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WO2007018013A1 - Matériau de plaque d’impression - Google Patents

Matériau de plaque d’impression Download PDF

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Publication number
WO2007018013A1
WO2007018013A1 PCT/JP2006/313935 JP2006313935W WO2007018013A1 WO 2007018013 A1 WO2007018013 A1 WO 2007018013A1 JP 2006313935 W JP2006313935 W JP 2006313935W WO 2007018013 A1 WO2007018013 A1 WO 2007018013A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
printing
particles
acid
printing plate
Prior art date
Application number
PCT/JP2006/313935
Other languages
English (en)
Japanese (ja)
Inventor
Takahiro Mori
Original Assignee
Konica Minolta Medical & Graphic, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Priority to JP2007529469A priority Critical patent/JPWO2007018013A1/ja
Publication of WO2007018013A1 publication Critical patent/WO2007018013A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08—Developable by water or the fountain solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/266—Polyurethanes; Polyureas

Definitions

  • the present invention relates to a printing plate material, and more particularly to a printing plate material capable of image formation by a computer 'to plate (CTP) method and developable on a printing press.
  • CTP computer 'to plate
  • DI direct imaging
  • An infrared laser recording system having a wavelength of near infrared to infrared rays is mainly used for image formation of a thermal processless plate.
  • thermal processless plates There are two types of thermal processless plates that can form images using this method: an ablation type and a thermal fusion image layer development type.
  • a printing plate material for CTP that can be developed with dampening water or ink on a printing press using thermoplastic particles and a binder of a water-soluble polymer compound in a heat-sensitive image forming layer.
  • the exposed portions of these image forming layers are improved in water resistance and mechanical strength by thermal fusion of thermoplastic particles, and are less soluble and dispersible in dampening water, and are also pulled by ink tack. Since it is not peeled off, it remains as an image portion on the support during printing.
  • the unexposed portion of the image forming layer is removed by dissolving or dispersing in dampening water, or peeling off by ink tack and transferring into ink.
  • thermoplastic particles are also plasticized by pressure
  • the image-forming layer that has been subjected to pressure such as scratches is still pressed between the thermoplastic particles and pressed against the uneven surface of the substrate.
  • the ink adherence that is, it is easy to cause scratch marks (stained areas where the image forming layer is rubbed)! ⁇ . For this reason, it was necessary to handle the printing plate material very delicately, and it was easy to cause a decrease in productivity, such as the frequency of plate re-production due to the occurrence of contamination.
  • these printing plate materials may not have sufficient image portion strength and adhesion strength between the image portion and the substrate surface, and printing durability and chemical resistance may be insufficient. It was.
  • particles used in the image forming layer particles containing an epoxy group-containing compound or microcapsules containing an epoxy group-containing compound are used. It is known that by causing a cross-linking reaction with the functional group on the surface of the material, the strength of the image area and the adhesive strength between the image area and the substrate surface are improved, so that the printing durability is improved. (See Patent Document 3).
  • Patent Document 1 JP-A-9-123387
  • Patent Document 2 JP-A-9-123388
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-46361
  • An object of the present invention is to provide a printing plate material capable of on-press development and having high sensitivity and excellent printing durability.
  • a printing plate material having a heat-sensitive image forming layer developable on a printing machine on a substrate having a hydrophilic surface, wherein the heat-sensitive image forming layer comprises (A) two or more epoxies in the molecule A printing plate material comprising a water-soluble compound having a group and (B) an imidazole compound.
  • thermosensitive image-forming layer further comprises (C) a compound which is a solid at 25 ° C which is substantially insoluble in water and has a particle diameter (major axis) in the range of 1 ⁇ to 5 / ⁇ .
  • the printing plate material according to any one of (1) to (3), wherein the printing plate material comprises particles.
  • a printing plate material capable of on-press development can be provided that has high sensitivity and excellent printing durability.
  • the present invention provides a printing plate material having a thermal image-forming layer that can be developed on a printing machine on a substrate having a hydrophilic surface, wherein the thermal image-forming layer comprises (A) two or more in the molecule. It contains a water-soluble compound having an epoxy group and (B) an imidazole compound.
  • the heat-sensitive image forming layer contains (A) a water-soluble compound having two or more epoxy groups in the molecule and (B) an imidazole compound in combination.
  • a printing plate material having high sensitivity and excellent printing durability can be provided.
  • the heat-sensitive image forming layer in the heated portion forms an ink-thickness image by image-like heating, and the heat-sensitive image forming layer in the non-heated portion is removed and is hydrophilic.
  • the surface of the layer can be exposed to form an image as a printing plate.
  • the thermal image forming layer is removed on a printing press. That is, the heat-sensitive image forming layer is a layer that can be developed on a printing machine.
  • developer on a printing press means that the image forming layer in the non-image area can be removed by dampening water and / or printing ink in lithographic printing after exposure on the printing press.
  • the heating method includes a method using a heat source and a method using heat generated by light exposure with a laser or the like, and an image forming method using heat generated by light exposure with a laser or the like is preferable.
  • the water-soluble compound having two or more epoxy groups in the molecule according to the present invention has two or more epoxy groups in the molecule and dissolves 0.1 lg or more in 25 ° C water lOOg. Refers to a compound
  • water-soluble compound having two or more epoxy groups in the molecule include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglyceryl polyglycidyl ether, sorbitol polyglycidyl ether, Examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and propylene glycol diglycidyl ether.
  • the water-soluble compound having two or more epoxy groups in the molecule it is preferable to dissolve more than lg in 25 ° C water lOOg, and more preferable to dissolve more than 10g of water.
  • a water-soluble compound having two or more epoxy groups in the molecule is more water-soluble and has better on-press developability and scratch resistance.
  • (A) is preferably a compound that is liquid at 25 ° C from the standpoint of on-press development.
  • the content of (A) in the image forming layer is preferably in the range of 5% by mass to 80% by mass, particularly preferably 15% by mass to 50% by mass.
  • the imidazole compound according to the present invention means a derivative of imidazole and includes a derivative in the form of a salt. In addition, it can be used with V or deviation of water-insoluble imidazole compounds and water-soluble imidazole compounds.
  • imidazole compound include the following.
  • Water-soluble imidazole compounds imidazole, 1-methylimidazole, 2-methylimidazole, 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole
  • Water-insoluble imidazole compounds 2-phenol imidazole, 2-undecyl imidazole, 2 heptadecyl imidazole, 2 phenol 4-methylimidazole, 1 benzyl 2-methylimidazole, 1 benzyl 2-phenol -Ruimidazole, 1-Cyanethyl 2-Methylimidazole, 1-Cyanoethyl 2-Ethyl 4-Methylimidazole, 2, 4 Diamino 1- 6- [2,1-Methylimidazolyl 1 (1,)] 1-ethyl triadiene, 2 Fe-Louimidazo Carboxylic acid with monoisoisocyanuric acid, 2—Ferreux 4, 5 Dihydroxymethylimidazole, 2—Fuel-Luimidazoline, 1—Cyanethyl 1—Fue-Ruimidazolid trimellitite
  • water-soluble imidazole compound As (B), it is preferable to use a water-soluble imidazole compound from the viewpoints of sensitivity, resolution, and on-press developability.
  • water-soluble has the same meaning as the water-solubility described in (A) above.
  • the particulate dispersion unit that is preferably contained in the image forming layer in a particulate dispersed form includes sensitivity, resolution, From the standpoint of on-press development, it is preferable that the major axis of the particles is 5 ⁇ m or less. 3 ⁇ m or less It is more preferable that it is in the range of 10 ⁇ to 2 / ⁇ ⁇ .
  • the content of (i) in the heat-sensitive image forming layer is preferably in the range of 5% by mass to 60% by mass, particularly preferably 10% by mass to 50% by mass.
  • the content ratio of ( ⁇ ) and ( ⁇ ) (( ⁇ ) ⁇ ( ⁇ )) is preferably 0.1 to 20, and more preferably 0.3 to 5.
  • the amount of the thermal image forming layer is preferably 0.1 to 5 gZm 2 , more preferably 0.2 to 2 gZm 2 .
  • the amount with the hydrophilic layer, and more preferably it is 0. 5 ⁇ 15gZm 2 is preferably tool l ⁇ 8gZm 2.
  • the thermal image-forming layer according to the present invention further has (C) a particle size (major axis) of Inn!
  • the strength of the image-forming layer comprising particles of a compound that is substantially insoluble in water in the range of ⁇ 5 ⁇ m and is solid at 25 ° C. (hereinafter may be simply abbreviated as (C)), The on-press developability is preferred.
  • substantially insoluble in water means that the amount dissolved in 25 ° C. water lOOg is less than 0.1 lg.
  • the “particle diameter (major axis)” of the particle refers to the longest diameter of the particle and can be specified by a tomographic electron micrograph of the thermal image forming layer.
  • (C) mainly functions as a filler.
  • organic particles, inorganic particles, organic-inorganic composite particles !, misalignment can also be used, and the particle shape is spherical, polyhedral, spindle-shaped, needle-shaped, flat-plate-shaped. , And irregular shapes! /, Any shape! /
  • composition of the surface and the inside may be changed, or surface treatment may be performed! Moreover, fine irregularities may be formed on the surface, which may be nonporous or porous.
  • the content of (C) in the heat-sensitive image forming layer is preferably in the range of 1% by mass to 70% by mass, particularly preferably 10% by mass to 50% by mass.
  • the organic particles include wax particles, thermoplastic polymer particles and other thermoplastic particles, hydrophilic polymer particles such as low-thermoplastic crosslinked polymer particles, cellulose particles, chitosan particles, Ca alginate particles, and core-shell particles. And particles in the form of microcapsules having a core containing a liquid compound at room temperature.
  • the organic particles particles of blocked isocyanate compounds can be preferably used.
  • the blocked isocyanate compound is a reaction compound of an isocyanate compound and a blocking agent for an isocyanate group.
  • the blocked isocyanate compound is preferably a compound obtained by further reacting a polyol with the reaction compound of the isocyanate compound and the blocking agent.
  • the isocyanate compound is a compound having an isocyanate group.
  • the isocyanate compound include aromatic polyisocyanates [diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), Polyphenylene polymethylene polyisocyanate (crude MDI), naphthalene diisocyanate (NDI), etc.; Aliphatic polyisocyanate [1, 6 hexamethylene diisocyanate (HDI), lysine diisocyanate Alicyclic polyisocyanate [isophorone diisocyanate (IPDI), dicyclohexylenomethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, etc.]; aromatic aliphatic Polyisocyanates [xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), etc.]; , Isocyanurate groups, car
  • Polyisocyanate compounds described in JP-A-10-72520 can also be preferably used.
  • tolylene diisocyanate is particularly preferable because of its fast reactivity.
  • a blocking agent is a compound having a group that undergoes an addition reaction with an isocyanate group to form a urethane bond or a urea bond.
  • an alcohol-based blocking agent such as methanol or ethanol
  • a phenol-based blocking agent such as phenol or talesol
  • formaldoxime Acetaldoxime
  • methyl ethyl ketoxime methyl isobutyl ketoxime
  • cyclohexanone talented oxime acetoxime
  • dicetinolemonosoxime benzophenone talented oxime
  • Active methylene block such as acid amide block agent, dimethyl malonate, methyl acetate acetate, etc.
  • Mercaptan blocking agents such as butyl mercaptan, imide blocking agents such as succinic acid imide and maleic acid imide, imidazole blocking agents such as imidazole and 2-methylimidazole, and urea blocking agents such as urea and thiourea N-phenol carnominic acid such as phenol, rubamic acid blocking agents such as phenol, amine blocking agents such as diphenylamine and arlin, and imine blocking agents such as ethyleneimine and polyethyleneimine. Can be mentioned. Among these, it is particularly preferable to use an oxime block agent.
  • the addition amount of the blocking agent is 1.0 to 1.1 equivalents of the isocyanate group of the isocyanate compound by combining the active hydrogen group in the blocking agent and the active hydrogen group of the polyol described below. It is preferable to contain so that it may become.
  • the dissociation temperature of the blocking agent is preferably 80 to 200 ° C, more preferably 80 to 160 ° C, and more preferably 80 to 130 ° C.
  • the blocked isocyanate compound a compound obtained by further adding a polyol to the adduct of the above blocking agent is preferably used.
  • the storage stability of the blocked isocyanate compound can be improved. Further, the image strength is improved when an image is formed by heating, and the printing durability is improved.
  • Polyols include propylene glycol, triethylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, neopentino glycol, 1,6-hexylene glycol, butanediol, hexamethylene glycol, xylylene.
  • Polyhydric alcohols such as lenglycol, sorbitol, sucrose, polyether polyols and polytetramethylene ether polyols obtained by addition polymerization of ethylene oxide or propylene oxide to these polyhydric alcohols or polyamines, or both.
  • Polycarbonate polyols, polyprolacton polyols, and the above polyhydric alcohols such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, sebacic acid, fumar Acid, maleic acid, polybasic acid and Po Li ester polyols obtained by reacting such Azerain acid, polybutadiene polyols, acrylic polyols, castor oil, grafting Bulle monomer polyether polyol or polyester polyol Polymer polyols, epoxy-modified polyols, and the like obtained in this manner.
  • propylene glycol triethylene glycol, glycerin, trimethylomonoremethane, trimethylolpropane, pentaerythritol, neopentyl glycol, 1,6-hexylene glycol, butanediol, hexamethylene glycol, xylylene glycol
  • a polyol having a molecular weight of 50 to 5000 such as sorbitol can be preferably used, and a low molecular weight polyol having a molecular weight of 50 to 500 can be particularly preferably used.
  • the amount of polyol attached is preferably 1.0 to 1.1 equivalents relative to the isocyanate group of the isocyanate compound combined with the active hydrogen in combination with the polyol and the blocking agent as described above.
  • the range in which the hydroxyl group in the polyol is from 0.1 to 0.9 equivalents relative to the isocyanate group of the isocyanate compound is preferred. Particularly in this range, the storage stability of the blocked isocyanate compound is particularly high. improves.
  • the isocyanate compound is heated to about 40 to 120 ° C. in an inert gas atmosphere under water-free conditions, and a blocking agent is added while stirring.
  • a predetermined amount is dropped and mixed, and the reaction is allowed to take several hours while stirring.
  • any solvent may be used.
  • known catalysts such as organometallic compounds, tertiary amines, metal salts and the like can also be used.
  • the organometallic catalyst for example, a tin-based catalyst such as stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, or a lead-based catalyst such as 2-ethylethylhexanoate, etc.
  • a tin-based catalyst such as stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, or a lead-based catalyst such as 2-ethylethylhexanoate, etc.
  • metal salt catalysts include, for example, cobalt naphthenate, naphthalene Examples thereof include calcium phthalate and lead naphthenate lithium oxide.
  • the amount of these catalysts to be used is generally
  • the blocked isocyanate compound is preferably a compound with a polyol.
  • the blocking agent and the polyol are reacted with the isocyanate compound.
  • the isocyanate compound and the polyol may be reacted first, and then the remaining isocyanate group and the blocking agent may be reacted.
  • the isocyanate compound and the blocking agent may be reacted first. Later, the remaining isocyanate groups may be reacted with the polyol.
  • the preferred average molecular weight of the blocked isocyanate compound is preferably a weight average molecular weight of 500 to 2000, more preferably 600 to 1000. Within this range, the balance between reactivity and storage stability is good.
  • the blocked isocyanate compound for example, a surfactant and water are added to the blocked isocyanate compound, and the mixture is vigorously mixed and stirred using a homogenizer or the like to obtain a dispersion. It is preferably used in the form of particles in the dispersion.
  • surfactant examples include, for example, key-on surfactants such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium succinate dialkyl ester sulfonate, and polyoxyethylene alkyl ester.
  • key-on surfactants such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium succinate dialkyl ester sulfonate, and polyoxyethylene alkyl ester.
  • Nonionic surfactants such as polyoxyethylene alkylaryl ethers, or alkylbetaine type salts such as lauryl betaine and stearyl betaine salts, lauryl mono- ⁇ -alanine, lauryl di (aminoethyl) glycine, Examples include both amino acid type surfactants such as octyldi (aminoethyl) glycine. These can be used alone or in combination of two or more. Of these, a nonionic surfactant is preferred.
  • the solid content of the aqueous dispersion of the blocked isocyanate compound is preferably 10 to 80% by mass.
  • the addition amount of the surfactant is preferably 0.01 to 20% by mass in the solid content of the aqueous dispersion.
  • the force organic solvent can be removed as an aqueous dispersion.
  • inorganic particles include colloidal metal oxides such as colloidal silica, alumina sol, titasol, and zircoyu sol, and particle diameters of about 1 to 0.2 / zm, silica, alumina, aluminosilicate, titer, and zircoyua.
  • metal oxide particles examples thereof include metal oxide particles, and these may be porous or nonporous.
  • composite particles such as metal carbide and metal nitride can also be used. Carbon black, graphite, carbon nano Particles such as tubes and fullerenes can also be used.
  • inorganic particles particularly metal oxide colloid particles and blocked isocyanate compound particles can be preferably used as (C).
  • the metal oxide colloidal particles also include sensitivity and printing durability.
  • (C) particles of a compound which is a solid at 25 ° C. and is substantially insoluble in water having a particle diameter (major axis) in the range of 1 ⁇ to 5 / ⁇ ⁇ is an inorganic compound.
  • a case where it is a blocked isocyanate compound is also a preferred embodiment, and a case where this blocked isocyanate compound is a compound of tolylene diisocyanate and a low molecular weight polyol is a particularly preferred embodiment.
  • the heat-sensitive image forming layer may contain a water-soluble resin having a functional group capable of reacting with an epoxy group.
  • a water-soluble resin having a functional group capable of reacting with an epoxy group.
  • polyacrylic acid and polyacrylic acid salt which are preferably polycarboxylic acids, can be preferably used.
  • the mass average molecular weight of the water-soluble resin is preferably in the range of 10,000 to 5 million, more preferably in the range of 100,000 to 5 million, and in the range of 1 million to 500 Vise is more preferable.
  • the heat-sensitive image forming layer contains (A) and (B) in combination, the non-image area that is not exposed has on-press developability.
  • (A) and (B) react to form a water-resistant image area, so that the effect of the present invention that is excellent in printing durability can be exhibited. It is guessed.
  • the heat-sensitive image forming layer preferably contains a photothermal conversion material described later.
  • a printing plate material capable of forming an image by, for example, an infrared laser can be obtained.
  • an infrared absorbing dye is preferred.
  • the content of the infrared-absorbing dye must be considered in consideration of the contamination of the printing press during on-press development depending on the degree of coloring of the dye with visible light. Preferably, it is not less than 0.0OOlg / m 2 and less than 0.2 g / m 2 , and more preferably less than 0.05 gZm 2 . Also, use a dye that is less colored with visible light. V, I prefer to do that, not to mention! /
  • infrared absorbing dyes include cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinones, which are general infrared absorbing dyes And organic compounds such as phthalocyanines, phthalocyanine-based, naphthalocyanine-based, azo-based, thiamid-based, dithiolinole-based and indo-phosphorus-based organometallic complexes.
  • JP-A-3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-36094, JP-A-3-36095, JP-A-3-42281, JP-A-3 42281 Compounds described in JP-A-97589, JP-A-3-103476, and the like. These can be used alone or in combination of two or more.
  • the compounds described in No. 219667 can also be preferably used.
  • the heat-sensitive image forming layer according to the present invention is preferably formed by coating from an aqueous coating solution.
  • the infrared absorbing dye to be contained is preferably water-soluble.
  • the heat-sensitive image forming layer according to the present invention may contain a material having a catalytic function for accelerating the reaction of the epoxy group due to heat.
  • the material having a catalytic function for example, organometallic compounds, tertiary amines, metal salts and the like can be used.
  • thermosensitive image forming layer according to the present invention may further contain microcapsules enclosing hydrophobic thermoplastic particles or a hydrophobic material.
  • the heat-sensitive image forming layer may contain a surfactant.
  • S-type or F-type surfactants can be used, but in particular, surfactants containing Si element are used. It is preferable that there is no concern of causing print stains.
  • the content of this surfactant is preferably from 0.01 to 3% by mass, more preferably from 0.03 to 1% by mass of the heat-sensitive image forming layer (solid content as the coating solution).
  • an acid phosphoric acid, acetic acid, etc.
  • alkali sodium hydroxide, silicate, phosphate, etc.
  • the thermal image forming layer may contain a lubricant.
  • Lubricants can be included.
  • known waxes are preferable. Among them, low ink fatty acid amides, fatty acid Ca, fatty acid Zn and the like are preferable.
  • the thermal image forming layer is preferably formed by coating using an aqueous coating solution.
  • the lubricant is preferably added to the coating solution as an aqueous dispersion.
  • the content of the lubricant is preferably 0.1 to 30% by mass of the heat-sensitive image forming layer.
  • the substrate having a hydrophilic surface according to the present invention is a substrate having a surface from which the heat-sensitive image forming layer is removed at the time of printing, and has a surface that can become a non-image portion.
  • a substrate having a hydrophilic surface layer or a substrate having a hydrophilic layer containing a hydrophilic substance can be used.
  • a known material used as a substrate for a printing plate can be used as long as the surface characteristics are as described above, for example, a metal plate, a plastic, and the like.
  • examples thereof include a film, paper treated with polyolefin, a composite substrate obtained by appropriately bonding the above materials, and the like.
  • the thickness of the substrate is not particularly limited as long as it can be attached to a printing press! /
  • a metal plate whose surface is hydrophilized is preferably used as the base material according to the present invention.
  • Examples of the metal plate include forces such as iron, stainless steel, and aluminum.
  • aluminum or an aluminum alloy (hereinafter, both referred to as an aluminum plate) is preferred from the relationship between specific gravity and rigidity. Gucarole, known roughening treatment, anodizing treatment Of surface hydrophilization! / A product that has been subjected to any treatment (so-called aluminum grained plate) is more preferable.
  • Examples of the aluminum grained plate include a grained plate obtained by the method disclosed in JP-A-10-869.
  • the aluminum alloy that can be used as the base material according to the present invention various alloys can be used.
  • An alloy of a metal such as iron and aluminum is used.
  • the aluminum plate that can be used as the base material according to the present invention is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment).
  • a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, and the like are used.
  • An alkaline aqueous solution such as caustic soda can also be used for the degreasing treatment.
  • an alkaline aqueous solution such as caustic soda
  • dirt and acid film can be removed, which cannot be removed only by the above degreasing treatment.
  • an alkaline aqueous solution such as caustic soda
  • smut is generated on the surface of the substrate.
  • the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof. It is preferable to apply a desmut treatment.
  • the roughening method include a mechanical method and a method of etching by electrolysis.
  • the mechanical surface roughening method used is not particularly limited, but a brush polishing method and a Houng polishing method are preferred.
  • the roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and, for example, a volcanic ash having a particle diameter of 10 to: LOO ⁇ m. While supplying a slurry in which particles are uniformly dispersed in water, the brush can be pressed.
  • For roughing by Houng polishing for example, volcanic ash particles with a particle size of 10 to 100 m are uniformly dispersed in water, injected by applying pressure from a nozzle, and then obliquely collided with the surface of the substrate for roughening. be able to.
  • the surface of the base material is soaked, soaked in an aqueous solution of acid or alkali in order to remove abrasives, aluminum scraps formed, etc.
  • the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like.
  • the base include sodium hydroxide, potassium hydroxide, and the like. Among these, it is preferable to use an alkaline aqueous solution such as sodium hydroxide.
  • the amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m 2 .
  • the electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable.
  • the acidic electrolytic solution an acidic electrolytic solution that is usually used in an electrochemical roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used.
  • the electrochemical surface roughening method for example, the methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used.
  • This roughening method is generally preferably selected from the range of 10 to 30 volts that can be applied by applying a voltage in the range of 1 to 50 volts.
  • Current density is preferably selected from the range of the force 50 to 150 A / dm 2 which may be used range from 10 to 200 A / dm 2.
  • the electric quantity can be in the range of 100 to 5000 CZdm 2 , but the range force of 100 to 2000 C / dm 2 is also preferably selected.
  • the temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but it is preferable to select a range force of 15 to 45 ° C.
  • a force that can be applied by applying a voltage in the range of 1 to 50 volts is in the range of 10 to 30 volts. It is preferable to select the force.
  • Current density the force 20 may be in the range of 10 to 200 A / dm 2: Range force LOOA / dm 2 also preferably selected.
  • Quantity of electricity is preferably selected from the range of the force 100 ⁇ 2000C / dm 2 which may be in the range of 100-500 OC / dm 2.
  • the temperature for the electrochemical surface roughening method can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.
  • the concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass.
  • the electrolyte includes nitrates, chlorides, amines, aldehydes as needed. Examples thereof include phosphoric acid, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid and the like.
  • the current density is preferably selected from the range of forces 50-150 AZdm 2 which can use the range of 10-200 A / dm 2 .
  • the amount of electricity can be in the range of 100 to 5000 C / dm 2 , but is preferably selected from the range of 100 to 2000 CZdm 2 , more preferably 200 to 1000 CZdm 2 .
  • the temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but it is also preferable to select a range force of 15 to 45 ° C.
  • the hydrochloric acid concentration in the electrolytic solution is preferably 0.1 to 5% by mass.
  • the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface.
  • the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like.
  • the base include sodium hydroxide, potassium hydroxide, and the like.
  • an aqueous alkali solution it is preferable to use an aqueous alkali solution.
  • the amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m 2 .
  • the mechanical surface roughening method and the electrochemical surface roughening method may each be used alone to roughen the surface, or the mechanical surface roughening method followed by the electrochemical surface roughening method. To roughen the surface.
  • an anodizing treatment is preferably performed.
  • the anodizing treatment method that can be used in the present invention, a known method without particular limitation can be used.
  • an oxide film is formed on the substrate.
  • the anodic oxidation treatment a method in which an aqueous solution containing sulfuric acid and Z or phosphoric acid or the like at a concentration of 10 to 50% is used as an electrolytic solution and electrolysis is performed at a current density of 1 to 10 AZdm 2 is used.
  • Anodized coating amount of the formed, L ⁇ 50mgZdm 2 are suitable, preferably 10 ⁇ 40mgZdm 2.
  • the amount of anodic oxidation coating is, for example, by immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of acid-chromium (IV): 1 g of water) to dissolve the oxide film. In addition, it is obtained from the measurement of mass change before and after dissolution of the coating on the plate.
  • the anodized base material may be subjected to a sealing treatment as necessary.
  • These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and acetic acid ammonium treatment. .
  • water-soluble rosin for example, polybuluphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyattaric acid, A water-soluble metal salt (for example, zinc borate) or a primer coated with a yellow dye, an amine salt or the like is also suitable.
  • a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used is also preferably used.
  • plastic film used as the base material examples include films of polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, cellulose esters, and the like.
  • polyester films such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polyethylene naphthalate (hereinafter sometimes abbreviated as PEN) are used as base materials. are preferably used.
  • the preferred polyester film is an unstretched polyester film, a uniaxially stretched polyester film, or a biaxially stretched polyester film.
  • a longitudinally stretched polyester film uniaxially stretched in the film extrusion direction (longitudinal direction) is particularly preferred.
  • easy adhesion treatment or undercoat layer coating can be performed to give various functions.
  • Examples of the easy adhesion treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment.
  • the undercoat layer a layer containing gelatin or latex or the like is preferably provided on the polyester film support.
  • the antistatic undercoat layer described in paragraph Nos. 0044 to 0116 of JP-A-7-191433 is preferably used.
  • the conductive polymer-containing layer described in paragraph Nos. 0031 to 0073 of JP-A-7-20596 is a conductive layer such as the metal oxide-containing layer described in paragraph Nos. 0074 to 0081 of JP-A-7-20596. It is preferred to have it! / ⁇ .
  • the conductive layer may be coated on the side of slippage as long as it is on the polyester film support, but is preferably coated on the opposite side of the image forming functional layer with respect to the support.
  • this conductive layer is provided, the chargeability is improved, the adhesion of dust and the like is reduced, and the whiteout failure during printing is greatly reduced.
  • a hydrophilic layer is provided on the substrate to form a substrate having a hydrophilic surface.
  • the hydrophilic layer preferably has a porous structure.
  • hydrophilic layer having a porous structure In order to form a hydrophilic layer having a porous structure, the following materials for forming a hydrophilic matrix are preferably used.
  • the material for forming the hydrophilic matrix is preferably a metal oxide.
  • the metal oxide preferably contains fine metal oxide particles, for example, colloidal silica, alumina sol, titer sol, and other metal oxide sols.
  • the form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form, and the average particle size is preferably an average particle size in the range of 3 to: LOOnm.
  • LOOnm Several different kinds of metal oxide fine particles can be used in combination.
  • the surface of the particles may be surface-treated.
  • the metal oxide fine particles can be used as a binder by utilizing the film forming property. It is suitable for use in a hydrophilic layer where the decrease in hydrophilicity is less than when an organic binder is used. [0123] (Colloidal silica)
  • colloidal silica can be particularly preferably used.
  • Colloidal silica has the advantage of high film forming properties even under relatively low temperature drying conditions, and can provide good strength.
  • the colloidal silica preferably includes a necklace-shaped colloidal silica, which will be described later, and a fine particle colloidal silica having an average particle size of 20 ⁇ m or less. Further, the colloidal silica preferably exhibits alkalinity as a colloid solution.
  • Necklace-shaped colloidal silica is a general term for an aqueous dispersion of spherical silica having an order of primary particle size of 111.
  • Spherical colloidal silica having a primary particle size of 10 to 50 nm has a length of 50 to 400 nm. It means the combined “pearl necklace” colloidal silica.
  • the pearl necklace shape (namely, pearl necklace shape) means an image power in a state where silica particles of colloidal silica are joined together and shaped like a pearl necklace.
  • the hydrophilic layer may contain porous metal oxide particles having a particle size of less than 1 m as a porous material having a hydrophilic layer matrix structure.
  • porous metal oxide particles the following porous silica, porous aluminosilicate particles, or zeolite particles can be preferably used.
  • the porous silica particles are generally produced by a wet method or a dry method.
  • the gel obtained by neutralizing the aqueous silicate solution can be obtained by drying and pulverizing, or by pulverizing the precipitate deposited after neutralization.
  • silicon tetrachloride is burned with hydrogen and oxygen, and silica is deposited.
  • the porosity and particle size of these particles can be controlled by adjusting the production conditions.
  • those obtained by a wet gel force are particularly preferred.
  • Porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, amorphous composite particles synthesized by hydrolysis using aluminum alkoxide and silicon alkoxide as main components. The ratio of alumina to silica in the particles can be synthesized in the range of 1: 4 to 4: 1. It can also be Those produced by adding other metal alkoxides as composite particles of three or more components can also be used in the present invention. The porosity and particle size of these composite particles can also be controlled by adjusting the production conditions.
  • the porosity of the particles is preferably 0.5 mlZg or more in terms of pore volume, more preferably 0.8 mlZg or more, and more preferably 1.0 to 2.5 mlZg. preferable.
  • the pore volume is closely related to the water retention of the coating film, and the larger the pore volume, the better the water retention and the greater the water volume latitude that will resist smearing during printing, but it will be greater than 2.5 mlZg. Since the particles themselves become very brittle, the durability of the coating film decreases. Conversely, if the pore volume is less than 0.5 mlZg, the printing performance may be slightly insufficient.
  • the pore volume is measured by using Auto Soap 1 (manufactured by Kantachrome), and by measuring nitrogen adsorption using a constant volume method, the voids of the powder are filled with nitrogen.
  • the amount of nitrogen adsorption when the relative pressure is 0.998 is also calculated.
  • Zeolite is a crystalline aluminosilicate, and is a porous body having a pore size of 0.3 nm to: Lnm, and having a three-dimensional network structure void.
  • the hydrophilic layer matrix structure constituting the hydrophilic layer can contain layered clay mineral particles.
  • the layered mineral particles include kaolinite, halloysite, talc, smetite (montmorillonite, piderite, hectorite, sabonite, etc.), clay minerals such as vermiculite, my strength (mica), chlorite, and hyde mouth tar.
  • Sites, layered polysilicates such as kanemite, macatite, eyelite, magadiite, cayeite).
  • the higher the charge density of the unit layer (unit layer) the higher the polarity and the higher the hydrophilicity.
  • the charge density is preferably 0.25 or more, more preferably 0.6 or more.
  • the layered mineral having such charge density include smectite (charge density of 0.25 to 0.6; negative charge), vermiculite (charge density of 0.6 to 0.9; negative charge), and the like.
  • synthetic fluoromica is preferable because it can be obtained with stable quality such as particle size.
  • synthetic fluorine mica those which are free swellable are more preferable, which are swellable.
  • the size of the plate-like layered mineral particles is as follows.
  • the average particle size (maximum length of the particles) is 1 when the particles are contained in the layer (including those that have undergone the swelling process and dispersion peeling process). It is preferable that the average aspect ratio is 50 or more.
  • the particle size is in the above range, the continuity and flexibility in the planar direction, which are the characteristics of the thin layered particles, are imparted to the coating film, and cracks can enter to make a tough coating film in a dry state. . Further, in a coating solution containing a large amount of particulate matter, sedimentation of the particulate matter can be suppressed by the thickening effect of the layered clay mineral.
  • the coating film may become non-uniform and the strength may be locally reduced.
  • the aspect ratio is not more than the above range, the number of tabular grains with respect to the added amount is reduced, the viscosity is insufficient, and the effect of suppressing sedimentation of the particles is reduced.
  • the content of the layered mineral particles is preferably 0.1 to 30% by mass, more preferably 1 to 10% by mass, based on the entire layer.
  • swellable synthetic fluoromica is preferred because smectite is effective even when added in a small amount.
  • the layered mineral particles may be added to the coating liquid as a powder! /, But in order to obtain a good degree of dispersion even with a simple preparation method (no need for a dispersion step such as media dispersion) In addition, it is preferable to prepare a gel in which layered mineral particles are swelled alone in water and then add it to the coating solution.
  • a silicate aqueous solution can also be used as another additive material.
  • Alkali metal silicates such as Na, Ca and Li are preferred.
  • the SiO / M O ratio is the p of the entire coating solution when the caate is added.
  • inorganic polymers or organic-inorganic hybrid polymers using metal alkoxides by the so-called sol-gel method can also be used.
  • sol-gel method For the formation of inorganic polymers or organic-inorganic hybrid polymers by the sol-gel method, see, for example, the force described in “Application of the sol-gel method” (published by Sakuo Sakuo, published by Z. Known methods described in the literature used for Bow I can be used.
  • the hydrophilic layer may contain a water-soluble resin.
  • water-soluble resin include conjugates of polysaccharides, polyethylene oxide, polypropylene oxide, polybutyl alcohol, polyethylene glycol (PEG), polybutyl ether, styrene-butadiene copolymer, and methyl methacrylate-butadiene copolymer.
  • Resins such as polymer-based latex, acrylic polymer latex, vinyl polymer latex, polyacrylamide, polypyrrolidone, and the like.
  • polysaccharides starch, celluloses, polyuronic acid, pullulan and the like can be used.
  • Cellulose derivatives such as methylcellulose salt, carboxymethylcellulose salt, hydroxyethylcellulose salt and the like are preferred.
  • Sodium salt and ammonium salt are more preferable. This is because an effect of forming the surface shape of the hydrophilic layer in a preferable state can be obtained by incorporating the polysaccharide into the hydrophilic layer.
  • the surface of the hydrophilic layer preferably has a concavo-convex structure with a pitch of 0.1 to 20 m like the aluminum grain of the PS plate.
  • This concavo-convex improves water retention and image area retention.
  • Such a concavo-convex structure can be formed by containing an appropriate amount of a filler having an appropriate particle size in the hydrophilic layer matrix.
  • the alkaline colloidal silica and the aqueous solution described above are added to the coating solution for the hydrophilic layer. It is preferable that a structure having better printability can be obtained by forming a phase separation when the hydrophilic polysaccharide is applied and dried by adding a hydrophilic polysaccharide.
  • the shape of the concavo-convex structure depends on the type and amount of alkaline colloidal silica, the type and amount of water-soluble polysaccharides, the type and amount of other additives, and the solid content of the coating liquid. It is possible to appropriately control the concentration, wet film thickness, drying conditions, and the like.
  • the water-soluble coagulum added to the hydrophilic matrix structure part is present in a state where at least a part thereof is water-soluble and can be eluted in water. This is because even if a water-soluble material is cross-linked by a cross-linking agent or the like and becomes insoluble in water, its hydrophilicity is lowered and printability may be deteriorated.
  • the cationic resin that may contain the resin include polyalkylene polyamines such as polyethyleneamine and polypropylenepolyamine or derivatives thereof, tertiary amino groups and quaternary ammonia. Examples thereof include acrylic resin having a group and diacrylamine.
  • the thionic coagulant may be added in the form of fine particles, for example, a cationic microgel described in JP-A-6-161101.
  • the coating liquid used for coating the hydrophilic layer can contain a water-soluble surfactant for the purpose of improving the coating property, etc.
  • An activator can be used, but it is particularly preferable to use a surfactant containing Si element because there is no fear of causing printing stains.
  • the content of the surfactant is preferably from 0.01 to 3% by mass, more preferably from 0.03 to 1% by mass, based on the entire hydrophilic layer (solid component as the coating solution).
  • the hydrophilic layer may contain a phosphate.
  • the hydrophilic layer coating solution is preferably alkaline, it is preferable to add the phosphate as trisodium phosphate or disodium hydrogen phosphate. By adding phosphate, the effect of improving the mesh opening during printing can be obtained.
  • the amount of phosphate added is preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass, as an effective amount excluding hydrates.
  • the heat-sensitive image forming layer preferably contains a photothermal conversion material described later.
  • an infrared absorbing dye is preferred.
  • the content of the infrared-absorbing dye must be considered in consideration of the contamination of the printing press during on-press development depending on the degree of coloring of the dye with visible light.
  • it is not less than 0.0OOlg / m 2 and less than 0.2 g / m 2 , and more preferably less than 0.05 gZm 2 .
  • it is preferable to use a dye that is less colored with visible light.
  • infrared absorbing dyes include cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinones, which are general infrared absorbing dyes.
  • Organic compounds such as pigments Phthalocyanine-based, naphthalocyanine-based, azo-based, thiamid-based, dithiolinole-based and indo-phosphorus organometallic complexes.
  • JP-A-3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-36094, JP-A-3-36095, JP-A-3-42281, JP-A-3 42281 Compounds described in JP-A-97589, JP-A-3-103476, and the like. These can be used alone or in combination of two or more.
  • the compounds described in No. 219667 can also be preferably used.
  • the heat-sensitive image forming layer according to the present invention is preferably water-soluble as the infrared-absorbing dye to be contained when it is preferably formed by coating from an aqueous coating solution.
  • the printing plate material according to the present invention preferably forms an image using laser light.
  • a gas laser may be used as the laser, it is particularly preferable to use a semiconductor laser that emits light in the near infrared region.
  • An apparatus suitable for scanning exposure is any apparatus as long as it can form an image on the surface of a printing plate material in accordance with an image signal from a computer using the semiconductor laser. Also good.
  • the printing plate material held along the cylindrical surface inside the fixed cylindrical holding mechanism is used in the circumferential direction of the cylinder (mainly using one or more laser beams from the inside of the cylinder). (Scanning direction) and moving in the direction perpendicular to the circumferential direction (sub-scanning direction) to expose the entire surface of the printing plate material, (3) on the surface of a cylindrical drum that rotates around the axis as a rotating body
  • the held printing plate material is scanned in the circumferential direction (main scanning direction) by rotating the drum using one or more laser beams, such as a cylindrical outer cover, and in the direction perpendicular to the circumferential direction (sub-scanning) And a method of exposing the entire surface of the printing plate material.
  • the exposure method (3) is used.
  • the image-exposed printing plate material can be subjected to general lithographic printing using dampening water and printing ink.
  • an aqueous solution containing the following components is preferably used.
  • pH adjusters such as water-soluble organic acids, inorganic acids and their salts
  • the printing plate material of the present invention can be printed by imagewise heating such as image exposure with an infrared laser to form an image, followed by development with dampening water or dampening water and printing ink on a printing press. .
  • the printing plate material after image formation is directly attached to the plate cylinder of the printing press, or image formation is performed after the printing plate material is attached to the printing plate cylinder, and a water supply roller and Alternatively, the non-image portion of the heat-sensitive image forming layer can be removed by bringing the ink supply roller into contact with the printing plate material.
  • Removal of the non-image area (unexposed area) of the heat-sensitive image forming layer on the printing press can be performed by contacting a watering roller or an ink roller while rotating the plate cylinder. It can be performed by various sequences as shown in FIG.
  • the amount of water adjustment that can be adjusted to increase or decrease the amount of dampening water required for printing is divided into multiple stages. Or you can change it steplessly.
  • the heat-sensitive image-forming layer according to the present invention is a layer obtained by applying and drying a specific blocked isocyanate compound mixture, so that it can be stored even in a relatively high temperature environment.
  • An aluminum plate (material 1050, tempered H16) with a thickness of 0.24 mm is immersed in a 1% by weight sodium hydroxide aqueous solution at 50 ° C and dissolved so that the dissolution amount is 2 g / m 2. After washing with water, it was immersed in a 5 mass% nitric acid aqueous solution at 25 ° C for 30 seconds, neutralized, and then washed with water.
  • the distance between the electrode and the sample surface at this time was 10 mm.
  • the electrolytic surface-roughening treatment was divided into 10 times, and the amount of electricity processed (at the time of anode) was set to 60 CZdm 2 for a total amount of electricity treated at 600 CZdm 2 (for anode).
  • a 4-second pause was provided between each surface roughening treatment.
  • a hydrophilic layer coating solution to be described later was applied to the surface of the lower layer of the aluminum plate coated with this lower layer using a wire bar and dried at 120 ° C. for 1 minute.
  • the dry weight of the hydrophilic layer was set to 4 gZm 2 .
  • the aluminum plate coated and formed up to the hydrophilic layer was aged at 60 ° C. for 48 hours to obtain Substrate 2.
  • Hydrophilic layer lower layer coating solution composition solid content 20% by mass (Numerical values not shown in the table indicate parts by mass)
  • Colloidal silica (alkaline): Snowtex XS
  • Kiichipon black pigment particles SD9020
  • Si-based surfactant FZ2161 manufactured by Niuni Rikiichi 4.00
  • the materials excluding the surfactants in the table below were mixed and dispersed for 10 minutes at 10,000 rotations using a homogenizer. Next, a surfactant was added thereto, and the mixture was weakly stirred and then filtered to obtain a hydrophilic layer coating solution having a solid content of 30% by mass.
  • Hydrophilic layer coating solution composition solid content 30% by mass (Numerical values not indicated in the table indicate parts by mass)
  • Each printing plate material was brazed and fixed to an exposure drum.
  • a laser beam with a wavelength of 830 nm and a spot diameter of about 18 / zm was used for exposure, and an image was formed with 175 lines at 2400 dpi (dpi represents 2.5 dots per 54 cm).
  • the exposed image includes a solid image and a dot image of 1 to 99%.
  • the exposure energy was varied from 300 mj / cm 2 to 600 mj / cm 2 in increments of 50 mj / cm 2 , and the above image was exposed at each exposure energy.
  • the printing paper was changed to high-quality paper (Shirao), and printing was performed up to 10,000 sheets.
  • a good image is defined as having a density of 1.5 or higher when there is no background stain and the solid image portion exposed with any exposure energy of 300 to 600 mjZcm 2 .
  • the 500th printed material was observed, and the image formation sensitivity was evaluated for each of the solid image and the 3% halftone dot image, and used as an index of sensitivity.
  • the evaluation index was as follows. The results are shown in Table 4.
  • Blocked isocyanate dispersion WB-700 (Mitsui Takeda Chemical Co., Ltd., isocyanate compound: TDI (tolylene diisocyanate) with trimethylolpropane, blocking agent: oxime, dissociation temperature: 120 ° While stirring, 10.0 parts by mass of C, solid content (44% by mass), the mixture was diluted with 75.0 parts by mass of pure water.
  • WB-700 Mitsubishi Chemical Co., Ltd.
  • isocyanate compound TDI (tolylene diisocyanate) with trimethylolpropane
  • blocking agent oxime
  • dissociation temperature 120 ° While stirring, 10.0 parts by mass of C, solid content (44% by mass), the mixture was diluted with 75.0 parts by mass of pure water.
  • Water-insoluble infrared-absorbing dye having the following structure dissolves in IPA. Since it does not dissolve in the water ZIPA mixed solvent having the above ratio, the dye precipitates immediately after dropping the IPA solution. At this time, since the dye is considered to selectively precipitate on the surface of the dispersed blocked isocyanate compound, the above-mentioned aqueous dispersion contains the blocked isocyanate compound and the water-insoluble infrared absorbing dye. It is considered to be an aqueous dispersion of a composite dispersion.
  • the image forming layer coating solutions (12) and (13) were respectively applied to the hydrophilic layer surface of the substrate 2 and dried at 55 ° C. for 1 minute. Drying with the amount of the image forming layer was adjusted to 0. 4gZm 2. Next, this was subjected to an aging treatment at 55 ° C. for 48 hours to obtain printing plate materials 12 to 14.
  • Example 6 Each printing plate material was exposed and printed in the same manner as in Example 1, and the appropriate image formation sensitivity was evaluated for the 3% halftone dot image of each printing plate material. The results are shown in Table 6.
  • Each printing plate material was brazed and fixed to an exposure drum.
  • a laser beam with a wavelength of 830 nm and a spot diameter of about 18 m was used for exposure, and an image was formed with 2400 dpi (dpi represents the number of dots per 2.54 cm) and 175 lines.
  • the exposed image includes a solid image and a dot image of 1 to 99%.
  • the exposure energy was the exposure energy of the appropriate image formation sensitivity for each of the printing plate materials 12-13.
  • the printing plate material after exposure was directly attached to the plate cylinder, and printing was performed up to 30,000 sheets using the same printing conditions and printing sequence as the PS plate.
  • Printed material was sampled every 1000 sheets, and the degree of image deterioration in the 3% halftone image area and solid image area was confirmed.
  • the point at which halftone dot breakage was 30% or more when observed with a magnifying glass was defined as the printing end point, and the number of sheets was defined as the number of printing endurances.
  • the printing plate material of the present invention can form images with high sensitivity, that is, with low exposure energy, and high printing durability can be obtained even with images formed with low exposure energy. Squeezes.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne un matériau de plaque d’impression qui peut présenter des propriétés de développement de presse, une forte sensibilité et une excellente durabilité d’impression. Le matériau de plaque d’impression comprend un matériau de base possédant une surface hydrophile et une couche de formation d’image thermique, présentant des propriétés de développement de presse, disposée sur le matériau de base. Ledit matériau de plaque d’impression se caractérise en ce que la couche de formation d’image thermique comprend (A) un composé soluble dans l’eau contenant un ou plusieurs groupes époxy dans sa molécule et (B) un composé imidazole.
PCT/JP2006/313935 2005-08-09 2006-07-13 Matériau de plaque d’impression WO2007018013A1 (fr)

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