and the amount of the composition containing a hydrophilic organic compound.

[0061]

[Table 2]

The amount of the composition containing the hydrophilic organic polymer compound was measured by a gravimetric method or X-ray fluorescence.

Next, a production example of ink resin particles (PL) for ink jet recording will be described.

Production Example 1 Production of Resin Particles (PL-1) Dispersion stabilizing resin (Q-1, Mw: 50,000, having the following structure)
0) 10 g, 100 g of vinyl acetate and Isopar H3
70 ° C. while stirring 84 g of the mixed solution under a nitrogen stream.
Was heated. 0.8 g of 2,2′-azobis (isovaleronitrile) (abbreviated AIVN) as a polymerization initiator
Was added and reacted for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Further, 0.5 g of this initiator was added and reacted for 2 hours.
The temperature was raised to 00 ° C and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 90% and an average particle size of 0.23 μm and having good monodispersibility. Particle size is CAPA-
500 (manufactured by Horiba, Ltd.).

[0065]

Embedded image

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 60 minutes), and the sedimented resin particles were collected and dried. The weight average molecular weight (Mw: GPC value in terms of polystyrene) of the resin particles is 2
× 10 ⁵ , and the glass transition point (Tg) was 38 ° C.

First, an oil-based ink was prepared in the following manner. <Oil-based ink (IK-1)> dodecyl methacrylate /
Acrylic acid copolymer (copolymerization ratio; 95/5 weight ratio)
0 g, 10 g of nigrosine and 30 of Shellsol 71
g was placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with the glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

Preparation of Resin Particles for Ink 6 g (as solid content) of resin particles (PL-1) of Example 1, 2.5 g of the above nigrosine dispersion, FOC-1400 (Nissan Chemical Co., Ltd.)
G), and octadecene-half-maleic acid octadecylamide copolymer 0.0
A black oil-based ink was prepared by diluting 8 g to 1 liter of Isopar G.

Next, the recording apparatus described in International Patent WO93 / 11866 is filled with the ink, an oily ink is discharged onto a direct-drawing type lithographic printing plate to form an image, and the image is heated by a xenon flash fixing device. To make a lithographic printing plate.

After printing 10,000 sheets of the printing plate obtained by the above method with a printing machine SOR-M manufactured by Heidel, the non-image area of the printed matter was evaluated for soiling (ground smearing) as follows.

…: Non-image portion is not stained with ink Δ: Non-image portion is slightly stained with ink ×: Non-image portion is stained with ink

At this stage, the degree of deterioration (printing durability) of the image area on the printed matter was evaluated as follows.

…: No deterioration of the image area △: the area of the image area is slightly reduced ×: the area of the image area is reduced

Further, after the printing plate was removed from the printing machine and left for 30 minutes, printing was restarted again. At this time, the way in which ink was removed from the non-image area was evaluated as follows.

…: The ink is quickly dispensed in the non-image area Δ: the ink is dispensed in the non-image area is slightly slower X: the ink is dispensed in the non-image area is slower

In addition to this, the printing plate obtained by the above method was left in a room at a temperature of 40 ° C. and a humidity of 80% for 8 hours, and then printed on a Heidel printing machine SOR-M for 1,000 sheets.
The stain (non-image stain) of the non-image portion of the printed matter after printing was evaluated as follows.

…: Non-image area is not stained with ink even if water is lowered by two scales from normal value. △: Non-image area is slightly stained with ink when water is lowered by two scales from normal value. The non-image portion is not stained if the value is set. Δ: The non-image portion is slightly stained with ink even if the water is set to the normal value. getting dirty

Table 3 shows the evaluation results of the examples and the comparative examples.

[0079]

[Table 3]

From Table 3 above, the direct-printed lithographic printing plates of Examples 1 to 11 were excellent in all of the soiling property, the wiping property, the printing durability, and the aging stain. On the other hand, the direct-drawing lithographic printing plates of Comparative Examples 1 and 2 were excellent in printing durability, but were inferior in background stainability, wiping property, and aging stainability. Moreover, the direct drawing lithographic printing plates of Comparative Examples 3 to 6 were inferior in all of the soiling property, the wiping property, the printing durability, and the staining with time.

[0081]

As described above, the direct-lithographic printing plate of the present invention has a hydrophilic property from the beginning by the aluminum support and the hydrophilic organic polymer compound, and becomes hydrophilic during or after image writing. There is no step of increasing the hydrophilicity, changing to hydrophilicity, or removing the lipophilic component, and the hydrophilic organic polymer compound in the hydrophilic organic polymer compound-containing layer provided on the aluminum support is all By adsorbing on the support, it does not fall off by washing with water, and when writing (or forming) an image, the adhesion between the image area and the support is sufficiently ensured, and the hydrophilic property is maintained. Since the amount of the organic high molecular compound is an appropriate amount, there is no problem that the hydrophilic organic high molecular compound swells with dampening water or ink to deteriorate image accuracy. Further, since all of the hydrophilic organic polymer compound is adsorbed on the support, the organic polymer compound is not eluted into the dampening water during printing, so that there is no problem in printing. Therefore, the direct-drawing lithographic printing plate of the present invention has both good image adhesion and non-image portion hydrophilicity, so that the printing equipment used with good workability can be simplified.

Continued on the front page F-term (reference) 2H084 AA25 AA40 AE05 BB02 CC05 2H096 AA06 BA01 BA20 CA03 CA20 DA10 EA04 EA23 LA30 2H114 AA04 AA14 AA22 AA28 AA30 BA10 DA04 DA22 DA23 DA41 DA42 DA43 DA44 DA46 DA51 DA53 GA35 EA01

Claims (3)

[Claims] Claims 1. A hydrophilic organic polymer compound-containing layer is provided on an anodized aluminum support, and the hydrophilic organic polymer compound in the layer is all adsorbed on the support. A direct drawing type lithographic printing plate characterized by the following. 2. The direct drawing type lithographic printing plate according to claim 1, wherein the printing image is formed by an ink jet system in which an oil-based ink is ejected by utilizing an electrostatic field. 3. A hydrophilic organic polymer compound comprising a composition containing a hydrophilic organic polymer compound coated on an anodized aluminum support, followed by washing with water to remove an excess amount of the composition. The method for producing a direct-drawing lithographic printing plate according to claim 1, wherein a content layer is provided.