JP5639378B2 - Printing method of heat-sensitive lithographic printing plate - Google Patents

Description

  The present invention relates to a method for printing a thermal lithographic printing plate.

  With the recent development of computers and peripheral devices, a planographic printing plate making method using various digital printers has been proposed. As a plate making method of such a lithographic printing plate, for example, plate making with a dry electrophotographic laser printer as described in JP-A-6-138719, JP-A-6-250424, etc., JP-A-9- Making a plate using an on-demand ink jet printer using a hot-melt ink as described in Japanese Patent No. 58144, or making a plate using a thermal printer using a thermal transfer ink ribbon as described in Japanese Patent Laid-Open No. 63-166590 Things to do are known.

  The plate making method by the above various digital printers is different from the conventionally known plate making method of a lithographic printing plate having a silver halide emulsion layer, or the plate making method of a lithographic printing plate in which a photosensitive resin is applied to the surface of the water retention layer, There is an advantage that a lithographic printing plate can be made easily and easily because there is no restriction of safe light for handling and no development processing with an alkali developer is required after image recording.

  However, all the printing plates described above form a printing plate by transferring a grease-sensitive (that is, lithographic printing ink fillability) recorded image to the surface of a support provided with a water retention layer. There are the following problems.

1) Since a layer for forming an image is hydrophilic, adhesion of toner, ink or the like is not sufficient. For example, there are problems such as insufficient transfer toner image density and whiteout transfer image.
2) The transfer image is not sufficiently fixed and the printing durability is insufficient. In particular, there are problems such as omission of part of small point characters and small dots of halftone dot images.
3) A small amount of toner is irregularly transferred to the non-image area or the thermal transfer ink ribbon is rubbed, thereby causing problems such as generation of thin print stains as a whole.

  In order to solve the above problem, there has been proposed a heat-sensitive lithographic printing plate capable of directly forming an image with a thermal head or the like without using a thermal transfer ribbon or the like, for example, Japanese Patent Application Laid-Open No. 58-199153 (Patent Document 1) or Japanese Patent Application Laid-Open No. Direct thermal lithographic plate capable of forming an image portion by bringing a water-soluble polymer compound and a heat-meltable material described in JP-A-174395 (Patent Document 2) and the like into contact with a thermal head or the like in an image forming layer An image-forming layer comprising a photothermal conversion substance and heat-meltable particles or a thermoplastic polymer described in a printing plate, for example, JP-A No. 2000-190649 (Patent Document 3), JP-A No. 2000-301847 (Patent Document 4), etc. Heat-sensitive lithographic printing plates and the like that are capable of forming an image portion by being irradiated with an infrared laser and heated in an image-like manner are known. In forming the non-image part of these heat-sensitive lithographic printing plates, there are a type in which the non-heated part is removed with an aqueous liquid such as dampening water and a type in which the non-image part is not removed.

  However, such heat-sensitive lithographic printing plates generally have a difference in hydrophilicity / lipophilicity between the non-image area and the image area, so that it is difficult to obtain a clear printed image and the printing durability is insufficient. Or a background stain (print stain) is likely to occur.

  As a heat-sensitive lithographic printing plate from which a clear image having a high image density can be obtained, for example, inorganic pigments, thermoplastic resins and hot-melt materials as described in JP-A-63-64747 (Patent Document 5) are used. A heat-sensitive lithographic printing plate having an image forming layer is known. Further, the thermosensitive lithographic printing plate described in Patent Document 3 and Patent Document 4 described above contains heat-melting fine particles that exhibit lipophilicity in order to improve the balance between the lipophilicity of the image area and the hydrophilicity of the non-image area. A method of coating with a substance having a specific thermal conductivity and a device for hydrophobizing hydrophilic groups of a hydrophilic polymer using a chelate reaction by heat are disclosed. However, it is difficult to control the reaction in any case, and the difference in hydrophilicity / lipophilicity between the non-image area and the image area has not reached a satisfactory level. Therefore, even in such a method, the problem has not been solved yet in terms of clear printed images, printing durability, and printing stains.

  On the other hand, as a method for imparting hydrophilicity to a non-image portion of a lithographic printing plate with respect to the problem of printing smearing, a plate surface treatment solution of JP-A-5-289341 (Patent Document 6) and JP-A-7-56349 have been disclosed. Plate surface processing liquid (Patent Document 7), fixing agent disclosed in Japanese Patent Publication No. 45-29001, neutralizing liquid disclosed in Japanese Patent Publication No. 61-28987 (Patent Document 8), and inorganic surface particles such as a desensitizing liquid. A method using a liquid is known.

  On the other hand, in addition to the above-mentioned problems such as printing durability and printing stains, there are problems such as fingerprint stains and missing fingerprints as general problems of lithographic printing plates. That is, as described in JP-A-2005-97546, JP-A-2006-18308, JP-A-2008-250198, and JP-A-2009-083106, during the work from plate making to printing. When touching the plate surface of the printing plate with a hand, there is a problem that fingerprint-like printing stains occur in the case of non-image areas (fingerprint stains). There is (fingerprint missing). This problem can be avoided if the plate surface of the printing plate is not touched, but the efficiency of plate making and printing operations is significantly reduced. Although fingerprint smudges and missing fingerprints are fundamentally caused by the difference in hydrophilicity / lipophilicity between the non-image area and the image area, there are various causes, and in particular, the above-mentioned thermal lithographic printing plate is a difficult problem to solve. Met.

JP 58-199153 A JP 59-174395 A JP 2000-190649 A Japanese Patent Laid-Open No. 2000-301846 JP-A 63-64747 JP-A-5-289341 JP 7-56349 A Japanese Patent Publication No. 61-28987

  An object of the present invention is to provide a printing method for a heat-sensitive lithographic printing plate having an image forming layer containing at least a thermoplastic resin and a water-soluble polymer compound on a water-resistant support, in which fingerprint smearing and fingerprint omission are improved. Is to provide a method.

  The object of the present invention is to form an image portion by imagewise heating an image forming layer of a lithographic printing plate having an image forming layer containing at least a thermoplastic resin and a water-soluble polymer compound on a water-resistant support. And then performing printing after applying a plate surface treatment solution containing at least one kind of inorganic fine particles and a saccharide having a polymerization degree of 4 or less to the plate surface before starting printing. it can.

  According to the present invention, in a printing method of a heat-sensitive lithographic printing plate having an image forming layer containing at least a thermoplastic resin and a water-soluble polymer compound on a water-resistant support, printing with improved fingerprint stain and fingerprint omission It becomes possible to provide a method.

  The heat-sensitive lithographic printing plate according to the present invention has an image forming layer containing at least a thermoplastic resin and a water-soluble polymer compound on a water-resistant support. When such heat-sensitive lithographic printing plate images are heated, the heat-melting fine particles contained in the portion are melted together with the water-soluble polymer compound, and the heated portion becomes hydrophobic as a whole. It is supposed to convert. Accordingly, since the portion to which heat is applied is converted into hydrophobicity, it becomes possible to receive ink at the time of printing. However, even in the unheated part forming the non-image part, hydrophobic heat-melting fine particles are present, and this inventor believes that this is a cause of fingerprint smearing easily occurring in the non-image part. Estimated. When a plate surface treatment liquid containing inorganic fine particles is applied to the plate surface before the start of printing, fingerprint smearing is reduced, but this alone is still insufficient.

  On the other hand, the reason for the image portion is not clear, but depending on the printing conditions and the type of ink, it is easy for missing fingerprints to occur. In particular, when a plate surface treatment liquid containing inorganic fine particles is applied to the plate surface before the start of printing in order to improve fingerprint smearing in the non-image area, the phenomenon of fingerprint loss is significant, and the content of inorganic fine particles in the plate surface treatment liquid The larger the number, the worse the fingerprint loss. As described above, it has been difficult to solve the phenomenon of fingerprint smearing and fingerprint omission in the prior art. The present inventors have found a printing method capable of simultaneously solving fingerprint smearing and fingerprint omission by applying one type of plate surface treatment liquid to the plate surface.

  The plate surface treatment liquid used in the present invention will be described. The inorganic fine particles contained in the plate surface treatment liquid used in the present invention are preferably those having a particle diameter of 0.1 μm or less that can be easily dispersed and stabilized in water. Examples of such inorganic fine particles include fine particles of silica, alumina, zirconia, titania, and the like, but silica fine particles and alumina fine particles are particularly preferable in preventing printing stains. Among them, colloidal silica is most preferable. For example, from Nissan Chemical Industries, Snowtex XS, Snowtex XL, Snowtex YL, Snowtex ZL, Snowtex MP-2040, Snowtex C, etc. It is commercially available as a dispersion of various inorganic fine particles from Nissan Chemical Industries, Ltd. under the trade names such as alumina sol 100 and alumina sol 520.

  When the concentration of the inorganic fine particles is too high, fingerprint loss is likely to occur as described above, and when the concentration is too low, it is difficult to obtain the effect of imparting hydrophilicity. May become clogged and fingerprint smudges may occur. Therefore, the plate surface treatment liquid used in the present invention preferably contains 1 to 50 g / L of inorganic fine particles (as oxide). More preferably, it is the range of 2-30 g / L.

  The saccharide having a polymerization degree of 4 or less used in the plate surface treatment liquid of the present invention is a monosaccharide composed of 2 to 4 monosaccharides or glycoside bonds. The monosaccharide is preferably a pentose or hexose. If the degree of polymerization is too large, the number of printed sheets until the missing of the fingerprint in the image portion becomes invisible increases, so it is 4 or less, preferably 3 or less. Moreover, it is preferable that saccharides having a polymerization degree of 4 or less do not have a substituent such as a carboxyl group, an amino group, or an ester group. In addition, the sugar alcohol obtained by hydrogenation is included in this invention.

  Specific examples of saccharides having a polymerization degree of 4 or less used in the plate surface treatment liquid of the present invention include arabinose, ribose, xylose, allose, galactose, glucose, mannose, talose, fructose, tagatose, sorbose, sucrose, lactose, maltose, isorose Examples include maltose, inulobiose, trehalose, maltotriose, xylitol, sorbitol, maltitol, and reduced water candy. These saccharides may be used alone or in combination of two or more. If the amount of these saccharides is too small, the effect is weakened. Therefore, the preferable content is 1 g / L or more, and the more preferable amount is 5 g / L or more. There is no particular upper limit on the content, but 100 g / L or less is appropriate for economic reasons.

  The plate surface treatment liquid used in the present invention preferably contains a high-boiling water-soluble organic solvent in addition to inorganic fine particles and saccharides having a polymerization degree of 4 or less. As the high-boiling water-soluble organic solvent, it is preferable to use a polyol compound or a glycol derivative. Examples of the polyol compound include ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol and the like. Examples of the glycol derivative include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 200 to 600), dipropylene glycol, tripropylene glycol, a copolymer of ethylene oxide and propylene oxide, and the like. Furthermore, alkyl ethers of these compounds such as methyl, ethyl, propyl and butyl can be mentioned. The content of these high-boiling water-soluble organic solvents is preferably in the range of 1 to 200 g / L, more preferably in the range of 5 to 100 g / L.

  The plate surface treatment liquid used in the present invention can contain a surfactant for adjusting the surface tension in consideration of the impartability to the plate surface.

  The plate surface treatment liquid used in the present invention preferably has a pH adjusted to 3 to 8, more preferably a pH range of 4 to 7. Buffering agents can be included to adjust to these pH ranges. Examples of the pH buffer include weak acids such as phosphoric acid, acetic acid, succinic acid, citric acid, tartaric acid, malic acid and gluconic acid and salts thereof, and weak bases such as diethanolamine and triethanolamine and salts thereof.

  The plate surface treatment liquid used in the present invention can contain a chelating agent for the dissolution stability of polyvalent metal salt, prevention of aggregation of inorganic fine particles, and other reasons. As the chelating agent, aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and salts thereof, and hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, gluconic acid, and salts thereof can be used. In addition, aminopolyphosphonic acids and salts thereof, hydroxyphosphonic acids and salts thereof, polyphosphoric acid and salts thereof can also be used.

  Furthermore, the plate surface treatment liquid used in the present invention may contain a preservative, a preservative, a colorant, a rust preventive agent and the like in addition to the compound.

  In the printing method of the present invention, the above-mentioned plate surface treatment liquid is applied to the plate surface before starting printing, and as this method, a method of impregnating the surface treatment solution with absorbent cotton or the like and performing hand etching, a certain amount of plate surface treatment Applying the liquid to the plate surface with a bar coater, or using an etching converter that immerses the printing plate in a liquid bath storing the plate surface processing solution and squeezes the excess plate surface processing solution with a roll pair, etc. it can. The timing of applying the plate surface treatment liquid to the printing plate may be any time as long as it is after image formation until printing. However, printing is usually performed after the printing plate is mounted on the printing machine (plate printing). This is done until it starts or just before printing.

  Next, the heat-sensitive lithographic printing plate according to the present invention will be described in detail. As a method for forming an image portion of such a heat-sensitive lithographic printing plate, a direct heat-sensitive type in which the image forming layer is heated in an image-like manner by directly contacting means such as a thermal head, or a photothermal conversion agent is further added to the image forming layer. And a photothermal conversion type in which heating is performed by exposing in an image-like manner. In addition, as a method for forming the non-image area, a water retention layer containing inorganic fine particles typified by colloidal silica and the image forming layer are provided in this order on a water-resistant support. After obtaining an image by the forming method, the image is developed with a developer, or developed on a printing machine, and the wet-heating type in which an unheated portion (non-image portion) of the image forming layer is removed, or a water retention layer There is a dry type in which an unheated portion (non-image portion) after image formation is provided as it is as a portion for imparting water retention. Among them, the direct heat-sensitive image forming type is preferable in that an image portion having high energy transmission efficiency and excellent oleophilicity and printing durability is obtained, and is a dry type in that waste liquid is not generated in development processing. It is preferable.

  Further, even if it is a dry type thermosensitive lithographic printing plate, it may of course be composed of only a single layer, and a hydrophilic layer including a thermosensitive coloring layer or hydrophilic inorganic fine particles for obtaining visibility as a lower layer. A layer for improvement and an undercoat layer may be provided.

  The heat-sensitive lithographic printing plate used in the present invention has an image forming layer containing at least a thermoplastic resin and a water-soluble polymer compound. Any water-soluble polymer compound possessed by the image forming layer can be used as long as it retains water during printing and has a binder element that can exist as a layer. Specific examples include the following.

  Natural products include starches and derivatives thereof, seaweed mannan, agar, and algae such as sodium alginate, mannan, pectin, tragacanth gum, karaya gum, xanthine gum, guarbin gum, locust bin gum, gum arabic, etc. Micropolysaccharides such as homopolysaccharides such as glucan, xanthan gum and levan, heteropolysaccharides such as succinoglucan, pullulan, curdlan and xanthan gum, glue, gelatin, casein, collagen and other proteins, chitin and derivatives thereof, etc. Is mentioned.

  Semi-natural products (semi-synthetic products) include celluloses such as hydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose, modified gums such as carboxymethyl guar gum, and baked starches such as dextrin, oxidized starches, and esterified starches. Modified starches and the like.

  Synthetic products include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, partially acetalized polyvinyl alcohol, modified polyvinyl alcohols such as allyl-modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl ethyl ether, Modified polyvinyl ethers such as polyvinyl isobutyl ether, polyacrylic acid salts, polyacrylic acid ester partial saponified products, polymethacrylic acid salts, polyacrylic acid derivatives such as polyacrylic acid and polymethacrylic acid derivatives, polyethylene glycol, polyethylene oxide, Polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, carboxyvinyl polymer, styrene / maleic acid copolymer , Styrene / crotonic acid copolymer, include water-soluble polymers exemplified in P1~P24 described in JP 2006-247937.

  These water-soluble polymer compounds may be used alone or in combination of two or more. Particularly, gelatin and polyvinyl alcohol rich in film formation and modified products thereof are preferably selected for maintaining the hydrophilicity of the non-image area. The blending amount is preferably 0.5 to 30% by mass, more preferably 3 to 25% by mass with respect to the total solid content of the image forming layer. If the amount is less than 0.5% by mass, the hydrophilicity of the non-image area may not be obtained, and printing may be easily smudged. If the amount exceeds 30% by mass, the thermal sensitivity is lowered, and the oil sensitivity of the image part is lowered. In some cases, sufficient printing durability may not be obtained. Among these hydrophilic resins, gelatin, modified or unmodified polyvinyl alcohol, and cellulose derivatives can be advantageously used. In particular, the use of gelatin is preferable because of its excellent balance between water retention and strength.

  As the gelatin used for the image forming layer according to the present invention, any gelatin made from animal collagen can be used, but gelatin made from collagen obtained from pig skin, cow skin, and cow bone is preferred. The type of gelatin is not particularly limited, but in addition to lime-processed gelatin and acid-processed gelatin, JP-B-38-4854, JP-B-39-5514, JP-B-40-12237, and JP-B-42-26345. US Pat. No. 2,525,753, US Pat. No. 2,594,293, US Pat. No. 2,614,928, US Pat. No. 2,763,639, US Pat. No. 3,118, 766, U.S. Pat. No. 3,132,945, U.S. Pat. No. 3,186,846, U.S. Pat. No. 3,312,553, British Patent 1,033,189, etc. These can be used singly or in combination of two or more.

  In order to improve the water resistance and mechanical strength of the non-image area, the image forming layer preferably contains a curing agent (waterproofing agent) according to the type of the water-soluble polymer compound. As the curing agent, melamine resin, epoxy resin, polyisocyanate compound, aldehyde compound, silane compound, chromium alum, divinyl sulfone, and the like that can impart water resistance by promoting the crosslinking of the resin can be used. In some cases, for example, inorganic compounds such as chromium alum, formalins, glyoxal, malealdehyde, aldehydes such as glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, mucochloric acid, 2,3-dihydroxy-1, Aldehyde-related compounds such as 4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salts and compounds having active halogen such as 2,4-dihydroxy-6-chloro-s-triazine salts, divinyl Sulfone, divinyl ketone and N, N, N-tria One or two of various compounds such as liloyl hexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups and epoxy groups in the molecule, and dialdehyde starch as a polymer hardener It is preferable to use more than one species. In the case of polyvinyl alcohol, it is preferable to use aldehydes such as formalin, glyoxal, malealdehyde, and glutaraldehyde. Particularly preferably, in the case of gelatin, divinyl sulfone is glyoxal in the case of polyvinyl alcohol.

  The blending amount of the curing agent is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, based on the solid content of the water-soluble polymer compound, from the viewpoint of avoiding fluctuations in characteristics over time when stored. It is preferable that

  The thermoplastic resin contained in the image forming layer according to the present invention will be described. The thermoplastic resin according to the present invention is a solid organic polymer compound made of a chain polymer and exhibiting plasticity upon heating, and refers to an aqueous dispersion of the organic polymer compound. Representative examples include synthetic rubber latex including modified products such as styrene butadiene copolymer, acrylonitrile butadiene copolymer, methyl methacrylate butadiene copolymer, styrene acrylonitrile butadiene copolymer, styrene methyl methacrylate butadiene copolymer. Styrene maleic anhydride copolymer, methyl vinyl ether maleic anhydride copolymer, polyacrylic acid copolymer, polystyrene, styrene / acrylic acid ester copolymer, polyacrylic acid ester, polymethacrylic acid ester, acrylic Aqueous dispersions such as acid ester / acrylic acid ester copolymers and low melting point polyamide resins can also be used. These thermoplastic resins can be used alone or in combination of two or more. In view of the affinity with the printing ink vehicle (binder component), the thermoplastic resin is preferably a synthetic rubber latex, and in particular, a styrene-butadiene copolymer and a modified product thereof are desirable. A preferable blending amount is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass with respect to the total solid content of the image forming layer. Moreover, in order to make the melting and fusing effect due to heat easy to develop, it is preferable to use a thermoplastic resin having a glass transition temperature of 50 to 150 ° C., more preferably 55 to 120 ° C. If the glass transition temperature is less than 50 ° C., a phase change occurs in a liquid state during the production process, and oleophilicity is exhibited also in the non-image area, which may cause printing background stains. When the temperature exceeds 150 ° C., the polymer is hardly melted by heat, and it may be difficult to form a strong image with a relatively small output laser or a small thermal printer.

  The thermoplastic resin is finely divided and is solid or dispersed in water. Examples include polymer latex that can be dispersed in an aqueous solvent. Examples of the dispersed state include those in which fine particles of a water-insoluble hydrophobic polymer are dispersed, or polymer molecules that form molecular states or micelles. In any case, it can be suitably used. These average particle diameters are preferably 1 to 50000 nm, more preferably 5 to 1000 nm. The particle size distribution of the polymer latex is not particularly limited, and may be a wide particle size distribution or a monodispersed particle size distribution. By heating, they are melted or fused together to change from the fine particle form and integrate.

  These thermoplastic resins can be used as a mixture of two or more as required, or may be a plurality of layers. A resin that self-crosslinks when heated is particularly preferred. The amount of the thermoplastic resin contained in the image forming layer of the heat-sensitive lithographic printing plate according to the present invention is optimized depending on the balance with the water-soluble polymer compound used and the desired sensitivity. It is preferable to set it as 50-1000 mass parts with respect to 100 mass parts of compounds, More preferably, you may be 100-500 mass parts.

  The heat-sensitive lithographic printing plate according to the present invention preferably contains a color former in order to obtain the visibility of the image area. Specific examples of the color former (electron-donating dye precursor) include (a) 3,3′-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal) as a triarylmethane compound. Violet lactone), 3,3′-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- ( p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-Dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethyl Minophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3- (P-dimethylaminophenyl) -3- (1-methylpyrrol-2-yl) -6-dimethyl-aminophthalide and the like: (b) 4,4'-bis-dimethylaminobenzhydrin benzyl ether as a diphenylmethane compound N-halophenyl leucooramine, N-2,4,5-trichlorophenyl leucooramine, etc .: (c) as xanthene compounds, rhodamine B-anilinolactam, rhodamine Bp-nitroanilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, -Diethylamino-7-octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3-diethylamino-7- (3,4-dichloroanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-ethyl- Tolylamino-6-methyl-7-anilinofluorane, 3-ethyl-tolylamino-6-methyl-7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilino) fluorane, etc .: (d) thiazine compounds As benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue Etc .: (e) 3-methyl-spiro-dinaphthopyrans, 3-ethyl-spiro-dinaphthopyrans, 3,3′-dichloro-spiro-dinaphthopyrans, 3-benzyl-spiro-dinaphthopyrans, 3-methylnaphtho- ( 3-methoxy-benzo) -spiropyran, 3-propyl-spiro-dibenzopyran and the like. Two or more of these may be used in combination.

The layer that contains the color former may be a layer that is applied to the surface of the heat-sensitive lithographic printing plate on which the image forming layer is applied, but is preferably included in the image forming layer. The amount of the color former is optimized depending on the balance with the water-soluble polymer compound used and the desired sensitivity, but may be in the range of 0.01 to 10 g / m ² , preferably 0.1 to 1 g. / M ² .

  Further, when the heat-sensitive lithographic printing plate according to the present invention contains the above color former, the developer such as a phenol derivative or an aromatic carboxylic acid derivative is developed in order to cause the color former to be heated to develop a color. It is preferable to contain an agent. Specific examples of the developer include 4-cumylphenol, hydroquinone monobenzyl ether, 4,4'-isopropylidenediphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'- Dihydroxydiphenyl-2,2-butane, 4,4′-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) heptane, bis (4 -Hydroxyphenylthioethoxy) methane, 1,5-bis (4-hydroxyphenylthio) -3-oxapentane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,4-bis [α -Methyl-α- (4'-hydroxyphenyl) ethyl] benzene, 1,3-bis [α-methyl-α- (4'-hydride) Xylphenyl) ethyl] benzene, 4,4'-dihydroxydiphenyl sulfide, bis (4-hydroxy-3-methylphenyl) sulfine, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone 2,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenylsulfone, 4-hydroxy-3 ', 4'-tetramethylenebiphenylsulfone, 3,4-dihydroxyphenyl-p-tolylsulfone, 4,4'-dihydroxybenzophenone, benzyl 4-hydroxybenzoate, N, N'-di-m-chlorophenylthiourea, N- (Fe Phenolic compounds such as (noxyethyl) -4-hydroxyphenylsulfonamide, zinc [4- (3- (p-tolylsulfonyl) propyloxy] salicylate, 4- [2- (p-methoxyphenoxy) ethyloxy] zinc salicylate, 5- [P- (2-p-methoxyphenoxyethoxy) cumyl] Zinc salts of aromatic carboxylic acids such as zinc salicylate and zinc p-chlorobenzoate, and organic acidic substances such as antipyrine complexes of zinc thiocyanate.

The layer containing the developer is preferably contained in the same layer as the layer containing the color former, and is preferably contained in the image forming layer together with the color former. The amount of the developer is optimized depending on the balance with the water-soluble polymer compound used and the desired sensitivity, but may be in the range of 0.01 to 10 g / m ² , preferably 0.5 to 5 g / m ² .

  The image forming layer according to the present invention may further contain a photothermal conversion substance in addition to the thermoplastic resin and the water-soluble polymer compound. By including a photothermal conversion substance, writing with active light such as an infrared laser as well as a thermal head is possible. As the photothermal conversion substance, a material that efficiently absorbs light and converts it into heat is preferable. Depending on the light source used, for example, when using a semiconductor laser that emits near infrared light as the light source, Near-infrared light absorbers having an absorption band are preferable, for example, organic compounds such as carbon black, cyanine dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes, And metal compounds such as phthalocyanine-based, azo-based, and thioamide-based organometallic complexes, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide.

  The image forming layer according to the present invention preferably contains at least one selected from compounds represented by the following general formulas (1) to (4). By containing these compounds, when the surface of the image forming layer is applied with heat, the melting start temperature of the thermoplastic resin is lowered, and an image part having excellent oleophilicity on the plate surface is obtained with less energy, and a clear printed image is obtained. Sufficient printing durability can be obtained. Further, when the image forming layer is the outermost layer, sticking can be improved at the same time.

  The compound represented by the general formula (1) will be described below.

In the above formula, X ₁ represents —O— or —CO—O—, and R _{1 to} R ₆ represent a hydrogen atom, an alkyl group, and an aryl group, respectively. n shows the integer of 1-10. The substituents R _{1 to} R ₃ and R _{4 to} R ₆ may be bonded to each other to form an aromatic ring.

Among the compounds represented by the general formula (1), compounds in which X ₁ is —O— are preferable, and R ₁ and R ₆ are particularly a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R _{2 to} R _5. A compound in which is a hydrogen atom and n is an integer of 1 to 4 is particularly preferably used. A preferable compounding amount is 30 to 130% by mass, more preferably 50 to 100% by mass with respect to the thermoplastic resin. This compound may be used alone or in combination of two or more.

Examples of the compound represented by the general formula (1) include the following compounds, but the present invention is not limited thereto.
(1) 1- (1-naphthoxy) -2-phenoxyethane (2) 1- (2-naphthoxy) -4-phenoxybutane (3) 1- (2-isopropylphenoxy) -2- (2-naphthoxy) ethane (4) 1- (4-Methylphenoxy) -3- (2-naphthoxy) propane (5) 1- (2-methylphenoxy) -2- (2-naphthoxy) ethane (6) 1- (3-methylphenoxy ) -2- (2-naphthoxy) ethane (7) 1- (2-naphthoxy) -2-phenoxyethane (8) 1- (2-naphthoxy) -6-phenoxyhexane (9) 1-phenoxy-2- ( 2-Phenylphenoxy) ethane (10) 1- (2-methylphenoxy) -2- (4-phenylphenoxy) ethane (11) 1,4-bisphenoxybutane (12) 1,4-bis (4-methyl) Enoxy) butane (13) 1,2-bis (3,4-dimethylphenoxy) ethane (14) 1-phenoxy-3- (4-phenylphenoxy) propane (15) 1- (4-tert-butylphenoxy)- 2-phenoxyethane (16) 1,2-bisphenoxyethane (17) 1- (4-methylphenoxy) -2-phenoxyethane (18) 1- (2,3-dimethylphenoxy) -2-phenoxyethane (19 ) 1- (3,4-dimethylphenoxy) -2-phenoxyethane (20) 1- (4-ethylphenoxy) -2-phenoxyethane (21) 1- (4-isopropylphenoxy) -2-phenoxyethane (22 ) 1,2-bis (2-methylphenoxy) ethane (23) 1- (2-methylphenoxy) -2- (4-methylphenoxy) ethane ( 4) 1- (4-tert-Butylphenoxy) -2- (2-methylphenoxy) ethane (25) 1,2-bis (3-methylphenoxy) ethane (26) 1- (3-methylphenoxy) -2 -(4-Methylphenoxy) ethane (27) 1- (4-ethylphenoxy) -2- (3-methylphenoxy) ethane (28) 1,2-bis (4-methylphenoxy) ethane (29) 1- ( 2,3-dimethylphenoxy) -2- (4-methylphenoxy) ethane (30) 1- (2,5-dimethylphenoxy) -2- (4-methylphenoxy) ethane (31) phenoxyacetic acid-2-naphthyl ( 32) 2-naphthoxyacetic acid-4-methylphenyl (33) 2-naphthoxyacetic acid-3-methylphenyl

  Next, the compound represented by the general formula (2) will be described.

In the above formula, R ₇ represents an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. The naphthalene ring in the formula may further have a substituent, and examples of preferable substituents include an alkyl group, an aryl group, a halogen group, a hydroxy group, an alkoxy group, an aryloxy group, and an alkyloxycarbonyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group and the like.

Among the substituents represented by R ₇ in the general formula (2), an alkyl group having 4 to 20 carbon atoms, an aryl group having 4 to 24 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, and a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group is more preferred. In the general formula (2), among the substituents that the naphthalene ring may further have, a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, or a 7 to 20 carbon atom. An aryloxycarbonyl group and a carbamoyl group having 2 to 25 carbon atoms are more preferable. A preferable compounding amount is 30 to 130% by mass, more preferably 50 to 100% by mass with respect to the thermoplastic resin. This compound may be used alone or in combination of two or more.

Examples of the compound represented by the general formula (2) include the following compounds, but the present invention is not limited thereto.
(1) 1-benzyloxynaphthalene (2) 2-benzyloxynaphthalene (3) 2-p-chlorobenzyloxynaphthalene (4) 2-p-isopropylbenzyloxynaphthalene (5) 2-dodecyloxynaphthalene (6) 2 Decanoyloxynaphthalene (7) 2-Myristoyloxynaphthalene (8) 2-p-tert-butylbenzoyloxynaphthalene (9) 2-Benzoyloxynaphthalene (10) 2-Benzyloxy-3-N- (3-dodecyl Oxypropyl) carbamoylnaphthalene (11) 2-benzyloxy-3-N-octylcarbamoylnaphthalene (12) 2-benzyloxy-3-dodecyloxycarbonylnaphthalene (13) 2-benzyloxy-3-p-tert-butylphenoxy Carbonyl naphthalene

  Next, the compound represented by the general formula (3) will be described.

In the above formula, R ₈ and R ₉ represent a hydrogen atom, a halogen group, an alkyl group having 4 or less carbon atoms, or an alkoxy group. X ₂ represents a simple bond or —O—, and n represents an integer of 1 to 4.

Examples of the compound represented by the general formula (3) include the following compounds, but the present invention is not limited thereto.
(1) dibenzyl oxalate (2) bis (p-methylbenzyl) oxalate
(3) Bisoxalate (p-chlorobenzyl)
(4) Bisoxalate (m-methylbenzyl)
(5) Bisoxalate (p-ethylbenzyl)
(6) Bisoxalate (p-methoxybenzyl)
(7) Bisoxalate (2-phenoxyethyl)
(8) Bis oxalate (2-o-chlorophenoxyethyl)
(9) Bis oxalate (2-p-chlorophenoxyethyl)
(10) Bis-oxalate (2-p-ethylphenoxyethyl)
(11) Bisoxalate (2-m-methoxyphenoxyethyl)
(12) Bisoxalate (2-p-methoxyphenoxyethyl)
(13) Bis-oxalate (4-phenoxybutyl)

  Among these exemplified compounds, preferred specific examples include dibenzyl oxalate, bis (p-methylbenzyl) oxalate, bis (p-chlorobenzyl) oxalate, bis (m-methylbenzyl) oxalate, and bisoxalate. (P-ethylbenzyl) and bis (p-methoxybenzyl) oxalate. A preferable compounding amount is 30 to 130% by mass, more preferably 50 to 100% by mass with respect to the thermoplastic resin. This compound may be used alone or in combination of two or more.

  The compound represented by the general formula (4) will be described below.

In the above formula, R ₁₀ , R ₁₀ ′, R ₁₁ and R ₁₁ ′ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, or an aryloxy group. .

Examples of the compound represented by the general formula (4) include the following compounds, but the present invention is not limited thereto.
(1) 1,2-bisphenoxymethylbenzene (2) 1,3-bisphenoxymethylbenzene (3) 1,4-bis (2-methylphenoxymethyl) benzene (4) 1,4-bis (3-methyl Phenoxymethyl) benzene (5) 1,3-bis (4-methylphenoxymethyl) benzene (6) 1,3-bis (2,4-dimethylphenoxymethyl) benzene (7) 1,3-bis (2,6 -Dimethylphenoxymethyl) benzene (8) 1,4-bis (2-chlorophenoxymethyl) benzene (9) 1,2-bis (4-chlorophenoxymethyl) benzene (10) 1,3-bis (4-chloro Phenoxymethyl) benzene (11) 1,2-bis (4-octylphenoxymethyl) benzene (12) 1,3-bis (4-octylphenoxymethyl) benzene 13) 1,3-bis (4-isopropylphenyl phenoxymethyl) benzene (14) 1,4-bis (4-isopropylphenyl phenoxymethyl) benzene

  Preferred examples among these exemplary compounds include 1,2-bisphenoxymethylbenzene, 1,4-bis (2-methylphenoxymethyl) benzene, 1,4-bis (3-methylphenoxymethyl) benzene, 1,4-bis (2-chlorophenoxymethyl) benzene may be mentioned. A preferable compounding amount is 30 to 130% by mass, more preferably 50 to 100% by mass with respect to the thermoplastic resin. This compound may be used alone or in combination of two or more.

  Among the compounds represented by the general formulas (1) to (4), the compounds represented by the general formulas (1), (2), and (4) are preferable in that excellent printing durability can be obtained. The compounds represented by (1) and (2) are preferred, and the most preferred compound is the compound represented by the general formula (1). These may be used alone or in combination.

  The compounds represented by the above general formulas (1) to (4) are substances that are solid at room temperature, but are preferably used after being subjected to fine dispersion treatment in order to increase the reactivity with heat. As a fine dispersion treatment method, a bead mill such as a roll mill, a colloid mill, a ball mill, an attritor, a sand mill, or the like, which is a wet dispersion method generally used at the time of coating production, can be used. In the bead mill, ceramic beads such as zirconia, titania and alumina, metal beads such as chrome and steel, and glass beads can be used. The dispersed particle diameter is preferably from 0.1 to 1.2 μm in median diameter, particularly preferably from 0.3 to 0.8 μm.

  For the purpose of preventing the sticking phenomenon, a heat-meltable substance may be used in the layer constituting the surface on the image drawing side of the heat-sensitive lithographic printing plate according to the present invention. As the hot-melt material, an organic compound having a melting point of 50 to 150 ° C. is preferable. For example, waxes such as carnauba wax, microcrystalline wax, paraffin wax, polyethylene wax, lauric acid, stearic acid, oleic acid, palmitic acid, behen Acids, fatty acids such as montanic acid, and esters and amides thereof can be used.

  The heat-sensitive lithographic printing plate according to the present invention may be provided with an undercoat layer in order to improve the adhesion between the image forming layer and the support as described above. The layers constituting the surface on which the image is drawn, such as the image forming layer and the water retention layer of the heat-sensitive lithographic printing plate according to the present invention, are coated with titanium oxide, silicon dioxide, and aluminum oxide for the purpose of preventing printing stains. An inorganic substance such as can be contained. The ratio to be contained is appropriately determined in a desired range depending on various conditions such as printing ink, dampening water, printing speed, and printing pressure used for printing.

  The heat-sensitive lithographic printing plate according to the present invention is provided with a function of improving conductivity and antistatic property as necessary, an anti-curl layer for preventing curling as a printing plate, and a curl promoting layer for imparting desired curling. Etc. can be provided in plural.

  In the layer constituting the heat-sensitive lithographic printing plate according to the present invention, two or more anionic, cationic, betaine or nonionic surfactants may be used in combination as a coating aid, a matting agent, Thickeners and antistatic agents can also be used.

  As the water-resistant support, for example, a plastic film, resin-coated paper, water-resistant paper or the like can be used. Specifically, polyolefins such as polyethylene and polypropylene, polyethersulfone, polyester, poly (meth) acrylate, polycarbonate, polyamide, and polyvinyl chloride plastic film, resin-coated paper with these plastics laminated or coated on the surface, melamine Paper that has been water-resistant by a wet paper strength agent such as formaldehyde resin, urea formaldehyde resin, or epoxidized polyamide resin can be used.

  The thickness of the support is preferably about 100 to 300 μm from the viewpoint of the recording suitability of the thermosensitive plate making apparatus and the lithographic printing press suitability. In addition, the surface of these supports can be subjected to a surface treatment for improving adhesion with a layer coated as an upper layer, or can be subjected to a dyeing treatment for improving visibility. The preferred support in the present invention is resin-coated paper or polyethylene terephthalate.

  The surface of such a water-resistant support may be subjected to treatments such as plasma treatment, corona discharge treatment, deep ultraviolet irradiation treatment, and subbing treatment in order to enhance adhesion with the image forming layer. The subbing layer provided on the water-resistant support by the subbing treatment is composed of an acetal resin such as polyvinyl butyral, a polyester resin having a hydroxyl group at the end of the molecular chain, (meth) acrylic acid / (meth) acrylic acid ester A resin selected from a polymer, a vinylidene chloride / vinyl chloride copolymer, and the like can be contained. The thickness of the undercoat layer is usually about 0.1 to 10 μm in dry film thickness.

  The layer constituting the heat-sensitive lithographic printing plate according to the present invention is produced by coating and drying a coating liquid prepared by mixing each material and dissolving or dispersing in an appropriate solvent on a support by a known coating method. To do. The preferred solvent is water, but in order to prevent the image forming layer (and the intermediate layer) from being thermally denatured by the heat during drying, the drying treatment is preferably performed in an atmosphere of 50 ° C. or lower for about 30 seconds to 10 minutes. .

  Hereinafter, the present invention will be described in detail with reference to examples. In the description, “parts” and “%” are based on mass unless otherwise indicated.

Example 1
A 150 μm-thick double-sided polyethylene coated paper (RC paper) is corona discharge processed, and then an image-forming layer coating liquid having the following formulation is applied to produce a heat-sensitive lithographic printing plate having an image-forming layer having a dry film thickness of 3 μm. Produced.

<Image forming layer coating solution>
Water-soluble polymer compound: Gelatin (Nippi IK3000) (12% aqueous solution)
80 parts, fine particles of thermoplastic resin; carboxy-modified styrene-butadiene copolymer (DIC Corporation)
Lackstar 7132-C) (solid content 45%) 30 parts, 1,2-bis (3-methylphenoxy) ethane (KS-232, KS-232) dispersion (30% dispersion) 30 parts, developer 4-hydroxy-4'-isopropoxydiphenyl sulfone (Nippon Soda Co., Ltd. D-8) dispersion (30% aqueous dispersion) 30 parts, color former; 3-dibutylamino-6-methyl-7-anilino 9 parts fluoran (Yamamoto Kasei ODB2) dispersion (30% aqueous dispersion) hardener; 1.2 parts divinyl sulfone

The thermal lithographic printing plate produced by the above method is used in a test printing mode (printing speed 2 inches / second, applied energy 18.6 mJ / second) of a direct thermal printer (Toshiba TEC barcode printer B-433 line type thermal head 300 dpi). mm ² ). Images were recorded.

  The image portion and the non-image portion were pressed with a finger before and after applying the plate surface treatment liquid to the plate surface with respect to the heat-sensitive lithographic printing plate on which image formation was performed in this way, and fingerprint smudges or missing fingerprints were evaluated. An etching converter HP-420e (manufactured by Iwasaki Tsushinki Co., Ltd.) was used as a method for applying the plate surface treatment liquid to the plate surface. This is an apparatus for applying the plate surface treatment liquid to the plate surface by immersing the printing plate in a liquid bath in which the plate surface treatment liquid is stored and squeezing the excess plate surface treatment liquid with a roll pair.

The plate surface treatment liquids used were the following (a) to (o).
<Plate surface treatment liquid (a)>
・ Sodium hydroxide 3g / L
・ Succinic acid 5g / L
・ Propylene glycol 20g / L
・ Colloidal silica aqueous dispersion 20g / L
・ Anionic surfactant 0.05g / L
As the colloidal silica aqueous dispersion, Snowtex C (20% dispersion as an oxide, particle size 10 to 20 nm) manufactured by Nissan Chemical Industries, Ltd. was used. As the anionic surfactant, Hytenol 227L (polyoxyethylene lauryl sulfate sodium salt 27% aqueous solution) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used. The pH was 5.6.

<Plate surface treatment liquid (b)>
5 g of glucose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (c)>
5 g of fructose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (d)>
5 g of arabinose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (e)>
5 g of sucrose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (f)>
5 g of lactose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (g)>
5 g of maltose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (h)>
5 g of trehalose was added to 1 L of the plate surface treatment solution (a).
<Plate surface treatment liquid (i)>
5 g of maltotriose was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (j)>
5 g of sorbitol was added to 1 L of the plate surface treatment solution (a).
<Plate surface treatment liquid (k)>
5 g of maltitol was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (l)>
10 g of trehalose was added to 1 L of the plate surface treatment solution (a).
<Plate surface treatment liquid (m)>
5 g of dextrin (average polymerization degree of 6 or more) was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (n)>
5 g of cyclodextrin (polymerization degree 6 to 8) was added to 1 L of the plate surface treatment liquid (a).
<Plate surface treatment liquid (o)>
5 g of pullulan (degree of polymerization of 10 or more) was added to 1 L of the plate surface treatment liquid (a).

  RYOBI3200CCD (Ryobi Imagics Co., Ltd.) is used as the printing machine, SLM-OD (Mitsubishi Paper Co., Ltd.) 10% diluted solution is used as the dampening solution, and Pearl Coat (Mitsubishi Paper Co., Ltd.) is used as the paper. It was. For ink, F-Gloss Black H (DIC) was used for evaluation of the image area (fingerprint missing), and F-Gross Purple S (DIC Corporation) was used for evaluation of the non-image area (fingerprint smear). )It was used. The printing was started by rotating 20 times without feeding the paper while keeping the swim roller in contact with the plate cylinder, moistening the entire plate, and then feeding the paper as usual to start printing.

  The evaluation of missing fingerprints was performed by counting the number of prints that could not be confirmed as missing fingerprints on the printed matter discharged from the printing press immediately after the start of printing, and evaluating the number of lost fingerprints. The smaller the number, the better the resistance to missing fingerprints. Regarding fingerprint smudges, the number of sheets on which non-image area fingerprint smears could not be confirmed in the printed matter discharged from the printing press immediately after the start of printing was counted and evaluated as the number of fingerprint smudge recovered. The smaller the number, the better the resistance to fingerprint contamination. The results are shown in Table 1.

(Example 2)
Instead of the colloidal silica aqueous dispersion (Snowtex C) of Example 1, a colloidal alumina aqueous dispersion (Alumina Sol 100 manufactured by Nissan Chemical Industries, Ltd. (20% dispersion as oxide, particle size 10 to 20 nm)) was used. A plate surface treatment solution was prepared in the same manner as described above, and printing was performed in the same manner as in Example 1. Evaluation of fingerprint omission and fingerprint smudge performance was performed in the same manner as in Example 1. As a result, almost the same results as in Table 1 were obtained except that the fingerprint smudge performance was slightly inferior.

  From the above results, according to the printing method of the present invention, it is possible to provide a printing method for a thermal lithographic printing plate in which fingerprint smearing and fingerprint omission are improved.

Claims (1)

  After forming an image portion by imagewise heating an image forming layer of a lithographic printing plate having an image forming layer containing at least a thermoplastic resin and a water-soluble polymer compound on a water-resistant support, before starting printing A printing method for a heat-sensitive lithographic printing plate, comprising printing after applying a plate surface treatment liquid containing inorganic fine particles and at least one saccharide having a polymerization degree of 4 or less to a plate surface.