JPS6119026B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a photosensitive printing plate. Conventionally, when exposing a photosensitive printing plate to light through an original image, the surface of the photosensitive layer of the photosensitive printing plate, or the surface of the resin layer (hereinafter simply referred to as photosensitive printing) if the plate has a resin layer on top of the photosensitive layer. In order to completely adhere the original image to the surface of the plate (referred to as the surface of the plate), a photosensitive printing plate and the original image are placed one on top of the other between a rubber sheet and pressure-bonded glass, and a vacuum is created between the rubber sheet and the pressure-bonded glass to achieve close contact. (hereinafter referred to as the vacuum contact method) is used. Conventional photosensitive printing plates are
Because its surface is smooth, when the original image is attached using the vacuum adhesion method, it adheres from the periphery, which prevents degassing in the center, and therefore allows the original image to be completely adhered to the entire surface of the photosensitive printing plate. It took an extremely long time. If image exposure is applied while the adhesion is incomplete, a clear image cannot be obtained in the portion where the adhesion is incomplete, and therefore a clear printed matter cannot be obtained.
Since the time required for adhesion reduces the efficiency of plate-making work, it has been desired for a long time to shorten the time. Photosensitive printing plates and methods for producing the same that shorten the adhesion time are disclosed in British Patent Nos. 1495361 and 1512080, as well as Japanese Patent Application Laid-open Nos. 51-96604 and 51-111102.
No. 52-29302. That is,
It is disclosed that the time required for vacuum adhesion can be significantly shortened by providing a matte layer on the surface of a photosensitive printing plate that is removed during development.
However, in order to manufacture a photosensitive printing plate with such a structure, compared to the case of manufacturing a photosensitive printing plate without a matte layer, coating and drying steps are added to provide a matte layer. Moreover, it has the disadvantage of requiring special coating equipment to provide the matte layer.
As a result, manufacturing costs increased. On the other hand, Japanese Patent Application No. 53-69489 discloses a photosensitive printing plate in which a fine particle substance as a matting agent is added to the photosensitive layer to make the surface of the photosensitive layer matte, thereby shortening the vacuum adhesion time. There is. In the case of such photosensitive printing plates, there are no manufacturing defects as in the case of photosensitive printing plates provided with a matte layer that is removed during development, but there are problems such as a decrease in printing durability and poor tone reproducibility. It had drawbacks such as deterioration. In order to solve the above-mentioned drawbacks, Japanese Patent Application No. 30,606/1987 discloses a photosensitive printing plate in which fine particles are embossed on the surface of the photosensitive layer, thereby shortening the vacuum contact time. The photosensitive lithographic printing plate obtained in this way has a shape in which the particulate matter is attached to the surface of the photosensitive layer, that is, the particulate matter is not substantially buried in the photosensitive layer. Even if the exposed areas harden, the particulate material thereon is not fixed strongly enough and is removed during development. As a result, there is no reduction in printing durability, and there is no problem of poor tone reproducibility.
However, it has been found that this method has the following new drawbacks. (1) A photosensitive coating liquid with such a structure maintains a stable dispersion state if the time from preparation to application is short, but if it is left for a long time from preparation to application, it may cause agglomeration, sedimentation, floating, etc. Fluctuations in the dispersion state are likely to occur. (2) A photosensitive printing plate obtained by coating a coating liquid in which the dispersion state fluctuates such as agglomeration, sedimentation, floating, etc. tends to have problems in appearance because the dispersion of fine particles is not uniform. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a photosensitive printing plate whose surface is matte without additional coating and drying steps. Another object of the present invention is to provide a method for producing a photosensitive printing plate in which particulate matter is embossed on the surface of the photosensitive layer. Another object of the present invention is to produce a photosensitive lithographic printing plate in which fine particulate matter remains in a stable dispersion state for a long period of time in a coating solution, and even after coating, the fine particulate matter is extruded onto the surface in a uniformly dispersed state. The purpose is to provide a method. The inventors of the present invention have conducted various studies to achieve the above objects, and as a result, they have arrived at the present invention. (a) forming a coating liquid layer by applying a coating liquid in which particulate matter is stably dispersed in a solvent solution of the constituent components of the uppermost layer; (b) drying the coating liquid layer; In this way, the stable dispersion state of the particulate matter in the coating solution is destroyed during the drying process, so that the particulate matter is provided in an extruded shape on the surface of the uppermost layer. In the method for producing a photosensitive printing plate with a matte surface, the coating liquid has an average particle size in the range of about 1/1000 to about 1/10 of the average particle size of the fine particle substance. This method is characterized in that the dispersion state of the fine particle substance in the coating liquid is stabilized by containing an aqueous polymer latex. Since the surface of the photosensitive printing plate obtained by using the manufacturing method of the present invention as described above is matted with fine particle substances, the time of contact with the original image by the vacuum contact method can be greatly shortened. I can do it. Moreover, since the particulate matter is not substantially embedded in the photosensitive layer of the photosensitive printing plate, matting by the particulate matter is efficiently achieved. In addition, because the particulate matter maintains a stable dispersion state in the coating solution for a long time, even if it is left for a long time from preparation to application, there will be no fluctuations such as agglomeration, sedimentation, or floating, and the particulate matter will remain stable even after application. It is possible to obtain a photosensitive printing plate in which is uniformly dispersed on the surface. Here, the time period during which the dispersed state is stable is preferably 1 hour or more, most preferably 3 hours or more. The photosensitive printing plate produced according to the present invention basically has a photosensitive layer provided on a support, and is used to create printing plates such as lithographic printing plates, letterpress printing plates, and intaglio printing plates. Preferably, the photosensitive printing plates used in the preparation of lithographic printing plates and intaglio printing plates are included. The supports include dimensionally stable plate-like materials conventionally used as supports for printing plates, and these can be suitably used in the present invention. Such supports include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), aluminum (including aluminum alloys), zinc,
Plates of metals such as iron, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include paper or plastic films laminated or vapor-deposited with metals such as those mentioned above. An appropriate support is selected from these supports depending on the type of printing plate. For example, in the case of a photosensitive printing plate, an aluminum plate, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 18327/1984, etc. are preferable. In the case of a photosensitive letterpress printing plate, polyethylene terephthalate film, aluminum plate, iron plate, etc. are preferable. The support is surface-treated as necessary. For example, in the case of a photosensitive lithographic printing plate, the surface of the support is subjected to hydrophilic treatment. There are various types of such hydrophilic treatment. For example, in the case of supports with plastic surfaces, so-called surface treatment methods such as chemical treatment, electric discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment (for example, US Pat.
No. 2764520, No. 3497407, No. 3145242, No. 3376208,
No. 3072483, No. 3475193, No. 3360448, British Patent No.
788365, etc.) and a method in which an undercoat layer is applied to the plastic after the surface treatment. A variety of coating methods have been developed, including a multi-layer method in which a hydrophobic resin layer that adheres well to plastic and has good solubility is applied as one layer, and a hydrophilic resin layer is applied as a second layer using the same polymer. There is a single layer method in which a resin layer containing hydrophobic groups and hydrophilic groups is applied. In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably. Additionally, U.S. Patent No.
As described in US Pat. No. 2,714,066, an aluminum plate is grained and then immersed in an aqueous sodium silicate solution, and as described in US Pat. No. 3,181,461, an aluminum plate is anodized. , those treated by immersion in an aqueous solution of an alkali metal silicate are also suitably used. The above-mentioned anodizing treatment is carried out by electrolysis using an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., or an organic acid such as oxalic acid, sulfamic acid, or a salt thereof alone or in combination of two or more kinds. This is carried out by passing an electric current through a liquid using an aluminum plate as an anode. Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve the adhesion with the photosensitive layer. This is done for the purpose of improvement. The photosensitive material provided on the support can be any material that changes its solubility or swellability in a developer before and after exposure. The typical ones will be explained below. (1) Composition made of diazo resin The diazo resin represented by the condensate of p-diazodiphenylamine and paraformaldehyde may be water-soluble or water-insoluble, but preferably water-insoluble and water-insoluble. Those soluble in common organic solvents are used. Particularly preferred diazo compounds include salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as phenol salts, fluorocaprates, and triisopropylnaphthalenesulfonic acid, 4,4-biphenyldisulfonic acid, 5 -Nitroortho-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-
Bromobenzenesulfonic acid, 2-chloro-5-
Nitrobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, 1-naphthol-
A compound having two or more diazo groups in one molecule, such as salts of sulfonic acids such as 5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and para-toluenesulfonic acid. . Other desirable diazo resins include a condensate of 2,5-dimethoxy-4-p-tolylmercaptobenzenediazonium containing the above salts and formaldehyde, 2,5-
Condensates of dimethoxy-4-morpholinobenzenediazonium and formaldehyde or acetaldehyde are included. Also preferred are the diazo resins described in British Patent No. 1312925. The diazo resin can be used alone as a photoresist for making a resist, but is preferably used in conjunction with a binder. Various polymer compounds can be used as such binders, including hydroxy, amino,
Those containing groups such as carboxylic acid, amide, sulfonamide, active methylene, thioalcohol, and epoxy are preferred. Preferred such binders include sierach as described in GB 1350521, hydroxyethyl acrylate units or hydroxyl acrylate units as described in GB 1460978 and US 4123276. Polymers containing ethyl methacrylate units as the main repeat unit, polyamide resins as described in US Pat. No. 3,751,257, phenolic resins as described in British Patent No. 1,074,392 and e.g. polyvinyl formal resins, Polyvinyl acetal resins such as butyral resins, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, polyaminostyrenes and polyalkyls. polymers containing amino groups, such as amino (meth)acrylates,
Celluloses such as cellulose acetate, cellulose alkyl ether, and cellulose acetate phthalate are included. The content of the binder in the photosensitive resist-forming composition is suitably 40 to 95% by weight. As the amount of binder increases (ie, as the amount of diazo resin decreases), the photosensitivity naturally increases, but the stability over time decreases. The optimum amount of binder is about 70-90% by weight. Additives such as phosphoric acid, dyes and pigments described in US Pat. No. 3,236,646 can also be added to the diazo resin composition. (2) Composition consisting of an o-quinonediazide compound A particularly preferred o-quinonediazide compound is o-quinonediazide compound.
- Naphthoquinone diazide compounds, such as U.S. Patent Nos. 2766118, 2767092,
No. 2772972, No. 2859112, No. 2907665,
Same No. 3046110, Same No. 3046111, Same No. 3046115
No. 3046118, No. 3046119, No. 3046119, No. 3046118, No. 3046119, No.
No. 3046120, No. 3046121, No. 3046122,
Same No. 3046123, Same No. 3061430, Same No. 3102809
No. 3106465, No. 3635709, No. 3635709, No. 3106465, No. 3635709, No.
It is described in many publications including the specifications of No. 3647443, and these can be suitably used. Among these, o-naphthoquinonediazide sulfonic acid ester or o-naphthoquinonediazidecarboxylic acid ester of an aromatic hydroxy compound, and o-naphthoquinonediazide sulfonic acid amide or o-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound are particularly preferred. In particular, the condensate of pyrogallol and acetone described in U.S. Pat. No. 3,635,709 is subjected to an ester reaction with o-naphthoquinone diazidesulfonic acid,
Polyester having a hydroxyl group at the terminal described in the specification of No. 4028111 is ester-reacted with o-naphthoquinonediazide sulfonic acid or o-naphthoquinonediazidecarboxylic acid, and described in the specification of US Pat. No. 4,139,384. A homopolymer of p-hydroxystyrene or a copolymer of this and other copolymerizable monomers with o-naphthoquinonediazide sulfonic acid or o-naphthoquinonediazidecarboxylic acid is very good. . Although these o-quinonediazide compounds can be used alone, it is preferable to use them in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak type phenolic resins, and specifically include phenol formaldehyde resins, o-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. Further, as described in U.S. Pat. No. 4,123,279, in addition to the above-mentioned phenol resin, phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and formaldehyde are used. It is even more preferable to use it in combination with a condensate. The alkali-soluble resin contains about 50 to about 85% by weight, more preferably about 85% by weight based on the total weight of the photosensitive resist-forming composition.
It can be contained in an amount of 60 to 80% by weight. The photosensitive composition made of the o-quinonediazide compound can further contain pigments, dyes, plasticizers, etc., if necessary. (3) Composition comprising a photosensitive azide compound A suitable photosensitive azide compound is an aromatic azide compound in which an azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group. In these, the azide group is decomposed by light to produce nitrene, which undergoes various reactions and becomes insolubilized. Preferred aromatic azide compounds include compounds containing one or more groups such as azidophenyl, azidostyryl, azidobenzal, azidobenzoyl and azidocinnamoyl, for example 4.
4'-Diazidochalcone, 4-azido-4'-(4
-azidobenzoylethoxy)chalcone, N.
N-bis-p-azidobenzal-p-phenylenediamine, 1,2,6-tri(4'-azidobenzoxy)hexane, 2-azido-3-chloro-benzoquinone, 2,4-diazido-4'-ethoxyazobenzene , 2,6-di(4'-azidobenzal)-4-methylcyclohexanone, 4.
4'-Diazidobenzophenone, 2,5-diazide-3,6-dichlorobenzoquinone, 2,5-
Bis(4-azidostyryl)-1,3,4-oxadiazole, 2-(4-azidocinnamoyl)thiophene, 2,5-di(4'-azidobenzal)cyclohexanone, 4,4'-diazidodiphenyl Methane, 1-(4-azidophenyl)-
5-furyl-2-penta-2,4-diene-1
-one, 1-(4-azidophenyl)-5-(4
-methoxyphenyl)-penta-1,4-dien-3-one, 1-(4-azidophenyl)-3
-(1-naphthyl)propen-1-one, 1-
(4-azidophenyl)-3-(4-dimethylaminophenyl)-propan-1-one, 1-(4
-azidophenyl)-5-phenyl-1,4-
Pentadien-3-one, 1-(4-azidophenyl)-3-(4-nitrophenyl)-2-propen-1-one, 1-(4-azidophenyl)-3-(2-furyl)-2-propene- 1-
1,2,6-tri(4'-azidobenzoxy)hexane, 2,6-bis-(4-azidobenzylidine-pt-butyl)cyclohexanone, 4,4'-diazidodibenzalacetone,
4,4'-Diazidostilbene-2,2'-disulfonic acid, 4'-azidobenzalacetophenone-
2-sulfonic acid, 4,4'-diazidostilbene-α-carboxylic acid, di-(4-azido-2'-hydroxybenzal)acetone-2-sulfonic acid, 4-azidobenzalacetophenone-2 −
Sulfonic acid, 2-azido-1,4-dibenzenesulfonylaminonaphthalene, 4,4'-diazide-stilbene-2,2'-disulfonic acid anilide, etc. can be mentioned. In addition to these low molecular weight aromatic azide compounds, there are also
No. 45-9613, No. 45-24915, No. 45-25713,
JP-A No. 50-5102, No. 50-84302, No. 50-
The azide group-containing polymers described in Patent Publications No. 84303 and No. 53-12984 are also suitable. These photosensitive azide compounds are preferably used together with a polymer compound as a binder. Preferred binders include alkali-soluble resins, such as natural resins such as silica and rosin, novolac type phenolic resins such as phenol formaldehyde resins and m-cresol formaldehyde resins, and polyacrylic acid, polymethacrylic acid, methacrylic acid-styrene resins, etc. Polymers, homopolymers of unsaturated carboxylic acids such as methacrylic acid-methyl acrylate copolymers, styrene-maleic anhydride copolymers, or copolymers of these with other copolymerizable monomers, polyvinyl acetate Examples include resins obtained by partially or completely saponified products of which are partially acetalized with aldehydes such as acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and carboxybenzaldehyde, and polyhydroxystyrene. Furthermore, organic solvent soluble resins including cellulose alkyl ethers such as cellulose methyl ether and cellulose ethyl ether can also be used as binders. The binder is preferably contained in an amount of about 10% to about 90% by weight based on the total weight of the composition comprising the photosensitive azide compound. The composition comprising the photosensitive azide compound may further contain dyes and pigments, plasticizers such as phthalates, phosphoric esters, aliphatic carboxylic esters, glycols, and sulfonamides, such as Michler's ketone, 9-fluorenone, 1 −
Nitropyrene, 1,8-dinitropyrene, 2-
Chloro-1,2-benzanthraquinone, 2-
Additives such as sensitizers such as bromo-1,2-benzanthraquinone, pyrene-1,6-quinone, 2-chloro-1,8-phthaloylnaphthalene, cyanoacridine, etc. can be added. (4) In the main chain or side chain of the polymer

【formula】 Composition consisting of a polymer compound containing groups As a photosensitive group in the polymer main chain or side chain

Those whose main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing [Formula] (for example, U.S. Patent No.
3030208, 3707373 and 3453237); derived from (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols; Polyvinyl alcohol, starch, cellulose, and similar materials; Cinnamate esters of hydroxyl-containing polymers such as
2752372, 2732301, etc.). These compositions may also contain sensitizers, stabilizers, plasticizers, pigments, dyes, and the like. (5) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) at least 2
It consists of a vinyl monomer having five terminal vinyl groups, (b) a photopolymerization initiator, and (c) a polymer compound as a binder. As the vinyl monomer of component (a),
No. 5093, Special Publication No. 14719, Special Publication No. 1971-28727
Acrylic or methacrylic esters of polyols, such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. ) acrylates, etc., or bis(meth)acrylamides such as methylene bis(meth)acrylamide and ethylene bis(meth)acrylamide, or unsaturated monomers containing urethane groups, such as di-(2'-methacryloxyethyl) -2,4-tolylene diurethane, di-
Examples include reaction products of diol mono(meth)acrylates and diisocyanates, such as (2'-acryloxyethyl)trimethylene diurethane. As the photopolymerization initiator of component (b), the compounds represented by the above general formula can be used, but other types can also be used. For example, "Light Sensitive Systems" by J. Courser, Vol.
Carbonyl compounds, as described in Chap.
Examples include organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. More specifically, it is disclosed in British Patent No. 1459563. On the other hand, various known polymers can be used as the binder for component (c). Specific binder details can be found in U.S. Patent No. 4,072,527
It is stated in the specification of the No. Furthermore, British patent no.
The chlorinated polyolefins described in US Pat. No. 1,459,563 are particularly preferred binders. Component (a) and component (c) have a weight ratio of 1:9 to 6:4
Contained in combination within the range. In addition, component (b) is the component
It is contained in a range of 0.5 to 10% by weight based on (a). The photopolymerizable composition further includes a thermal polymerization inhibitor,
It can contain plasticizers, dyes and pigments. The basic structure of the photosensitive printing plate produced by the method of the present invention is one having a photosensitive layer made of the above-mentioned photosensitive substance on a support, but one in which a resin layer is further provided on the photosensitive layer. can also be used. Specifically, there is one described in US Pat. No. 3,136,637. That is, it has a photosensitive layer and a lipophilic, hydrophobic, water-insoluble, and solvent-softening resin layer in this order on a support. Furthermore, it also includes photosensitive printing plates as described in British Patent No. 1478333 and British Patent No. 1478334, which have a similar structure. Various solvents can be used for the coating solution used to coat the top layer of the photosensitive printing plate.
Generally, both one type of organic solvent and a mixture of two or more types of organic solvents are included, but in either case, it is desirable that at least 10% by weight of water can be dissolved at 20°C. That is,
When a type of organic solvent is used, it is desirable that the type of organic solvent itself can dissolve 10% by weight or more of water at 20°C, while two or more types of organic solvents should be mixed together. When a mixed organic solvent is used, it is desirable that the mixed organic solvent is capable of dissolving 10% by weight or more of water at 20°C. Specific solvents or solvent systems include, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethyl acetate,
It can be selected from 2-ethoxyethyl acetate, dimethylformamide, methanol-ethylene dichloride, mixtures thereof, and the like. In the above methanol-ethylene dichloride mixed solvent, methanol can be replaced with ethanol, n-propanol, isopropanol, or a mixture thereof, and ethylene dichloride can be further replaced with methylene chloride, trichloroethane, monochlorobenzene, or a mixture thereof. can do.
Furthermore, other solvents can be additionally mixed with these solvents to the extent that they do not cause any problem. Such additional solvents include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, n-acetate, etc.
propyl, isopropyl acetate, n-butyl acetate,
Contains esters such as methyl amyl acetate, water, etc. The coating solution concentration of the photosensitive composition dissolved in these solvents generally ranges from about 0.1% to about 20% by weight, more preferably from 1 to 10% by weight. Preferred specific examples of particulate materials used in the present invention include, for example, polyethylene particles, polypropylene particles, ethylene-propylene copolymer particles, ethylene-vinyl acetate copolymer particles, polyethylene terephthalate particles, and crosslinked vinyl polymer particles. etc. are included. Crosslinked vinyl polymer particles are usually obtained by well-known suspension polymerization methods. One example is a hydrophobic vinyl monomer having one vinyl group (e.g. acrylic esters, methacrylic esters, styrene, styrene derivatives, acrylonitrile, etc.) and a polyfunctional monomer (1 to 30 parts by weight based on the monomer). For example, divinylbenzene, polyethylene glycol diacrylate (ethylene number n = 1 to 14), polyethylene glycol dimethacrylate (ethylene number n
= 1 to 14), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate,
pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, etc.) and dispersants normally used for suspension polymerization (e.g. inorganic powders such as zinc oxide, calcium carbonate talc, water-soluble polymers such as gelatin, polyvinyl alcohol, etc.) are dissolved. Add to the aqueous medium, deaerate and replace with nitrogen, raise the temperature to about 50-80°C with stirring, add a normal oil-soluble polymerization initiator (e.g. benzoyl peroxide, azobisisobutylnitrile, etc.), and add about 2～
A dispersion of crosslinked vinyl polymer particles is obtained by carrying out a polymerization reaction for 20 hours. Thereafter, crosslinked vinyl polymer particles can be obtained by solid-liquid separation and drying. The particle size (diameter) of the particulate material used in the present invention ranges from about 5μ to about 40μ in average particle size.
is appropriate, preferably in the range of 5 to 20μ. The amount of particulate matter to be present on the surface of the photosensitive printing plate can be selected from a wide range, but generally ranges from about 50 particles/ ^cm2 to about 500,000 particles/ ^cm2 , more preferably from 1000 to about 500,000 particles/cm2. Selected from a range of 100,000 pieces/ ^cm2 . Usually, the optimal range is determined by conducting a large number of trial experiments. The amount of fine particles dispersed in the coating solution to achieve this range varies depending on the coating amount of the top layer, but for example, if the photosensitive layer of a photosensitive lithographic printing plate is the top layer, In some cases, approximately
0.01% to about 20% by weight, preferably 0.1-10
% by weight. On the other hand, the aqueous polymer latex used in the present invention is well known in the field of polymers, and consists of fine polymer particles (referred to as latex particles) dispersed in an aqueous medium. In the present invention, the average particle size (diameter) of latex particles of the aqueous polymer latex is
1000 for the average particle size of the particulate material mentioned above.
The dispersion of particulate material in organic solvents is stabilized when an aqueous polymer latex in the range of 1 to 10 times smaller is used. Such aqueous polymer latex can be selected from a range in which the average particle size of the latex particles is from about 0.01μ to about 2μ, preferably from 0.01 to 1μ,
Most preferably, it is selected from the range of 0.02 to 0.5μ. The aqueous polymer latex used in the present invention can be obtained by emulsion polymerization of vinyl monomers in water. To give a specific example, a vinyl monomer containing about 0.1 to 20% by weight of a dispersant for emulsion polymerization (generally a surfactant is used) and about 2 to 50 parts by weight of water based on the vinyl monomer. The aqueous medium is degassed and replaced with nitrogen, emulsified, additives used in normal emulsion polymerization (e.g. molecular weight regulators, antioxidants, etc.) are added as needed, and finally an emulsion polymerization initiator (e.g. peroxide Hydrogen, potassium persulfate, etc.) are added and emulsion polymerization is carried out according to a conventional method to obtain an aqueous vinyl polymer latex. The above-mentioned monomers are not particularly limited as long as they are vinyl monomers, but the monomers for synthesizing the aqueous polymer latex will be described in detail below. As shown below, monomers are classified into three groups: (A) group (hydrophobic monomers), (B) group (hydrophilic monomers), and (C) group (crosslinking monomers). (A) group monomer; hydrophobic unsaturated vinyl monomer having one vinyl group, acrylic esters,
Monomers such as methacrylic esters, vinyl esters, styrenes, and olefins. Group (B) monomers: hydrophilic unsaturated vinyl monomers having one vinyl group, and monomers having functional groups such as an amino group, a carboxyl group, a sulfonic acid group, an amide group, and a hydroxyl group. Group (C) monomers; monomers with reactive crosslinking groups (epoxide group, hydroxymethylamide group, alkoxymethylamide group, acyloxymethylamide group, isocyanate group, etc.) and polyfunctionality with two or more vinyl groups Monomers. Suitable combinations of monomers when synthesizing an aqueous polymer latex include a homopolymer of group (A) monomers or a copolymer of a combination of two or more monomers, and one or more group (A) monomers and one or more types of monomers. copolymers in combination with monomers of group (B) and one or more of (A)
A copolymer formed by a combination of a group monomer, one or more group (C) monomers, and one or more group (B) monomers, and one or more group (A) monomers, and one or more group (C) monomers. Examples include copolymers formed by combinations of the following. The details will be explained below. Group (A) monomers include hydrophobic vinyl monomers having one vinyl group (hydrophobic here refers to 20
Refers to those having a solubility in water of 8% by weight or less at °C. ) refers to monomers such as acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins. Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2
-Phenoxyethyl acrylate, 2-chloroethyl acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-methoxyethyl acrylate, and 2-ethoxyethyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, acetoacetoxyethyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, Trimethylolpropane monomethacrylate, 2-methoxyethyl methacrylate, 2-
Mention may be made of ethoxyethyl methacrylate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl acetoacetate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, etc. can be mentioned. Examples of styrenes include styrene, methylstyrene, chloromethylstyrene, trifluoromethylstyrene, acetoxymethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, and bromustyrene. Examples of olefins include butadiene, isoprene, chloroprene, propylene, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, vinylidene fluoride, and the like. Other examples include acrylonitrile. Group (B) monomers refer to hydrophilic vinyl monomers having one vinyl group and monomers having functional groups such as an amino group, a carboxyl group, a sulfonic acid group, an amide group, and a hydroxyl group. The hydrophilic monomers mentioned here are monomers that are difficult to carry out in aqueous emulsion polymerization when used alone because of their high solubility in water. Examples of monomers having an amino group include:
Examples include dimethylaminomethyl acrylate, dimethylaminomethyl methacrylate, diethylaminomethyl acrylate, diethylaminomethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, tert-butylaminoethyl acrylate, and tert-butylaminoethyl methacrylate. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, methylenemalonic acid,
Monoalkyl itaconates (e.g. monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.), monoalkyl maleates (e.g. monomethyl maleate, monoethyl maleate, monobutyl maleate, monopropyl maleate, monooctyl maleate, etc.) , citraconic acid, sodium acrylate, ammonium acrylate, ammonium methacrylate, and the like. Examples of monomers having a sulfonic acid group include styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid (for example, acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, acryloyl oxybutylsulfonic acid, etc.), methacryloyloxyalkylsulfonic acids (e.g., methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, methacryloyloxybutylsulfonic acid, etc.), acrylamide alkylsulfonic acids (e.g., 2-acrylamide- 2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (e.g. 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, etc.)
2-methylbutanesulfonic acid, etc.). Examples of monomers having an amide group include acrylamide, methylacrylamide, propylacrylamide, and the like. Examples of monomers having hydroxyl groups include aryl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
-Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl ether of polyhydric alcohol, and the like. Other examples include N-acryloylpiperidine, vinylpyridine, vinylpyrrolidone, and maleic anhydride. Group (C) monomers include monomers with reactive crosslinking groups (epoxide group, hydroxymethylamide group, alkoxymethylamide group, acyloxymethylamide group, isocyanate group) and polyfunctional monomers with two or more vinyl groups. Refers to monomers. (C)
Group monomers are not used alone, but can be added to group (A) monomers or group (A) monomers and group (B) monomers to synthesize crosslinked polymer latexes. Examples of monomers having an epoxide group include glycidyl acrylate, glycidyl methacrylate, glycidyl p-vinylbenzoate, glycidyl crotonate, diglycidyl itaconate,
Examples include diglycidyl maleate, diglycidyl methylene malonate, glycidyl vinyl ether, allyl glycidyl ether, glycidyl-α-chloroacrylate, and the like. Examples of the monomer having a hydroxymethylamide group include hydroxymethylacrylamide and hydroxymethylmethacrylamide. Examples of monomers having an alkoxymethylamide group include methoxymethylacrylamide, methoxymethylmethacrylamide, ethoxymethylacrylamide, ethoxymethylmethacrylamide, butoxymethylacrylamide, butoxymethylmethacrylamide, hexyloxymethylacrylamide, and the like. Examples of monomers having an acyloxymethylamide group include acetoxymethylacrylamide, acetoxymethylmethacrylamide, propionyloxymethylacrylamide, and the like. Examples of the monomer having an isocyanate group include vinyl isocyanate and allyl isocyanate. Examples of polyfunctional monomers include divinylbenzene, polyethylene glycol diacrylate (ethylene number n = 1 to 14), polyethylene glycol dimethacrylate (ethylene number n = 1 to 14), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate. , pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and the like. Further, the polymer latex having epoxide groups may be partially hydrolyzed under acidic or basic conditions to have dihydroxy groups. A suitable monomer combination for synthesizing the aqueous polymer latex is a homopolymer of group (A) monomers or a copolymer of two or more monomers and at least 50% by weight of one or more group (A) monomers. or more, preferably 80% by weight or more and one or more (B)
The total of the copolymer with group monomers and one or more group (A) monomers and one or more group (C) monomers is at least 50% by weight or more, preferably 80% by weight or more.
Copolymer with (B) group monomer and (C) with (A) group monomer
Examples include copolymers with group monomers. Group (B) monomers, which are generally hydrophilic monomers, are used to improve the stability during emulsion polymerization and the stability over time of aqueous latexes. When dispersing aqueous polymer latex particles in an organic solvent, it is necessary that the latex particles are insoluble in the organic solvent used and do not aggregate in the organic solvent. Since latex particles may be soluble, insoluble, or non-agglomerated depending on the composition of the organic solvent used, the monomer composition constituting the latex particles cannot be uniquely limited. However, crosslinked latex polymers are generally more preferred. That is, one or more group (A) monomers and one or more group (C) monomers.
The total amount with the group monomers is 50% by weight or more, preferably
A copolymer of 80% by weight or more and one or more group (B) monomers or a copolymer of one or more group A monomers and one or more group C monomers is more preferred. The composition ratio of the (A) group monomer and (C) group monomer cannot be uniquely defined. Dispersants used in emulsion polymerization include general anionic, cationic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Those skilled in the art are well aware of these dispersants for emulsion polymerization, and to give some examples, for example, R-OSO ₃ M or R(-OCH ₂ CH ₂ ) for anionic surfactants. −lOSO ₃ M
(In the formula, R is an alkyl group having 8 to 30 carbon atoms, M is an alkali metal or ammonium, and l is a positive integer of 0 to 30.) Or (In the formula, R' is hydrogen or an alkyl group having 1 to 18 carbon atoms, R'' is an alkyl group having 1 to 18 carbon atoms, M is an alkali metal or ammonium, m is a positive integer from 0 to 30, and n is 0 , 3, or 4.)
Examples of nonionic surfactants include alkylbenzenesulfonic acid series as shown in the following formula, polyoxyethylene derivatives and higher fatty acid esters of sugars, and amphoteric surfactants include sulfobetaine series and amino acid series. The particle size of the aqueous polymer latex can be arbitrarily determined depending on factors such as the amount of dispersant for emulsion polymerization, the amount of monomer, the amount of polymerization initiator, stirring speed, and polymerization temperature. The above water-based polymer latex may be used in a coating solution for coating the top layer of a photosensitive printing plate in terms of solid content from about 0.0001% by weight to about 1% by weight based on the above organic solvent.
It is generally contained within a range of 10% by weight. As the amount decreases below the above 0.0001% by weight, the dispersion stability of the hydrophobic polymer particles decreases. On the other hand, as the amount exceeds 10% by weight, the latex particles of the aqueous polymer latex themselves tend to aggregate, and the dispersion stability of the particulate material is not improved any further. Therefore, more preferred amounts of aqueous polymer latex are from 0.005 to 5% by weight, most preferably from 0.01 to 2% by weight on the same basis as above. Furthermore, by including the aqueous polymer latex, the amount of water contained in the dispersion of the present invention is suitably about 10% by weight or less based on the organic solvent, and more preferably Preferably it is 3% by weight or less. Coating liquids containing dispersed particulate matter and aqueous polymer latex include, for example, doctor coat, roller coat, gravure coat, bead coat,
It can be coated onto the support by various means such as dip coating. Furthermore, drying of the coating liquid layer can be carried out in a conventional manner, and is carried out by evaporating the solvent at room temperature to high temperature. The preferred drying temperature range is approximately 20
°C to about 150 °C, with a range of 50 to 120 °C being more preferred. In the case of a photosensitive lithographic printing plate, the thickness of the photosensitive layer is preferably from about 0.1 g/m ² to about 7 g/m 2 , more preferably from 0.5 to 4 g/ ^{m 2 in} terms of weight after drying. Hereinafter, the present invention will be explained in more detail with reference to Examples. "%" in the examples indicates "% by weight" unless otherwise specified. The aqueous polymer latex used was prepared as follows. Temperature controller, stirrer, reflux condenser, heating device,
The inside of 10 sealed reaction vessels made of glass having a gas inlet was purged with nitrogen gas, and distilled water 7.2 and 90 g of surfactant A for emulsion polymerization described below were added and heated to 60° C. and dissolved by heating and stirring. Next, butyl methacrylate 1.1 is used as an ethylenically unsaturated vinyl monomer.
Kg, add 0.7Kg of glycidyl methacrylate,
Emulsification was carried out by stirring at 60° C. for 30 minutes at 50 to 200 revolutions per minute. Next, 1.3g of potassium persulfate as a polymerization initiator
Then, 0.4 g of sodium bisulfite was added and a polymerization reaction was carried out for 5 hours. The temperature of the reaction solution rose from 60°C to about 75°C due to the heat generated by the polymerization reaction. After polymerizing for 5 hours, the polymer was cooled to 40°C. The particle size of the aqueous polymer latex thus obtained is 0.03 to 0.07μ, and the solid content concentration is 20% by weight.
It was hot. Aqueous polymer latexes shown in Table 1 below were prepared in a similar manner. In addition, 0.36 of the 1.8 kg of aqueous polymer latex and vinyl monomer shown in Table 1
Kg was initially charged and emulsified by stirring, and at the same time as the polymerization initiator was added, the remaining 1.44 Kg was dropwise polymerized for 1 hour. Dispersants A to E for emulsion polymerization

[Table] Examples 1 to 4 and Comparative Example 1 An aluminum plate with a thickness of 0.24 mm was immersed in a 7% aqueous solution of tertiary sodium phosphate at 60°C to degrease it, and after washing with water, a solution of pumice suspended in water was added. While washing it, I scrubbed it with a nylon brush to make it grainy. JIS No. 3 sodium silicate (SiO ₂ /Na ₂ O) kept at 70℃ after washing with water.
(mole ratio) = 3.1 to 3.3) for 30 to 60 seconds. After thoroughly washing with water and drying, apply the next coating solution (C ₁ ) ~
(C ₆ ) is applied and dried to form a photosensitive lithographic printing plate C ₁ ~
Got _C6 .

[Table] However, each coating solution was applied after being allowed to stand for 1 hour after preparation. The coating weight after drying was 1.0 g/m ² . Photosensitive lithographic printing plate thus obtained
When the surfaces of C ₁ to _{C 5} were observed, it was found that in photosensitive lithographic printing plate C ₁ , particulate matter was extruded and stuck to the surface of the photosensitive layer, but the particulate matter was agglomerated with each other and dispersed uniformly. I hadn't done it. On the other hand, in all of the photosensitive planographic printing plates C ₂ to _{C 5} , the particulate matter was fixed to the surface of the photosensitive layer in an extruded form, and the particulate matter was uniformly dispersed. When each photosensitive lithographic printing plate was superimposed on a negative transparent original image and brought into close contact with it using the vacuum adhesion method, the results were 1/2 to 1/3 that of a photosensitive lithographic printing plate made without using fine particle substances. I was able to get it in close contact. Each plate with the original picture attached in vacuum was exposed to a metal halide lamp for 40 seconds from a distance of 1 meter.
After immersing the plate in the following developer at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed areas to obtain a lithographic printing plate. Benzyl alcohol 3.0g Sodium isopropylnaphthalene sulfonate
1.0 g Sodium silicate (40% aqueous solution) 1.0 g Water 95 g When printing was performed with each planographic printing plate, the planographic printing plates obtained from photosensitive planographic printing plates C ₁ to C ₅ had a printing life of 50,000 sheets. Ta. In addition, when the surface of the image area of each lithographic printing plate was observed under a microscope immediately after development, it was found that the photosensitive lithographic printing plate
In the lithographic printing plates obtained from _C1 to _C5 , the presence of particulate matter could not be confirmed in the image area. Examples 5 to 7 and Comparative Examples 2 to 4 In the same manner as in Example 1, except that six types of coating liquids (C ₆ ) to (C ₁₁ ) consisting of the following and were used as coating liquids for the photosensitive layer. Photosensitive lithographic printing plates C ₆ to C ₁₁ were prepared, respectively.

[Table] Each coating solution was applied after being allowed to stand for 1 hour after preparation. The coating weight after drying was 1.0 g/m ² . When the surface of the photosensitive layer of each photosensitive planographic printing plate was observed, it was found that fine particulate matter was extruded and adhered to the surface of the photosensitive layer in all photosensitive planographic printing plates, but photosensitive planographic printing plate C ₆ , C ₈ and C ₁₀ , the particulate matter was agglomerated and not uniformly dispersed, whereas the surface of the photosensitive lithographic printing plates C ₇ , C ₉ and C ₁₁ had particulate matter dispersed uniformly. Was. When we measured the time required for each photosensitive lithographic printing plate to adhere to the negative original using the vacuum adhesion method, we found that the time required to bring each photosensitive lithographic printing plate into close contact with the negative original image was 1/2 to 1/2 that of using a photosensitive lithographic printing plate that did not use particulate matter. It was shortened to 1/3. Each plate to which the original image was adhered was imagewise exposed in the same manner as in Example 1, and then developed in the same manner as in Example 1 to obtain a lithographic printing plate. Each lithographic printing plate had a printing life of 50,000 sheets. The surface of the image area of each lithographic printing plate was also examined, and it was found that no particulate matter was present. Examples 8 and 9 Photosensitive lithographic printing plates C ₁₂ and C were prepared in the same manner as in Example 1, except that two coating solutions C ₁₂ and C ₁₃ consisting of and below were used as coating solutions for the photosensitive layer, respectively. I made ₁₃ .

[Table] Each coating solution was applied after being allowed to stand for 1 hour after preparation. The coating weight after drying was 1.0 g/m ² . On the surface of the thus obtained photosensitive lithographic printing plate, the particulate matter was fixed in an extruded form, and moreover, the particulate matter was uniformly dispersed without agglomerating with each other. Examples 10 to 11 and Comparative Examples 5 to 6 A grained aluminum plate with a thickness of 0.3 mm was anodized in sulfuric acid to form an oxide film of about 2 g/m ² , thoroughly washed, dried, and then coated on top. Coating liquids (C ₁₄ ) to (C ₁₇ ) consisting of the following and drying were applied to approx.
Photosensitive lithographic printing plate C ₁₄ with a photosensitive layer of 2.5 g/m ²
~ _C17 was obtained.

[Table] Each coating solution was applied after being allowed to stand for 1 hour after preparation. When observing the surface of each photosensitive printing plate,
C ₁₄ and C ₁₆ had agglomerated fine particles and were not uniformly dispersed. On the other hand, fine particulate matter was uniformly dispersed on the surfaces of C ₁₅ and C ₁₇ . In addition, in all of the photosensitive lithographic printing plates, the particulate matter was fixed to the surface of the photosensitive layer in an extruded form. For each photosensitive printing plate, the time required to bring it into vacuum contact with a positive transparent original is 1/2 to 1/2 of the time required for a photosensitive lithographic printing plate that does not use particulate matter.
It was shortened to 1/3. Next, image exposure was carried out in the same manner as in Example 1.
When a lithographic printing plate was prepared by developing with a % sodium silicate aqueous solution and printed, it had a printing durability of 60,000 sheets, which was equivalent to the printing durability of a lithographic printing plate coated with a coating solution that did not contain a matting agent. It was hot. Furthermore, the tone reproducibility was also the same. Furthermore, when the image area after development was observed, it was confirmed that no polyethylene particles were present.

Claims (1)

[Scope of Claims] 1. The uppermost layer of a photosensitive printing plate having a photosensitive layer on a support is coated with (a) a coating solution containing fine particulate matter stably dispersed in a solvent solution of the constituent components of the uppermost layer; (b) drying the coating liquid layer, and thus, the stable dispersion state of the particulate matter in the coating liquid is destroyed during the drying process;
In a method for producing a photosensitive printing plate having a matte surface, the fine particulate material is provided in an extruded shape on the surface of the uppermost layer, wherein an average particle of the fine particulate material is contained in the coating liquid. By containing an aqueous polymer latex having an average particle size in the range of about 1/1000 to about 1/10 of the particle size, the dispersion state of the particulate matter in the coating liquid is stabilized. A method characterized by: