JPH04138459A - Planographic printing plate and production thereof - Google Patents

Abstract

PURPOSE:To allow the stable formation of the planographic printing plate by dry processing by polymerizing a polymerizable compd. selectively in parts to form polymerized latent images consisting of polymerized parts and unpolymerized part, roughening the surface of the unpolymerized parts and polymerizing the unpolymerized parts. CONSTITUTION:The polymerizable compd. 2 of the original plate for planographic printing having the polymerizable compd. and a polymn. initiator is polymerized selectively in parts to form the polymerized latent images consisting of the polymerized parts 2-a and the unpolymerized parts 2-b. The surface of the unpolymerized part is then roughened and the unpolymerized parts 2-b subjected to the surface roughening are polymerized. Fine rugged patterns are formed by the simple and rapid method in this way and the rugged parts are the hydrophilic parts which are liable to be wet. The smooth parts are the water-repellent parts. The planographic printing plate is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a lithographic printing plate and a method for manufacturing the same, and particularly to a lithographic printing plate manufactured by dry processing and a method for manufacturing the same.

[Conventional technology]

Conventionally, on lithographic printing plates, an image is usually formed in which the non-image areas are hydrophilic and the image areas are water repellent. To increase the print quality, dampening water is applied to prevent ink from adhering.The ink adheres only to the image area and is transferred to the printing paper, etc.

Examples of such lithographic printing plates include the Waipon plate, the 28-plate, the multilayer lithographic plate, the semi-intaglio plate, and the semi-letter plate. In either case, a photosensitive substance is coated on a metal plate such as aluminum, zinc, aluminum-iron-copper monochromium, etc., and an image is formed on the metal plate through processes such as image exposure and development.

In addition, fine irregularities are generally formed on the surface of a metal plate (graining), and these can be formed using various forces.Among these, electrolytic polishing using an electrolytic bath of sulfuric acid or phosphoric acid ( anodic oxidation) is widely used. This grain serves to improve the adhesion of the photosensitive material, and at the same time is extremely effective in improving the affinity for dampening water, that is, the water retention capacity.

Further 3M's Driography that does not use dampening water
There are waterless lithographic plates made by Toshi, Toshi, and Dai Nippon Printing, which are being put into practical use. These make use of the ink repellency of silicone rubber, and they are coated with silicone rubber on a metal plate such as aluminum. There are layers, and they are manufactured by exposure and development in the same way as described above. Waterless lithographic printing plates using fluororesin instead of silicone rubber are also being considered, and 3M has developed a DryDuplicating System.
It is announced as em.

[Problem to be solved by the invention]

However, in the case of conventional lithographic printing plates, the development process when forming the printing plate (resist image) is a wet process that requires the use of organic solvents and water, which requires maintenance and disposal of liquid waste. It involves complicated processes such as, and also poses a social problem of environmental pollution due to solvents.

There is also a developing method that utilizes the difference in tackiness caused by light, the so-called beer-apart processing, which eliminates the need for a wet process. , the equipment becomes complicated, and it is not favorable in terms of cost performance.

In addition, the grain method formed in the non-image area As mentioned above, in many cases, the force formed by electrolytic polishing is wet.
Also, it is difficult to form multiple grains with the same grain.

The object of the present invention is to solve the various problems mentioned above, and in particular, to produce a lithographic printing plate that can be formed easily, quickly, with good reproducibility, and stably by dry processing. The object of the present invention is to provide a method and a lithographic printing plate with good printing durability.

[Means to solve the problem]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a lithographic printing plate precursor having at least a polymerizable compound and a polymerization initiator is site-selectively polymerized according to the image, and the polymerized and unpolymerized areas are By taking advantage of the difference in hardness, it is possible to form a fine unevenness (rough surface) pattern in an extremely simple and quick method and by dry processing. The method of manufacturing the lithographic printing plate of the present invention will now be described, in which the lithographic printing plate of the present invention and the method of manufacturing the same were completed based on the discovery that the portion becomes a water-repellent portion and can be used for lithographic printing.

The method for producing a lithographic printing plate of the present invention includes: (a) site-selectively polymerizing the polymerizable compound to a lithographic printing plate precursor having at least a polymerizable compound and a polymerization initiator; (b) roughening the unpolymerized portion; and (c) polymerizing the roughened unpolymerization portion. That is.

In the present invention, during the process of site-selectively (desired pattern) polymerizing the polymerizable compound contained in the lithographic printing plate precursor, the polymerized portion is the "polymerized portion" as referred to in the present invention, The portion that is not polymerized is the "unpolymerized portion" as referred to in the present invention. And, the "polymerization part" and "
A desired pattern consisting of "unpolymerized parts" is the "latent image" in the present invention. In addition, the term "unpolymerized portion" includes not only the case where no polymerization occurs but also the case where the polymerization is substantially unpolymerized.

Hereinafter, embodiments of the method for manufacturing a lithographic printing plate of the present invention will be explained in detail with reference to the drawings.

First, as shown in FIG. 1(a), a lithographic printing plate precursor having a support 1 and a polymer layer 2 containing a polymerizable compound and a polymerization initiator is prepared. Here, since oxygen interferes with the generation of radicals during polymerization of the polymerizable compound in the polymerization layer, an oxygen barrier layer 4 made of polyester film, polyvinyl alcohol, etc. may be provided on the polymerization layer 2 as necessary. good.

Next, the polymer layer 2 is exposed to light including the absorption wavelength of the photopolymerization initiator contained in the polymer layer 2 through a suitable mask 5, so that the polymerizable compound in the polymer layer 2 is polymerized, and the mask is removed. Polymerized portion 2-a and unpolymerized portion 2- according to pattern 5
A latent image consisting of b is formed.

The mask used here is preferably a mask consisting of a transparent part and a non-transparent part. In other words, the polymerized and unpolymerized parts of the polymerized latent image each have approximately the same degree of polymerization (
It is desirable to use a mask that has a hardness. Further, analog exposure, digital exposure, etc. other than the mask exposure described above may be used.

Furthermore, instead of photopolymerization, thermal polymerization using a thermal head, thermal pen, etc. may be used. Furthermore, the polymerization rate can be increased by simultaneously performing exposure and heating.

In this process, when exposure is performed, examples of the light source include a tungsten lamp, a mercury lamp, a halogen lamp, a xenon lamp, and a fluorescent lamp. In addition, examples of exposure without using a negative mask include liquid crystal shutter array, CRT,
Examples include optical fiber tubes.

Next, as shown in FIG. 1(b), the rough surface forming medium 6 in which fine irregularities are formed is pressed against the planographic printing plate precursor 3 consisting of the polymerized portion 21 and the unpolymerized portion 2-b, so that the polymerized portion Using the difference in hardness between 2-a and the unpolymerized portion 2-b, fine irregularities on the rough surface forming medium 6 are transferred and formed. That is, the unpolymerized part 2-b is in a soft state, and the polymerized part 2-a has been polymerized and/or crosslinked by polymerization and is in a hard state. Appropriate pressure is applied to the rough surface forming medium 6 so that the fine irregularities of the rough surface forming medium 6 are not transferred and the fine irregularities of the rough surface forming medium 6 are transferred to the unpolymerized portion 2-b. Only fine irregularities are transferred and formed.

The roughening medium used here needs to be able to sufficiently withstand the load during pressing without destroying the minute irregularities on the roughening medium when pressed against the planographic printing plate master. Any material can be used as long as it meets the requirements, such as aluminum, zinc,
Metal plates such as copper and steel, plastic films such as polyethylene terephthalate, glass, glue, resin coated glue, glue covered with metal foil such as aluminum, rubber, and composites thereof, such as lf, metals with rubber elastic layers. board,
Plastic films, glass paper, etc., as well as aluminum, zinc, copper, nickel, chromium, and iron are plated, vapor-deposited,
Alternatively, a sputtered metal plate, plastic film, glass, paper, etc. can be used. There are eight methods for roughening these surfaces, which vary depending on the material of the roughening medium, including brush polishing, electrolytic polishing, ball polishing, chemical polishing, and honing. A rough surface may be formed by molding using a mold having a rough surface formed by the method described above.

The roughness of the surface formed by the above method is preferably 0.01 to 2 .mu.m in center line average roughness, and the average opening diameter is preferably 10 .mu.m or less. Further, a film of silicone resin, fluorine resin, or the like may be formed on the surface of the uneven portion of the rough surface forming medium 6 in order to improve mold release properties.

Furthermore, the rough surface forming medium 6 used in the present invention is shown in FIG. 1(b).
It is not limited to the shape of a flat plate as shown in Figure 2, but also the shape of a cylindrical desk roll.

In addition, in the polymerization synthesis of a lithographic printing plate precursor in which no rough surface is formed, the degree of the smooth portion is 10 in terms of center line average roughness.
00 people, more preferably 700 Å or less,
The optimum thickness is 500 Å or less.

The material obtained through the process up to (b) can be used as a lithographic printing plate as is.Since the hardness of the unpolymerized area is small, the rough surface formed on the unpolymerized area is rough during printing. , blankets, and ink suits are pressed by rollers Swimsuits are pressed by rollers, etc. The wettability may change from the initial state, leading to a decline in the image quality of printed matter and poor printing durability, so we will explain (c) below. It is preferable that the entire polymerized layer 2 is formed into a polymerized and/or crosslinked product of a polymerizable compound by the process described above.

That is, as shown in FIG. 1(c), using the same light source as in FIG. 1(a), light and/or heat is applied to the entire surface of the polymerized layer to cover the entire surface of the polymerized layer on the support with the polymerizable compound. Polymerized and/or crosslinked product.

In the present invention, using the electrophotographic method described below,
It is also possible to produce a lithographic printing plate by an image forming method as shown in FIG.

That is, as shown in FIG. 2, a conductor 7, a photoconductor 8, a support 1, and a polymer layer 2 are laminated, and the surface of the polymer layer 2 is charged by corona discharge. Next, as described above, the polymer layer 2 is exposed through a suitable mask 5 to light that includes the absorption wavelength of the photopolymerization initiator contained in the polymerization layer 2 and includes the absorption wavelength of the photoconductor 8, and the polymerization layer 2 is exposed to light that includes the absorption wavelength of the photoconductor 8. At the same time, the polymerizable compound in the layer 2 is polymerized to form a polymerized latent image consisting of a polymerized area Z-a and an unpolymerized area 2-b according to the pattern of the mask 5.Resistance of the photoconductor in the exposed area The value decreases, the amount of surface charge in that area decreases, and a charged latent image is obtained (FIG. 2(b)). Next, by heating, the unpolymerized part 2-b is deformed by heat and Coulomb attraction, and the amount of charge and/or the unpolymerized part 2-b is changed.
Fine irregularities are formed depending on the hardness of b, followed by cooling and peeling off the support and photoconductor to obtain a lithographic printing plate as shown in FIG. 2(d). The heating temperature is between the softening temperature of the unpolymerized portion and the softening temperature of the polymerized portion, and a high temperature is preferred as long as the softening and deformation of the polymerized portion does not occur.

Furthermore, in order to improve printing durability, the same manufacturing method as above was used.
It is preferable that the entire polymer layer of the lithographic printing plate is made of a polymer of polymerizable compounds (FIG. 2(d)).

During the above exposure, the light source is a light source that includes the absorption wavelength of the photopolymerization initiator contained in the polymerization layer and the absorption wavelength of the photoconductor, and the exposure is performed twice using a separate light source that includes the absorption wavelengths of each of the absorption wavelengths. It is also possible to perform exposure using a light source containing the absorption wavelength of the photopolymerization initiator, followed by exposure using a light source containing the absorption wavelength of the photoconductor, or in the reverse order as 2-n = rotational light. Good too.

Various materials are used as photoconductors: Sulfur, selenium, amorphous silicon; alloys such as selenium-tellurium, selenium-arsenic, selenium-sulfur; zinc oxide; inorganic compounds such as zinc or cadmium sulfides; gelatin; Silver halide: Those containing organic compounds such as anthracene, acenaphthene, and benzidine polyvinylcarbazole are preferred.

As a conductor in the embodiment of Figure 2, there is a wide range of conductive materials to choose from, such as aluminum, copper, stainless steel, platinum, gold, chromium, nickel, phosphor bronze, carbon, etc., conductive polymers, or Various types of polymers in which metal fillers are dispersed are used.

Next, the lithographic printing plate precursor used in the method for manufacturing a lithographic printing plate of the present invention will be described.

The lithographic printing plate precursor used in the present invention contains at least a polymerizable compound and a polymerization initiator.

As the polymerizable compound, a compound having at least one reactive vinyl group in one molecule can be used. One or more types selected from the group can be used.

The reactive vinyl groups of these compounds include styrene vinyl groups, acrylic acid vinyl groups, methacrylic acid vinyl groups, allyl vinyl groups, vinyl ethers, and ester vinyl groups such as vinyl acetate. Examples include unsubstituted vinyl groups.

Specific examples of polymerizable compounds that satisfy such conditions are as follows.

Example +f, styrene, methylstyrene, chlorthrene, bromostyrene, methoxystyrene, dimethylaminostyrene, cyanostyrene, nitrostyrene, hydroxystyrene, aminostyrene, carboxystyrene,
Acrylic acid, methyl acrylate, ethyl acrylate, cyclohexyl acrylate, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, phenyl methacrylate, cyclohexino methacrylate, vinylpyridine, N- Vinylpyrrolidone, N-vinylimidazole,
Monovalent monomers such as 2-vinylimidazole, N-methyl-2-vinylimidazole, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-chlorophenyl vinyl ether divinylbenzene, distyryl oxalate, distyryl malonate, distyryl succinate, distyryl glutarate,
distyryl adipate, distyryl maleate, distyryl fumarate, β,β°-dimethylglutarate distyryl, 2-bromoglutarate distyryl, a,α-dichloroglutarate distyryl, distyryl terephthalate,
Oxalic acid di(ethyl acrylate), oxalic acid di(methyl acrylate), malonic acid di(ethyl acrylate)
, malonic acid di(methyl ethyl acrylate), succinic acid di(ethyl acrylate), glutaric acid di(ethyl acrylate), adipic acid di(ethyl acrylate), maleic acid di(ethyl acrylate), fumaric acid di(ethyl acrylate), β,β′-dimethylglutarate di(
ethyl acrylate), ethylene diacrylamide, propylene diacrylamide, 1,4-phenylene diacrylamide, 1,4-phenylene bis(oxyethyl acrylate), 1.4-phenylene bis(oxymethyl ethyl acrylate), 1.4 -bis(acryloyloxyethoxy)cyclohexane, 1,4-bis(acryloyloxymethylethoxy)cyclohexane, 1,4
-Bis(acryloyloxyethoxycarbamoyl)benzene, 1,4-bis(acryloyloxymethylethoxycarbamoyl)benzene, 1,4-bis(acryloyloxyethoxycarbamoyl)cyclohexane, bis(acryloyloxyethoxycarbamoylcyclohexyl)methane, dioxalate (ethyl methacrylate)
, dioxalate (methyl ethyl methacrylate), di malonate (ethyl methacrylate), di malonate (methyl ethyl methacrylate), di succinate (ethyl methacrylate), di succinate (methyl ethyl methacrylate),
Glutaric acid di(ethyl methacrylate), adipic acid di(ethyl methacrylate), maleic acid di(ethyl methacrylate), fumaric acid di(ethyl methacrylate),
Fumaric acid di(methyl ethyl methacrylate), β, β°
-dimethylglutarate di(ethyl methacrylate), 1
．． 4-Phenylenebis(oxyethyl methacrylate)
, 1.4-bis(methacryloyloxyethoxy)cyclohexane acryloyloxyethoxyethyl vinyl ether and other divalent monomers pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tri(hydroxystyrene), dipentaerythritol hexaacrylate, Cyanuric acid triacrylate, cyanuric acid trimethacrylate, 1,1.1-)limethylolpropane triacrylate, 1,1.1-)limethylolpropane trimethacrylate, cyanuric acid triacrylate
(ethyl acrylate), 1,1.1-)limethylolpropane tri(ethyl acrylate), cyanuric acid tri(ethyl vinyl ether), 1,1.1-)limethylolpropane tri(toluene diisocyanate) and hydroxyethyl acrylate condensate, 1.1.1-)
A trivalent monomer such as a condensate of limethylolpropane tri(hexane diisocyanate) and p-hydroxystyrene.

Tetravalent monomers such as ethylene tetraacrylamide and propylene tetraacrylamide, pentavalent monomers such as dipentaerythritol monohydroxypentaacrylate, hexavalent monomers such as dipentaerythritol hexaacrylate, and oligomers. Alternatively, examples thereof include a polymerizable compound in which a reactive vinyl group is left at the end of the polymer, or a polymerizable compound in which a reactive vinyl group is attached to the side chain of an oligomer or polymer.

Note that it is also possible to use two or more of these polymerizable compounds in combination.

The polymerization initiator contained in the lithographic printing plate blank used in the present invention is a photopolymerization initiator and/or a thermal polymerization initiator.

As the thermal polymerization initiator, any known initiator may be used, such as an azo peroxide initiator.

Azo initiators are organic compounds having at least one nitrogen-nitrogen double bond in the molecule, such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylphenethylcarbonitrile, azobis-8ec - Amylonitrile, azobisphenylethane, azobiscyclohexylpropylonitrile, azobismethylchloroethane, trityl azobenzene, phenylazoisobutyronitrile, '9-(p-nitrophenylazo)-9-phenylfluorene, etc. I can do it.

The peroxide initiator includes almost all organic compounds having at least one oxygen-oxygen bond in the molecule. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-)limethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1°-bis(tert
-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1°-bis(tert-butylperoxy)cyclohexane, n-butyl-4,4-bis(te
rt-Butyflavoroxy)parerate, 2,2゛-bis(tert-butylperoxy)butane, tert-
Butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2-sibide lobaroxide, 1,1゜3.3-tetramethylbutyl hydroperoxide, tert-7-butyl peroxide, tert-butyl peroxide Mil peroxide, dicumyl peroxide, a, a'-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl -2,5-tert-butylperoxyhexyne-3, acetyl peroxide, imbutyryl peroxide, octanoyl peroxide, decanoyl peroxide,
lauroyl peroxide, 3,5.5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2- Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate carbonate, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, 7er7-butylperoxypivalate, tert-butylperoxyneodecanoate, tert-butylperoxyoctanoate, tert-butyl Peroxy
3,5,5-)limethylhexanoate, tert-butylperoxylaurate, 7ert-butylperoxybenzoate, di-tert-butylciberoxyisophthalate, 2,5-dimethyl-2,5-di( Examples include benzoylperoxy)hexane, tert-butylperoxymaleic acid, tert-butylperoxyisopropyl carbonate, etc. The present invention is not limited to these, and other known thermal polymerization initiators can be used. Agents can also be used.

Examples of the photopolymerization initiator include carbonyl compounds, sulfur compounds, halogen compounds, and redox photopolymerization initiators.

Specifically, carbonyl compounds include, for example, diketones such as benzyl, 4.4°-dimethoxybenzyl, diacetyl, and camphorquinone; for example, 4,4゛-bis(diethylamino)benzophenone, 4.4゛-dimethoxybenzophenone, etc. benzophenones; for example, acetophenones such as acetophenone and 4-methoxyacetophenone; benzoin alkyl ethers; for example, 2-chlorothioxanthone, 2,4-cyclothioxanthone, 2,4-diethylthioxanthone, thioxanthone-3-carboxylic acid-β -thioxanthone such as methoxyethyl ester; chalcones and styryl ketones having a dialkylamino group; 3,3°-carbonylbis(7-medoxycoumarin), 3,3'-carbonylbis(7-dinithylaminocoumarin) ) and other coumarins.

Examples of the sulfur compound include dibenzothiazolyl sulfide, decylphenyl sulfide, and disulfides.

Examples of halogen compounds include carbon tetrabromide quinolinesulfonyl chloride, S-) having a trihalomethyl group,
Examples include riazine.

Redox-based photopolymerization initiators include those used in combination with trivalent iron ion compounds (e.g. ferric ammonium citrate) and peroxide, and those used in combination with photoreducible dyes such as riboflavin and methylene blue and triethanolamine. , those using a combination of reducing agents such as ascorbic acid, and the like.

Moreover, among the photopolymerization initiators described above, more efficient photopolymerization can be carried out by combining two or more types of photopolymerization initiators.

Examples of such a combination of photopolymerization initiators include a combination of chalcone, styryl ketones, or coumarins having a dialkylamino group, and S-) riazine or camphorquinone having a trihalomethyl group.

The lithographic printing plate precursor used in the present invention can be prepared by dissolving the above-mentioned essential components in a solvent together with an appropriately used binder, and applying and drying the solution onto a support such as plastic or paper, or by using the binder itself. If the strength is maintained, the above-mentioned essential components can be contained in a film or sheet-like product formed from a binder without using the above-mentioned support, and the product can be formed as a single polymer layer.

The shape of the lithographic printing plate precursor of the present invention is not particularly limited, such as a flat plate or a cylindrical roll shape.

The polymer layer of the lithographic printing plate precursor in the present invention is 0.5μ
m to 2 foxes It is desirable to form a film to a thickness of about 1 μm to 0.1 mm before use.

The binder that can be used in the present invention can be selected from a wide range of resins.
Nitrocellulose People Cellulose esters such as cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate/propionate, cellulose acetate/butyrate; Methylcellulose people Ethylcellulose people Cellulose ethers such as propyl cellulose and butyl cellulose; Vinyl resins such as polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, and polyvinylpyrrolidone; Styrene-butadiene copolymer Styrene-acrylonitrile copolymer, styrene- Copolymer resins such as butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer; acrylic resins such as polymethyl methacrylate, polymethyl acrylate, polybutyl acrylate, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyacrylonitrile; polyethylene terephthalate, etc. polyesters; for example, poly(4,4-isopropylidene, diphenylene-two-1.
4-cyclohexylene dimethylene carbonate), poly(ethylenedioxy-3,3°-phenylene thiocarbonate), poly(4,4°-isopropylidene diphenylene carbonate coated terephthalate), poly(4,
4°-isopropylidene diphenylene carbonate),
Polyacrylate resins such as poly(4,4'-5ec-butylidene diphenylene carbonate), poly(4,4'isopropylidene diphenylene carbonate-block-oxyethylene), polyamides; polyimides, epoxy resins, phenolic resins Examples include polyolefins such as polyethylene, polypropylene, and chlorinated polyethylene, and natural polymers such as gelatin.

In addition, a photodiscoloration inhibitor, a solid latent arc surfactant antistatic agent, and the like may be added to the lithographic printing plate precursor used in the present invention, if necessary.

The preferred blending ratio of the above components in the lithographic printing plate precursor used in the present invention is: 1) The polymerization initiator is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 100 parts by weight of the polymerizable compound. Parts by weight to 20 parts by weight.

The lithographic printing plate of the present invention can be completed using the materials and manufacturing method described above.A material capable of controlling light transmission is contained in the polymer layer of a lithographic printing plate precursor in advance, and is directly written with a laser or the like. A lithographic printing plate can also be obtained by this method. Wet silver salt, dry silver salt, polymer liquid crystal, etc. are materials that can perform such light transmission control.Dry silver salt is used because dry processing is simple and allows for a large contrast in transmittance. Preference is given to using mono-γ-salts.

That is, a lithographic printing plate precursor comprising such a support is laminated with a photosensitive layer containing at least a photosensitive silver halide, an organic silver salt, a reducing agent, a polymerizable compound, and a photopolymerization initiator. (a) imagewise exposing the original plate, (b) heating the original plate, (c) exposing the entire surface of the original plate to polymerize the polymerizable compound, and separate the polymerized parts and unpolymerized parts. (d) roughening the unpolymerized portion; and (e) polymerizing the roughened unpolymerized portion. Manufactured by a method.

Hereinafter, aspects of the method for manufacturing the lithographic printing plate will be described in detail with reference to the drawings.

The process of (a) above is a process of writing an image using light, and as shown in FIG. 3(a), at least the photosensitive silver halide, organic silver salt, and L A desired image is exposed on the photosensitive layer 9 containing a polymerizable compound and a photopolymerization initiator by image exposure or digital exposure. As a result, silver nuclei 10 are generated on the photosensitive silver halide in the exposed area 9-a, forming a latent image. The generated silver nuclei 10 serve as a catalyst for the thermal reaction between the organic silver salt contained in the photosensitive layer 9 and the reducing agent.

The exposure conditions for writing this latent image are appropriately selected depending on the concentration of silver halide contained in the photoreceptor, so that desired characteristics such as sufficient contrast can be obtained in the resulting polymerized latent image. You can use it as Since photosensitive silver halide is used in this process, highly sensitive writing is possible.

In addition, in FIG. 3(a), if necessary, an oxygen barrier layer 4 may be laminated on the photosensitive layer in the same manner as described above. It also has the role of preventing sublimation.

Next, in the above step (b), when the photosensitive layer 9 on which the latent image is formed is heated, the exposed portion 9 is heated as shown in FIG. 3(b).
In -a, the silver nucleus 10 selectively acts as a catalyst, and the organic silver salt and the reducing agent react, and the organic silver salt is reduced to silver atoms 11, and at the same time, the reducing agent becomes an oxidant 12.

The heating in the step (b) is performed at a temperature of 60°C to 200°C, preferably 70°C to 150°C, for 1 second to 5 minutes, depending on the composition of the photosensitive layer, etc.
More preferably, the heat treatment may be performed for 3 seconds to 60 seconds. In general, high temperatures require short heating times; low temperatures require long heating times. As a heating means, a hot plate,
In addition to the method of using a heat roll, a thermal head, etc., a method of heating by supplying electricity to a heating element of the support, a method of heating by laser light irradiation, etc. can be used.

Subsequently, as shown in FIG. 3(C), in the process of (c) above, the entire surface of the photosensitive layer 9 is exposed to light to cleave the photopolymerization initiator contained in the photosensitive layer 9 and generate radical species. . This radical species causes a polymerization reaction of the polymerizable compound,
A polymerized portion is formed in the photosensitive layer 9. At this time, in the photosensitive layer 9, the black silver atoms 11 and/or the oxidized product 12 of the reducing agent absorb light, and the amount of light transmitted differs accordingly, so that the exposed area 9-a and the unexposed area 9-b A difference occurs in the state of formation of the polymer, and a polymerized latent image is formed due to the difference.

The reducing agent used here is a reducing agent that generates an oxidant that quenches the C1 radical, which has the ability to absorb the light of full-surface exposure and inhibit the polymerization of the polymerizable compound as described above. When a chemical agent is used, the radicals are quenched by the oxidant generated in the process (b) and polymerization is inhibited. No polymer is formed in the exposed area 9-a, and no polymer is formed in the unexposed area 9-b. Formation A polymerization latent image is formed, which differs in the formation state of the polymer depending on the amount of oxidant. Reducing agents that produce oxidants having different polymerization inhibiting abilities will be described later.

The light sources used in the above steps (a) and (C) include, for example, Jf, sunlight, tungsten lamp, mercury lamp, halogen lamp, xenon lamp, fluorescent lamp, L
ED, laser beam, etc. can be used, and direct writing or exposure through a mask as described above can be performed, and the wavelengths of light used in these processes may be the same or different. In addition, even if light of the same wavelength is used in steps (a) and (C), silver halide usually has a sufficiently higher photosensitivity than the photopolymerization initiator, so photopolymerization does not occur in step (a) above. Sufficient latent image writing can be performed with light of an intensity that does not cause this. It is more effective if a sensitizing dye is added at the time of forming the photosensitive layer according to the color distribution of each light source.

Further, in the step (c) above, a means for heating the lithographic printing plate precursor during exposure may be used. This is to promote polymerization, and it may be heated again or the residual heat from the process (b) above may be used, but the oxidation-reduction reaction between the organic silver salt and the reducing agent in the photosensitive layer is It is necessary to heat under conditions where this does not occur, and the conditions vary depending on the combination of the organic silver salt and the reducing agent.The heating temperature is about 120°C or lower, preferably 90°C or lower, and more preferably 60°C or lower.

Next, as shown in FIG. 3(d), an oxygen barrier layer 4 is formed.
After peeling off, the rough surface forming medium 6 in which fine irregularities are formed is pressed against the lithographic printing plate precursor 3 consisting of the polymerized part 91 and the unpolymerized part 9-b. Using the difference in hardness of b, the fine irregularities of the rough surface forming medium 6 are formed as shown in Fig. 3 (
Transfer formation is performed as shown in e). Thereafter, by exposing the entire surface to light in the same manner as described above, the entire photosensitive layer on the support is made into a polymer of the polymerizable compound, and a lithographic printing plate is obtained (Fig. 3 (f)
)).

In the method for producing a lithographic printing plate of the present invention as described above, the lithographic printing plate precursor includes a photosensitive layer containing at least a photosensitive silver halide, an organic silver salt, a reducing agent, a polymerizable compound, and a photopolymerization initiator. A material that uses layers
Examples include, but are not limited to, a polymeric layer having at least a polymerizable compound and a photopolymerization initiator on a ζf1 support,
Furthermore, a planographic printing plate precursor having a two-layer structure in which a dry silver salt layer containing at least a photosensitive silver halide, an organic silver salt, and a reducing agent is laminated, and a dry silver salt layer and a polymerization layer are formed on separate supports. It is also possible to use a planographic printing plate precursor having a two-layer structure in which each layer is formed and then laminated. In these cases, between the above manufacturing steps (C) and (d), a process of peeling off the imagewise exposed dry silver salt layer and the polymerized layer on which the polymerized latent image has been formed is required. The method is exactly the same as above.

Here, in order to make it easier to peel off the dry silver salt layer and the polymerized layer,
It is preferable to provide an intermediate layer made of polyethylene film, polyvinyl alcohol, etc. between the dry silver salt layer and the polymerized layer.

Next, materials contained in the lithographic printing plate precursor used in the above method will be explained.

The polymerizable compound, powder, binder, additives, etc. are the same as those in the above-mentioned manufacturing method, and the photopolymerization initiator corresponds to the above-mentioned photopolymerization initiator.

The photosensitive silver halide contained in the lithographic printing plate precursor used in the above method includes silver chloride, silver bromide, silver chlorobromide, silver iodobromide,
Examples include silver chloroiodobromide, which may be subjected to chemical sensitization or optical sensitization treatment as is applied to ordinary photographic emulsions.

Furthermore, the halogen composition within the particles may be uniform or may have a different multilayer structure. Two or more types of silver halides having different halogen compositions, grain sizes, grain size distributions, etc. may be used in combination.

Examples of organic silver salts include silver salts with aliphatic carboxylic acids, aromatic carboxylic acids, thiocarbonyl group compounds having a mercapto group or a-hydrogen, and imino group-containing compounds.

Aliphatic carboxylic acids such as acetic acid, butyric acid, succinic acid, sebacic acid, adipic acid, oleic acid, linoleic acid, linoleic acid, linoleic acid, tartaric acid, palmitic acid, stearic acid, behenic acid, camphoric acid etc. If there is a small number of carbon atoms, the silver salt is unstable, so an appropriate number of carbon atoms (for example, f1
Those having a carbon number of 16 to 26 are preferred.

Examples of aromatic carboxylic acids include quinolinic acid derivatives derived from benzoic acid, salicylic acid derivatives derived from naphthalenecarboxylic acid, gallic acid, tannic acid, phthalic acid, and pyromellitic acid derived from phenylacetic acid.

Examples of mercapto group or a-hydrogen-containing thiocarbonyl group compounds include 3-mercapto-4-pheny4cyl-1,2,4-)riazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercapto-5-aminothiadiazole, -Mercaptobenzothiazole, S-alkylthioglycolic acid (alkyl group having 12 to 23 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-
phenyl-4-thiopyridine, mercaptotriazine,
2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,2
, 4-) Riazole et al., U.S. Pat. No. 4,123.27
Examples include mercapto compounds described in No. 4.

As a compound containing an imino group, Japanese Patent Publication No. 44-30
Benzotriazole or its derivatives described in No. 270 or No. 45-18416, such as benzotriazole, alkyl-substituted benzimidazoles such as methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, and carboimides such as butylcarboimide benzotriazole. Benzotriazoles, nitrobenzotriazole Kai described in JP-A-58-4-118639 Sulfobenzotriazole, carboxybenzotriazole or salt thereof described in JP-A-58-115638
or hydroxybenzotriazole, etc., U.S. Pat.
Typical examples include 1,2,4-triazole, IH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof, which are described in No. 220,709.

Reducing agents include monophenols, bisphenols, trisphenols, tetrakisphenols, mononaphthols, bisnaphthols, dihydroxynaphthalenes, trihydroxynaphthalenes, dihydroxybenzenes, trihydroxybenzenes, and tetrahydroxybenzenes. , hydroxyalkyl monoethers, alkorbic acids, 3-pyrazolidones, pyrazolines, pyrazolones, reducing sugars, phenylenediamines, hydroxyamines, reductones, hydrooxamic acids, hydrazones, amidoximes, N
Specific examples of these compounds include JP-A-51-22431, U.S. Pat. No. 3.615.533, U.S. Pat. No. 904, No. 3.751.252,
Same No. 3.751.255, Same No. 3.782.949, Same No. 3,801,321, Same No. 3.794゜488
No. 3.893.863, No. 3.887.37
No. 6, Belgian Patent No. 786.086, U.S. Patent No. 3
．． 770.448, 3.819.382, 3.773.512, 3.928°686, 3.839.048, 3.887.378,
Japanese Patent Publication No. 51-35851, Japanese Patent Publication No. 50-36143, U.S. Pat. No. 3,827.889, U.S. Pat. No. 3,756.
No. 829, JP-A-50-36110, JP-A-50-1
No. 16023, JP-A-50-147711, JP-A-5
1-23721, JP 50-99719, JP 51-32324, JP 51-51933, JP 50-140113, JP 52-84727,
It is described in US Pat. No. 3,589,503.

Here, in order to increase the contrast in the amount of light absorbed (transmitted) between the exposed area and the unexposed area, an oxidant with a large molar extinction coefficient is preferable, and as a reducing agent to form such an oxidant, Aromatic hydroxy compounds are preferred. The aromatic hydroxy compounds will be explained in detail below.

The compounds represented by the following general formulas (I), (n), (m), (rv) and (V) quench radicals by oxidizing the reducing agent generated by the redox reaction with the organic silver salt. By doing so, it exhibits the ability to inhibit polymerization.

[However, in the above general formulas (r) to (m), R1, R2゜R
3.Rs and R6 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, an alkoxyl group-substituted or unsubstituted cycloalkyl group , R4 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a carboxyl group, a carboxylic acid ester group, and A represents an oxygen atom or a sulfur atom, R represents a hydrogen atom, an unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, and 2 represents a divalent linking group, which is an alkylidene group, a substituted or unsubstituted aralkylidene group, or a sulfur atom. , and n represents O or 1. ] The substituents R1 to R6 in the reducing agents represented by the general formulas (1) to (m) will be explained.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The substituted or unsubstituted alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms, preferably, for example, methyl, ethyl, propyl, l-propyl,
Butyl, 7-butyl, amyl, i-amyl, hexyl, thexyl, heptyl, octyl, -nonyl, dodecyl, stearyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxybutyl, i-propoxybutyl, t- Butoxyethyl, hexyloxybutyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, aminomethyl, dimethylaminomethyl,
Aminoethyl, dimethylaminoethyl, morpholinoethyl, piperidinoethyl, aminopropyl, diethylaminopropyl, dipropylaminoethyl, aminobutyl,
Morpholinbutyl and the like.

The substituted or unsubstituted aralkyl group has 7 to 19 carbon atoms, preferably benzyl, phenethyl, benzhydryl, trityl, phenylpropyl, naphthylmethyl, chlorobenzyl, dichlorobenzyl, methoxybenzyl, methylbenzyl, etc. be.

Substituted or unsubstituted aryl groups have 6 to 16 carbon atoms, such as phenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, cumenyl,
Mesityl, chlorophenyl, methoxyphenyl, fluorophenyl, etc.

The alkoxyl group has 1 to 18 carbon atoms,
Preferred are methoxy, ethoxy, propoxy, i-propoxy, butoxy groups and the like.

The substituted or unsubstituted cycloalkyl group has 5 to 18 carbon atoms, preferably cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl and the like.

The carboxylic acid ester group has 2 to 10 carbon atoms, preferably methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and the like.

The alkylidene group has 1 to 8 carbon atoms, and is preferably a methylene, ethylidene, butylidene, hexylidene group, or the like.

The aralkylidene group has 7 to 18 carbon atoms, preferably benzylidene, naphthylmethylene, p-
These include dimethylaminophenylmethylene, p-hydroxyphenylmethylene, p-tolylmethylene, and the like.

Specific examples of particularly preferred reducing agents among the reducing agents represented by the above-mentioned -Momonana (+) to (m) are listed below.The reducing agent used in the present invention is not limited to these.

Specific examples of the reducing agent represented by general formula (I) include lf, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol,
5-Methyl-4-methoxy-1-naphthol, 1.5-
Dihydroxynaphthalene, 4-chloro-1-naphthol, 5-chloro-1-naphthol, 4-methylthio-1-
Naphthol, 4-ethylthio-1-naphthol, 6-phenyl-4-methyl-1-naphthol, 6-phenyl-
4-methoxy-1-naphthol, 6-benzyl-1-naphthol, 6-benzyl-4-methoxy-1-naphthol, 4-methyl-1,7-dihydroxynaphthalene, 4
-Methoxy-6-benzyl-1-naphthol, 4-methoxy-6-cyclohexyl- 1-naphthol, 4-methylthio-6-cyclohexyl-1-naphthol, 3.4-dimethyl-1-naphthol, 4-benzyloxy- Examples include 1-naphthol.

- Specific examples of the reducing agent represented by Monka (n) include If, 8-hydroxyquinoline, 4,8-dihydroxyquinoline-2-carboxylic acid, 4-hydroxyquinoline-2-carboxylic acid, 4-methyl -8-hydroxyquinoline, 4-benzyl-8-hydroxyquinoline, 4.
Examples include 8-dihydroxy-5-methylquinoline.

Specific examples of the reducing agent represented by the general formula (m) include If, 2.2'-methylenebis(6-t-butyl-1,4-dihydroxybenzene), 2.2'-methylenebis(4-methoxybenzene), phenol), 2.2"-methylenebis(4,6-di-7-butylphenolbis(4
-methyl-6-t-butylphenol) 2,2゛-butylidenebis(4-methoxyphenol), " 111 2,2°-butylidenebis(6-7-butyl-1,4-
dihydroxybenzene), 2,2'-thiobis(4-methoxyphenol), 2,2'-thiobis(6-methyl-1,4-dihydroxybenzene), 2,2'-thiobis(4,6-di-t) -butylphenol), bis(2-hydroxy-5-
Methifrephenyl) phenylmethane, (3-7-butiflephenyl-5-methyl-2-hydroxyphenyl) (5-methoxy-2-hydroxyphenyl)methane, and the like.

[However, R in the above - Monana (■), (V) is a hydrogen atom,
Substituted or unsubstituted alkyl group Represents a substituted or unsubstituted aralkyl group, R? , R11 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and R9 represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted aralkyl group, Represents an alkyl group. n is 0 or 1. ] Specific examples of the reducing agent represented by general formula (1) include 1-methoxy-5-hydroxyanthracene, 1-ethoxy-5-hydroxyanthracene, 1-methoxy-4-methyl-5-hydroxyanthracene. ,1
-methoxy-4,8-dimethyl-5-hydroxyanthracene and the like.

Specific examples of the reducing agent represented by general formula (V) include: 4,4゛-dimethoxy-2,2°-binaphthol, 4,4゛-jethoxy-2,2°-binaphthol, 4
, 4°-dimethyl-2,2′-binaphthol, 4,4°
- Diethyl-2,2°-binaphthol, etc.Next, the reducing agents represented by the following -Momonena (vr) and (■) are the oxidants produced by the redox reaction with organic silver salts, which are photoresist. It is a reducing agent that exhibits the ability to inhibit polymerization by absorbing light in the absorption wavelength range of the polymerization initiator.

[However, - Monana (Vl) and (■) Higashi 1-1. +2 and +2' +1 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, r and ro each independently represent a hydrogen atom , a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, an alkoxyl group, m is an integer of 1 to 3, and Y is a monovalent to trivalent linking group, Substituted or unsubstituted aralkyl group Substituted amino group Alkylidene group Substituted or unsubstituted aralkylidene group Methine group, Z represents alkylidene group Substituted or unsubstituted aralkylidene group.
] In the general formulas (Vl) and (■), the unsubstituted alkyl group is a straight chain or branched alkyl group having 1 to 18 carbon atoms, such as (xl methyl, ethyl, propyl, i-
Propyl, butyl, 7-butyl, i-butyl, amyl,
Examples include piamyl, 5ec-amyl, thexyl, hexyl, heptyl, octyl, nonyl, dodecyl, stearyl, and the like.

The substituted alkyl group is an alkoxyalkyl group having 2 to 18 carbon atoms, a halogenoalkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, or a hydroxyalkyl group having 1 to 18 carbon atoms.
For example, alkoxyalkyl groups include methoxyethyl, ethoxymethyl,
Ethoxyethyl, ethoxypropyl, ethoxybutyl,
Examples include propoxymethyl, propoxybutyl, i-propoxypentyl, t-butoxyethyl, hexyloxybutyl, and the like.

Examples of the halogenoalkyl group include chloromethyl,
Examples include chloroethyl, bromoethyl, chloropropyl, chlorobutyl, chlorohexyl, chlorooctyl, and the like.

Examples of the hydroxyalkyl group include iL-roxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, and hydroxyheptyl.

Examples of aminoalkyl groups include: x1 aminomethyl, acetylaminomethyl, dimethylaminomethyl, aminoethyl, acetylaminoethyl, dimethylaminoethyl, diethylaminoethyl, morpholinoethyl, piperidinoethyl, diethylaminopropyl, dipropylaminoethyl, acetylaminopropyl , aminobutyl,
Examples include morpholinobutyl.

Examples of the cycloalkyl group include f1 cyclopentyl, cyclohexyl, and cycloheptyl.

Examples of the aralkyl group include benzyl, chlorobenzyl, and phenethyl.

The aryl group has 6 to 16 carbon atoms, preferably eg (fl phenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, cumenyl,
Mesityl, chlorophenyl, methoxyphenyl, fluorophenyl, etc.

The alkoxyl group has 1 to 18 carbon atoms,
Preferably methoxy, ethoxy, propoxy, l-
Propoxy, butoxy, etc.

Among the above, preferred substituents for R2 and R2' are chlorine atom, bromine atom, methyl, ethyl, i-propyl, t
-butyl, 5ec-amyl, thexyl, ethoxymethyl, ethoxyethyl, chloromethyl, hydroxymethyl,
Aminomethyl, dimethyl-aminomethyl, benzyl, and particularly preferred substituents are chlorine atom, 7-butyl, thexyl. Preferred substituents as rl are chlorine atom,
Methyl, ethyl, i-propyl, L-butyl, amyl,
These are thexyl, hydroxyl, chloromethyl, hydroxymethyl, benzyl, and cyclohexyl, and particularly preferred substituents are chlorine atom, methyl, 7-butyl, and thexyl.

Examples of the substituted or unsubstituted aralkyl group of the monovalent linking group include (fl benzyl, p-methoxybenzyl, p-N,N-dimethylaminobenzyl, p-pyrrolidinobenzyl, p-methylbenzyl, p-hydroxy Benzyl, p-chlorobenzyl, 3,5-cyclo-4-hydroxybenzyl, 3-methyl-5-t-butyl-4-
Hydroxybenzyl, 01p-dimethylbenzyl, 3.
Examples include 5-dimethyl-4-hydroxybenzyl, 2-hydroxy-3-t-butyl-5-methylbenzyl, and naphthylmethyl.

As a substituted amino group of a monovalent linking group, methylamino,
Dimethylamines Diethylamino, acetylamino, phenylamino, diethylamino, triadylamino and the like can be mentioned.

Examples of the alkylidene group of the divalent linking group include methylethylidene, propylidene, butylidene, and the like.

As the aralkylidene group of the divalent linking group, for example,
Examples include benzylidene, p-methylbenzylidene, and p-dimethylaminobenzylidene.

A preferable reducing agent in general formula (v+) is 2.6
-di-t-butyl-4-(2-hydroxy-3-t-butyl-5-methylbenzyl-4-(3.5-dichloro-4-hydroxybenzyl)phenol, 2-t-butyl-4-( 2-hydroxy-3,5-dimethylbenzyl)-5-methylphenol, 4,4'-methylenebis(2-methyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol) ), 4.4°-methylenebis(
2-t-butyl-5-methylphenol), 4,4°-
Methylenebis(2-7-butyl-6-methylphenol), 4,4°-ethylidenebis(2,6-di-t-butylphenol), 4.4'=ethylidenebis(2-t-
butyl-6-methylphenol), 4,4°-propylidenebis(2,6-di-t-butylphenol), 4,
4°-butylidene bis(2,6-di-7-butylphenol), 4.4'-butylidene bis(2-cyclohexyl-6-methylphenol), bis(3.5-di-L
-butyl-4-hydroxyphenyl)phenylmethane,
Bis(3.5-di-t-butyl-4-hydroxyphenyl) (4-methoxyphenyl)methane, bis(3.5-di-t-butyl-4-hydroxyphenyl) (4-methoxyphenyl)methane.
5-di-t-butyl-4-hydroxyphenyl) (4-
dimethylaminophenyl)methane and tris(3.5-di-t-butyl-4-hydroxyphenyl)methane.

As a preferable reducing agent in the general formula (■), for example, if
, 4,4°-methylenebis(2-methyl-1-naphthol), 4,4'-methylenebis(2-ethyl-1-
naphthol), 4.4'-methylenebis(2-t-butyl-1-naphthol), 4.4'-methylenebis(2
-t-butyl-6-methyl-1-naphthol), 4,4
°-ethylidenebis(2-methyl-1-naphthol),
4.4°-ethylidene bis(2-7-butyl-1-naphthol), bis(4-hydroxy-3-methylnaphthyl) phenylmethane, and the like.

These reducing agents represented by Monna (VT) and (■) are:
By selecting a photopolymerization initiator, a polymerized image with good contrast can be formed.

For example, as a reducing agent, 4,4'-methylenebis(2-
When using methyl-6-t-butylphenol), 4.4°-methylenebis(2.6-di-L-butylphenol), etc., a photopolymerization initiator sensitive to 380 nm to 390 nm, such as 2-chlorothioxanthone, 2
-Methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2, 4.
6-) Limethylbenzoyldiphenylphosphine oxide, benzyl and the like are preferred.

In addition, as a reducing agent, 4,4°-methylenebis(2-methyl-1-naphthol), 4,4°-methylenebis(2-
ethyl-1-naphthol), 4,4°-methylenebis(
When using a photopolymerization initiator sensitive at 400 nm to 500 nm, such as 2,4-cyclothioxanthone, camphorquinone, 3.3°-carbonylbis(7- Combinations of coumarins such as dimethylaminostyryl) and tris(trichloromethyl)triazine, 2-(p-dimethylaminostyryl)-4.5-diphenylthiazole and 3-
A combination with phenyl-5-isoxacilone, a combination of a merocyanine dye and 3-phenyl-5-isoxacilone, etc. are preferred.

The preferred blending ratio of the above components in the lithographic printing plate precursor suitably used in the present invention is as follows.

Preferably 0.001 to 2 mol of photosensitive silver halide, more preferably 0.05 mol to 1 mol of organic silver salt.
It is desirable to contain mol to 0.4 mol. In addition, the reducing agent is preferably 0.2 to 3 moles per mole of the organic silver salt.
It is desirable to contain it by mole, more preferably from 0.7 mole to 1.3 mole. The amount of the polymerizable compound is 10 to 1000 parts by weight, more preferably 20 parts by weight, per 100 parts by weight of the organic silver salt.
It is desirable to contain up to 500 parts by weight. It is desirable to use the photopolymerization initiator in an amount of 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polymerizable compound.

In addition, photochromic inhibitors, solid latent arc surfactants, antistatic agents, and the like may be added to the lithographic printing plate precursor, if necessary. Further, the shape of the lithographic printing plate precursor and the thickness of the photosensitive layer or the two layers of photosensitive layer/polymer layer are the same as described above.

Next, the lithographic printing plate of the present invention will be explained.

In the lithographic printing plate of the present invention, the surface of the layer containing at least a polymerizable compound and a polymerization initiator is composed of an image-like smooth part and a rough part, and at least the smooth part is formed by polymerization of the polymerizable compound. and/or a crosslinked cured product.

Depending on the shape of the unevenness on the rough surface of the lithographic printing plate, it is possible to create a so-called capillary state. In this case, when water is applied to the unevenness, the water is absorbed by capillary action, resulting in an ice detection state. Further, the smooth portion of the lithographic printing plate can have a high surface energy depending on the appropriate formulation of the polymerizable compound, and in this case becomes water repellent. Specifically, for example, if a polymerizable compound is formulated so that the smooth part has a contact angle of 70 to 90 degrees with water, the rough part will have a force τ of 40 to 20 degrees, which varies depending on the rough surface condition. It is possible to form a rough surface that lowers the contact angle to .

In this way, lithographic printing becomes possible by providing a difference in water wettability between the smooth portion and the rough surface portion. Furthermore, since the lithographic printing plate of the present invention is a cured product obtained by polymerizing and/or crosslinking a polymerizable compound, it has excellent printing durability.

F When performing lithographic printing using the lithographic printing plate of the present invention, it is sufficient to use an ordinary lithographic printing machine, while an offset printing machine used for light printing, a desk-top offset printing machine, etc. are suitable. . As the ink used here, a lipophilic ink can be used.

Lipophilic ink is an ink composed of dyes and pigments, resin, latent arc plasticizer, etc. Examples of the oil include vegetable oil, mineral oil, and the like. As a resin,
Examples include natural resins such as rosin and Shichilac, and synthetic resins such as phenolic and ketone resins.

The solvent is preferably a solvent that has appropriate dissolving power and diluting power for the resin contained in the ink, has a desired evaporation rate, and can provide the necessary viscosity and fluidity to the entire ink. Examples of such solvents include aliphatic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as toluene, esters such as methyl acetate and ethyl acetate, alcohols such as methyl alcohol and ethyl alcohol, and acetone. , ketones such as methyl ethyl ketone,
Various solvents such as glycols such as ethylene glycol, propylene glycol, and dipropylene glycol, glycol ethers, and glycol ether esters can be used. Moreover, these can also be mixed and used according to desired characteristics.

Plasticizers impart flexibility, pliability, and cold resistance to the dried ink film, and include phthalate esters such as dibutyl phthalate and dioctyl phthalate, esters such as adipic acid and citric acid, and chloride. Paraffin, castor pond, epoxy plasticizer, polyester plasticizer, etc. are used.

Examples of dyes and pigments include inorganic or organic pigments such as titanium oxide, carbon black, bronze powder, diazo yellow, and phthalocyanine blue. Further, as a powder colored developer other than dyes and pigments, for example, a powder in which dyes and pigments or metal powders are dispersed in a polymer compound such as polystyrene can be used. The average particle size of the dyes and pigments and other powdered color developers is preferably 0.1
μm-20, un, preferably 1 μm to 5 μm.

Furthermore, it is also possible to print using hydrophilic inks without using fountain solutions/oleophilic inks;
It is a water-soluble ink containing a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, or polyacrylamide, an auxiliary agent such as a surfactant, and water as a solvent.

When dampening water and lipophilic ink or hydrophilic ink are supplied to the predetermined dampening water reservoir and ink fountain of a lithographic printing plate, the lithographic printing plate of the present invention is mounted on the plate cylinder, and the printing press is operated, the dampening water is supplied. When water and lipophilic ink are used, due to the difference in wettability (contact angle) between the rough and smooth parts of the lithographic printing plate, the rough part becomes wet with dampening water, and the dampening water and lipophilic ink Due to the repulsion, the lipophilic ink does not adhere to the rough areas, but only to the smooth areas. This is transferred to a blanket, and then transferred to a sticky plastic film, etc. for printing. When a hydrophilic ink is used, the hydrophilic ink adheres only to the rough surface where the contact angle is low, and this is applied to the blanket as described above.
Adhesive Printed by transferring to plastic film, etc.

Furthermore, the present invention can be used not only as a lithographic printing plate but also as a projection image by taking advantage of the light reflecting and scattering properties of the rough surface. In this case, a gradation mask having a semi-transparent part such as a photographic negative film may be used as the mask for the above-mentioned image exposure, and if such a mask is used, gradation polymerization will be carried out accordingly. A tonally polymerized latent image is formed. A gradationally polymerized latent image is a gradationally polymerized latent image with a difference in hardness, and when this latent image is subjected to surface roughening treatment, a rough surface with gradationally unevenness is formed. That will happen. That is, a rough surface with different degrees of unevenness is formed corresponding to the gradation of the mask. The degree of light scattering and diffraction varies depending on the shape of the rough surface, and although it is possible to obtain images with gradation even when using ordinary lighting, images with gradation can be obtained using an overhead projector (OHP) or slide device.
(By simply performing general projection, it is possible to obtain an image with even more emphasized gradation on the screen.

Furthermore, when a Schlieren optical system is applied to this image, a higher contrast can be obtained, making the image even more desirable.

〔Example〕

The present invention will be explained below in more detail with reference to examples. The present invention is not limited in any way by these examples. Moreover, in the following description, "parts" represent parts by weight.

Examples Topolybutyral resin 1 part (trade name: Esletku BM-5, manufactured by Tanemizu Chemical Industry Co., Ltd.) Dipentaerythritol hexaacrylate 1 part (trade name: Kayarad DPHA, Nippon Kayaku Corporation)
)・2.4-diethylthioxanthone 0.
2 parts (product name: Kayacure DETX, manufactured by Nippon Kayaku)・Ethyl 4-dimethylaminobenzoate 0.
2 parts (trade name: Kayacure EPA, manufactured by Nippon Kayaku Masu) / 16 parts of methyl ethyl ketone Prepare a solution having the above composition, and apply the solution on a 50 μm thick polyester film to a dry film thickness of 4 μm.
A lithographic printing plate precursor was obtained by coating with an applicator, and then a negative image was placed on the lithographic printing plate precursor as a mask and exposed from the negative image side to form a polymerized latent image. The actual exposure was carried out for 0.5 seconds using a fluorescent lamp with a fluorescence peak at 380 nm as a light source with the light source 3 cm away from the lithographic printing plate precursor, and at the same time a thermal bias of 105°C was applied to promote polymerization. The negative image is peeled off from the original plate, and then the surface is roughened by anodic oxidation (average depth 1 μm, center line average roughness 0.5 μm, average aperture diameter 4 μm).
m) 0, 24mm thick aluminum plate ~1
Example 2 - Phosphoric acid dimethacrylate 0.2 part (trade name Kayamer PH-2, (manufactured by Nippon Kayaku), polybutyral resin 1 part (product name, S-LEC BL-2, manufactured by Tanemizu Chemical Industry ■), trimethylolpropane triacrylate 0.7 part (product name: N
K varnish f Le A-TMPr.

(manufactured by Shin Nakamura Chemical Industry ■) ・Benzyl methyl ketal 0.1 part (trade name, Irgacure 651, manufactured by Ciba Geigy) ・n-
Butanol 16 parts A solution having the above composition was prepared, and the solution was coated on an aluminum plate in the same manner as in Example 1 to obtain a lithographic printing plate precursor. Using a fluorescent lamp with a fluorescence peak at
After forming a polymerized latent image by applying a thermal bias of In order to improve the transferability of the surface, heat the surface to approximately 50°C while applying a blob pressure of ~1 kg/Cm2) →Additionally, expose the entire surface to the polymer for 0.2 seconds in the same manner as above. A lithographic printing plate of the present invention was obtained.

The contact angle of this lithographic printing plate with water was measured using a contact angle measuring device (
This lithographic printing plate was measured using a tabletop offset printing machine (product name: Sun Offset, manufactured by San Printing Machinery), and the angle was 90° for the smooth portion and 32° for the rough surface. ) Attempt to print by attaching it to a plate cylinder , Example 3 in which good printed matter was obtained・Silver bromide 0.7 part・
Silver behenate 4.5 parts, behenic acid 2.5 parts, phthalazinone 1.0 parts, 4.4°-
Methylenebis 3.2 parts (2-methyl-1-naphthol) - Polyvinyl butyral resin 5 parts (product name: S-LEC BM-5, manufactured by Tanemizu Chemical Industry Co., Ltd.) - Acrylic resin 5 parts (product name:
Dianal BR-105, manufactured by Mitsubishi Rayon■) ・10 parts of polyvinyl butyral-acrylic acid adduct (acryloyl group addition rate 26.7 molχ) ・15 parts of dipentaerythritol hexaacrylate (trade name: Kayarad DPIA, manufactured by Nippon Kayaku ■) )・3,3′-carbonylbis(7-dinithylaminocoumarin) 0.3 parts・Ethyl 4-dimethylaminobenzoate o, 2 parts (trade name: Kayacure EPA, manufactured by Nippon Kayaku ■)・Toluene/isopropylene Weigh out 150 parts of Patur (7:3) in a dark room, thoroughly dissolve and mix using a paint shaker, and apply the solution to a 50 μm thick polyester film with an applicator so that the dry film thickness is 5 μm. Next, a lithographic film was placed on the original plate and irradiated with a tungsten lamp from a distance of 5 cm for 2 seconds, the image-exposed lithic film was removed, and heat developed. Using a machine at 120℃, 20
It passed through the lithographic printing plate master in seconds. Then heat it to 55℃
Place it on a hot plate heated to
After forming a polymerized latent image, the surface was roughened by anodic oxidation (average depth 1 μm, center line average roughness 0.5 μm, average aperture diameter 4 μm).
A lithographic printing plate of the present invention was obtained by pressing a 24 mm thick aluminum plate against an original plate on which a polymerized latent image was formed at a pressure of ~1 kg/c+n2.

Example 4 - Silver bromide 0.7 parts - Silver behenate 4.5 parts - Behenic acid 2.5 parts - Phthalazinone 1.0 parts - 4,4'-methylenebis 3.2 parts (2,6-7- Butylphenol/polyvinyl butyral resin 7.5 parts (
Product name: S-LEC BL-λ manufactured by Tanemizu Chemical Industry ■) Acrylic resin 7.5 parts (product name: Dianal BR-93, manufactured by Mitsubishi Rayon) ・Trimethylolpropane triacrylate 20 parts (product name: NK
Ester A-TMPr, manufactured by Shin Nakamura Chemical Co., Ltd.), phosphoric acid dimethacrylate 3 parts (product name: Kayamer PM-λ, manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone 0.2 parts (product name: Kayacure DETX, Nippon Kayaku ■), 0.2 parts of ethyl 4-dimethylaminobenzoate (product name: Kayacure EPA, manufactured by Nippon Kayaku ■), 150 parts of xylene/n-butanol (7:3), and the above combination in a dark room. Weigh it out, thoroughly dissolve and mix using a paint shaker, and then add a solution of 0.0012 parts of the sensitizing dye compound represented by the pattern shown below in 1.0 parts of N,N-dimethylformamide to the above solution. added to the dispersion.

CM2C0O)i Next, this dispersion was coated on an aluminum plate with a dry film thickness of 5 μm.
Further, a 6 μm thick polyester film was laminated on the coated film to obtain the lithographic printing plate precursor of the present invention.
Laser beam printer (LBPP, manufactured by Tsuba Sekkei)
He-Ne laser (wavelength 633 nm/output 5
After that, the image was directly written on the plate using a heat developing machine for 120'Cl2O seconds, and then it was placed on a hot plate heated to 55°C to produce a fluorescence peak at 380nm. The original plate was peeled off from the laminated polyester film on which a polymerized latent image had been formed by irradiating it with a fluorescent lamp with a 3cm diameter for 3 seconds from a distance of 3cm, and a polyester matte film (average depth of 3μm, average centerline roughness of 1.3μm) was removed. In order to improve the transferability of the rough surface between the wrapped roll and the nip roll, we apply a lub pressure of 1 to 1 ℃ while heating it to about 50℃.
kg-cm2), and was further exposed to light for 0.2 seconds in the same manner as above to obtain the planographic printing plate of the present invention which was entirely polymerized.The contact angle of this planographic printing plate with water was measured using a contact angle measuring device (
This lithographic printing plate was measured using a tabletop offset printing machine (product name: Sun Offset, manufactured by San Printing Machinery) and was 88" for the smooth portion and 32" for the rough surface. ) Attempt to print by attaching it to a plate cylinder [Effects of the Invention] As explained above, by the method for producing a lithographic printing plate of the present invention, a lithographic printing plate that is simple, quick, reproducible, and stable by dry processing can be produced. In addition, if the photosensitive layer of the lithographic printing plate precursor contains photosensitive silver halide, highly sensitive writing is possible, and plate making can be performed by direct drawing writing with a laser (laser plate making). It is possible. Furthermore, since the lithographic printing plate of the present invention is a lithographic printing plate made of a cured product obtained by polymerizing and/or crosslinking a polymerizable compound, printing durability is also preferable.

Furthermore, the lithographic printing plate of the present invention also has the effect that it can be used as an image for projection.

[Brief explanation of drawings]

1 to 3 are schematic cross-sectional views showing aspects of each process of the method for manufacturing a lithographic printing plate of the present invention. 1. Support 7. Conductor 2. Polymerization layer 8. Photoconductor 2-a. Polymerization part
9...Photosensitive layer 2-b...Unpolymerized part 9-a
...Exposed area 3... Planographic printing plate master 9-b... Unexposed area 4... Oxygen barrier layer 10... Silver nucleus 5... Negative mask 11... Silver atom 6 - Rough surface forming medium 12... Oxidant r1ゝ）”

Claims (1)

[Claims] 1. For a lithographic printing plate precursor having at least a polymerizable compound and a polymerization initiator, (a) the polymerizable compound is site-selectively polymerized to separate the polymerized and unpolymerized areas. (b) roughening the unpolymerized area; and (c) polymerizing the roughened unpolymerized area. How to make the plate. 2. For a lithographic printing plate precursor containing at least a photosensitive silver halide, an organic silver salt, a reducing agent, a polymerizable compound, and a photopolymerization initiator, (a) a process of imagewise exposure; (b) heating the master plate; (c) a process of exposing the entire surface of the original plate to polymerize the polymerizable compound to form a polymerized latent image consisting of a polymerized part and an unpolymerized part; (d) roughening the unpolymerized part. (e) polymerizing the roughened unpolymerized areas. 3. The surface of the layer containing at least a polymerizable compound and a polymerization initiator consists of an image-like smooth portion and a rough surface portion, and at least the smooth portion is a cured product obtained by polymerization and/or crosslinking of the polymerizable compound. A lithographic printing plate featuring.