WO2020255918A1 - 水なし平版印刷版の染色方法、および平版印刷版用染色液 - Google Patents
水なし平版印刷版の染色方法、および平版印刷版用染色液 Download PDFInfo
- Publication number
- WO2020255918A1 WO2020255918A1 PCT/JP2020/023391 JP2020023391W WO2020255918A1 WO 2020255918 A1 WO2020255918 A1 WO 2020255918A1 JP 2020023391 W JP2020023391 W JP 2020023391W WO 2020255918 A1 WO2020255918 A1 WO 2020255918A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dyeing
- lithographic printing
- printing plate
- mass
- solution
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0069—Non aqueous dispersions of pigments containing only a solvent and a dispersing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/08—Damping; Neutralising or similar differentiation treatments for lithographic printing formes; Gumming or finishing solutions, fountain solutions, correction or deletion fluids, or on-press development
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/3042—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations
- G03F7/305—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations characterised by the brushing or rubbing means
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
Definitions
- the present invention relates to a method for dyeing a waterless lithographic printing plate and a dyeing solution for a lithographic printing plate.
- an image portion is usually dyed in order to determine the end point of development during or after development using an automatic developing machine or the like, that is, for the purpose of improving plate inspection. ..
- a method of spraying or immersing a dyeing solution containing a dye and dyeing only the image portion is usually used.
- a dyeing solution generally, at least one selected from basic dyes, disperse dyes, and acid dyes is used alone or in combination of two or more kinds such as water, alcohols, ketones, and ethers. Those dissolved or dispersed in a solvent are used. Further, in order to improve dyeability, organic acids, inorganic acids, amines, surfactants, dyeing aids and the like are added.
- Patent Document 1 a dyeing solution used for dyeing an image portion of a waterless lithographic printing plate contains an anionic surfactant having a branched structure having 3 to 30 carbon atoms.
- Patent Document 2 sludge is contained by containing one or more kinds of dipropylene glycol monoalkyl ether and tripropylene glycol monoalkyl ether in addition to an anionic surfactant having a branched structure having 3 to 30 carbon atoms. Attempts are being made to further improve the foaming prevention effect while suppressing the occurrence (see Patent Document 2).
- a dyeing solution containing an anionic surfactant having a branched structure having 3 to 30 carbon atoms as described in Patent Document 1 has a small decrease in dyeing concentration as a whole lithographic printing plate, but lithographic printing. There was a problem of "dyeing unevenness" in which a part of the plate had poor dyeing and the image area ratio was not displayed correctly. Further, when water contains a sparingly soluble organic solvent, sludge mainly composed of dye may be generated.
- the present invention is, as a first embodiment, a dyeing solution used for dyeing an image portion formed on a lithographic printing plate original plate, wherein (a) a dye, (b) the following general formula (1).
- a plate dyeing solution is provided.
- R 1- X (1)
- R 1 represents a linear alkyl group having 3 to 30 carbon atoms or a linear alkenyl group having 3 to 30 carbon atoms.
- X represents SO 3 Na, SO 3 K, COONa, COONH 4 or Indicates COOK.
- the present invention is a method of dyeing an image portion formed on a waterless lithographic printing plate using a dyeing solution containing an organic solvent as a second embodiment, wherein the image portion is covered with a polymer compound.
- a method for dyeing a waterless lithographic printing plate wherein the SP value ⁇ of the organic solvent and the SP value ⁇ of the polymer compound satisfy the relationship of
- the first embodiment of the present invention even if a large amount of plates are dyed, it is possible to obtain a dyeing solution for lithographic printing plates showing stable plate-testability with little decrease in dyeing concentration and less uneven dyeing. it can. Further, according to the second embodiment of the present invention, a method for dyeing a waterless lithographic printing plate, which exhibits stable plate-testability with little decrease in dyeing concentration and less uneven dyeing even when a large amount of plates are dyed. Can be provided.
- the dyeing solution for lithographic printing plates according to the first embodiment of the present invention will be described below.
- the lithographic printing plate dyeing solution according to the first embodiment of the present invention is used for dyeing an image portion formed by exposing and developing a lithographic printing plate original plate, and is reflected light of a non-image portion.
- the plate inspection property of the lithographic printing plate is improved by the difference (dyeing density) between the density and the reflected light density of the image portion.
- the dyeing solution for lithographic printing plates according to the present invention contains (a) a dye.
- a dye examples include basic dyes, acid dyes, direct dyes, disperse dyes, reactive dyes and the like, and one or more of these can be used. it can.
- the basic dye is preferably used because it has a high adsorption power to the image portion and a high dyeing concentration can be obtained.
- Examples of basic dyes include methyl violet, ethyl violet, basic fuxin, basic red 9, malakite green oxalate, brilliant green, Victoria blue B, crystal violet, basic green 1, basic blue 1, basic blue 7, and so on.
- Triphenylmethane basic dyes such as Basic Blue 20, xanthene basic dyes such as Rhodamine 6G, Rhodamine B, Rhodamine 123, Rhodamine 19, diphenylmethane basic dyes such as auramine, and azine basic dyes such as safranin.
- Oxazine-based dyes such as Basic Blue 3, Basic Yellow 28, Basic Red 13, Metin-based basic dyes such as Basic Violet 7, Basic Orange 2, Azo-based basic dyes such as Basic Brown 1, Basic Blue 17, Basic Blue 24.
- Thiadine dyes such as methylene blue can be mentioned.
- triphenylmethane-based basic dyes such as methyl violet, ethyl violet, basic fuchsin, basic red 9, Victoria blue B, crystal violet, basic blue 1, basic blue 7, and basic blue 20 are more preferable.
- the dye (a) it is preferable to use a dye having a maximum absorption wavelength ( ⁇ max ) in the wavelength range of 400 nm to 600 nm. Since many lithographic printing plates have a green color, the dyeing density of the image portion can be effectively increased by using such a dye because of the complementary color. Therefore, it is possible to efficiently increase the dyeing density of the image portion, and it is preferable because better plate inspection property can be obtained.
- ⁇ max maximum absorption wavelength
- the content of these (a) dyes is preferably 0.05% by mass or more in the dyeing solution.
- the content of the dye is more preferably 0.10% by mass or more in the dyeing solution.
- the content of the dye is more preferably 1.00% by mass or less in the dyeing solution.
- the dyeing solution for lithographic printing plates according to the first embodiment of the present invention contains (b) an anionic surfactant represented by the following general formula (1).
- R 1- X (1) (In the formula, R 1 represents a linear alkyl group having 3 to 30 carbon atoms or a linear alkenyl group having 3 to 30 carbon atoms. X represents SO 3 Na, SO 3 K, COONa, COONH 4 or Indicates COOK.)
- R 1 in the general formula (1) is a linear alkyl group having 3 to 30 carbon atoms or a linear alkenyl group having 3 to 30 carbon atoms.
- R 1 is preferably a linear alkyl group having 3 to 20 carbon atoms or a linear alkenyl group having 3 to 20 carbon atoms. Since it is linear, it has a higher effect of suppressing uneven dyeing as compared with those having branches.
- the number of carbon atoms of R 1 is 3 or more, the cleaning ability of the surfactant is improved, the sludge generation suppressing effect is sufficient when a large amount of lithographic printing plate is processed, and the dyeing concentration is improved, which is preferable.
- the number of carbon atoms is preferably 4 or more, and more preferably 6 or more. Further, when the carbon number of R 1 is 30 or less, the hydrophobicity does not become too large and the dissolution in the dyeing solution becomes easy, which is preferable.
- the number of carbon atoms is preferably 20 or less, and more preferably 12 or less, from the viewpoint of sufficiently obtaining the cleaning ability of the surfactant and suppressing uneven dyeing.
- X in the general formula (1) represents a hydrophilic group of an anionic surfactant and is at least one selected from the group consisting of SO 3 Na, SO 3 K, COONa, COONH 4 and COOK.
- X is preferably SO 3 Na or COONa, and more preferably SO 3 Na.
- anionic surfactant represented by the general formula (1) examples include sodium octadecane sulfonate, sodium hexadecane sulfonate, sodium pentadecane sulfonate, sodium tetradecane sulfonate, sodium dodecane sulfonate, and dodecane sulfonic acid.
- potassium behenate sodium stearate, ammonium stearate, stearic acid
- Potassium sodium oleate, ammonium oleate, potassium oleate, sodium linoleate, ammonium linolenate, potassium linoleate, sodium palmitate, ammonium palmitate, potassium palmitate, sodium myristate, potassium myristate, sodium laurate, Ammonium laurate, potassium laurate, sodium decanoate, ammonium decanoate, potassium decanoate, sodium nonate, potassium nonanoate, sodium octanate, potassium octanate, sodium heptate, ammonium
- the content of such an anionic surfactant is preferably 0.010% by mass or more in the dyeing solution in terms of suppressing the generation of sludge in the dyeing solution and further suppressing the decrease in dyeing concentration and uneven dyeing.
- the content of the anionic surfactant is more preferably 0.020% by mass or more in the dyeing solution. Further, it is preferably 2.0% by mass or less in the dyeing solution, and more preferably 1.0% by mass or less in the dyeing solution, in that the generation of foaming of the dyeing solution can be suppressed and the decrease in the dyeing concentration can be suppressed.
- the dyeing solution for lithographic printing plates according to the first embodiment of the present invention has (c) an organic solvent containing at least one of ethers and alcohols.
- ethers and alcohols include ethers such as cyclic ethers, monoethers and polyethers, and alcohols such as monohydric alcohols, dihydric alcohols and trihydric alcohols. Can be used alone or in combination of two or more.
- the ethers preferably used in the dyeing solution for flat plate printing plate according to the first embodiment of the present invention include ethylene glycol monoethyl ether and ethylene because the decrease in dyeing concentration is small and the effect of suppressing dyeing unevenness is large.
- dipropylene glycol monoalkyl ether or tripropylene glycol monoalkyl ether represented by the following general formula (2) is more preferably used because it has a greater effect of suppressing dyeing unevenness.
- R 2- (OC 3 H 6 ) n-OH (2) (In general formula (2), R 2 is any of CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , C 5 H 11 , and C 6 H 13 , and n is 2 or 3. In addition, (OC 3 H 6 ) may be independently branched or linear.)
- dipropylene glycol monoalkyl ether or tripropylene glycol monoalkyl ether examples include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and dipropylene.
- Glycol monohexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether and the like can be mentioned, and among these, n is 3 in the general formula (2).
- Tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether and other tripropylene glycol monoalkyl ethers are more preferable.
- the dyeing solution easily permeates the image portion of the lithographic printing plate, and the dyeing concentration.
- the solubility parameter (SP value) is 9.0 to 13.0 (cal / cm 3 ) 1/2 (18.45 to 26.65 (MPa)) from the viewpoint of increasing the size and improving the plate inspection property. 1/2 ) is preferable.
- the SP value can be calculated using the Fedors estimation method.
- alcohols include ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, n-hexanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, and tetra.
- examples thereof include ethylene glycol and tripropylene glycol.
- ethers include ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl.
- tripropylene glycol and 3-methyl-3-methoxybutanol are preferable in terms of stainability, safety, and cost.
- the SP values of alcohols and ethers are more preferably 9.5 to 12.5 (cal / cm 3 ) 1/2 (19.48 to 25.63 (MPa) 1/2 ).
- alcohols and ethers as organic solvents used in the dyeing solution for lithographic printing plates according to the first embodiment of the present invention have a vapor pressure of 2000 Pa or less at 1 atm and 20 ° C. preferable.
- alcohols or ethers and water are mixed as a solvent for the dyeing solution and used as a mixed solvent, if the vapor pressure of the alcohols and ethers at 20 ° C. is 2000 Pa or less, the generation of hedro is suppressed and staining is performed. This is because the decrease in concentration can be reduced. This is because the vapor pressure of water at 20 ° C. is 2330 Pa, so if alcohols or ethers having a vapor pressure of 2000 Pa or less at 20 ° C.
- alcohols or ethers that volatilize from the dyeing solution during the large-scale treatment of the plate. It is considered that the class is smaller than water, the dissolution stability of the dye in the dyeing solution is high, and the generation of hedro is suppressed.
- examples of such alcohols include n-propanol, n-butanol, 2-butanol, tert-butanol, n-hexanol, 3-methyl-3-methoxybutanol, tetraethylene glycol, tripropylene glycol and the like. Yes, 3-methyl-3-methoxybutanol is more preferred.
- ethers include ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, diethylene glycol monomethyl ether, and diethylene glycol.
- the content of the organic solvent containing at least one of (c) ethers and alcohols contained in the lithographic printing plate dyeing solution according to the first embodiment of the present invention is 3.0% by mass or more in the dyeing solution. It is preferably 30.0% by mass, more preferably 5.0% by mass to 25.0% by mass, and even more preferably 7.5% by mass to 20.0% by mass.
- C By setting the content of ethers and alcohols to 3.0% by mass or more, the dyeing solution easily permeates the image portion of the lithographic printing plate, and the dyeing concentration can be maintained in a high state. On the other hand, when it is set to 30.0% by mass or less, it is not disadvantageous from an economical point of view, and the non-image portion of the lithographic printing plate is less likely to be peeled off.
- the method for dyeing a lithographic printing plate using the lithographic printing plate dyeing solution according to the first embodiment is a method for dyeing a lithographic printing plate according to the first embodiment of the present invention with respect to a lithographic printing plate original plate during or after development. It is obtained by a method of dyeing an image portion with a dyeing solution for printing.
- the lithographic printing plate original plate, the lithographic printing plate manufacturing method, and the dyeing method are described later in ⁇ Planographic printing plate original plate used in the second embodiment> and ⁇ Planographic printing plate manufacturing method used in the second embodiment>.
- And ⁇ Dyeing method for lithographic printing plate according to the second embodiment> are described later in ⁇ Planographic printing plate original plate used in the second embodiment> and ⁇ Planographic printing plate manufacturing method used in the second embodiment>.
- the solubility parameter (SP value) ⁇ of the polymer compound contained in the image portion is used.
- the SP value ⁇ of the organic solvent satisfies the relationship of
- the organic solvent contained in the dyeing solution used in the second embodiment of the present invention slightly dissolves the image portion formed on the lithographic printing plate and allows the dye to penetrate into the image portion to improve the dyeability. Has an effect. Therefore, the SP value ⁇ of the polymer compound contained in the image portion and the SP value ⁇ of the organic solvent should be close to each other, and
- the SP value can be calculated using the Fedors estimation method.
- the SP value of each component is multiplied by the content ratio and totaled.
- the SP value be the value obtained.
- the dyeing solution used in the second embodiment of the present invention contains organic solvent 1 (SP value: ⁇ 1 ) and organic solvent 2 (SP value: ⁇ 2 ) in a mass ratio of 6: 4.
- the SP value ⁇ of the organic solvent is represented by ⁇ 1 ⁇ 0.6 + ⁇ 2 ⁇ 0.4.
- the polymer compound contained in the image portion preferably has an SP value of 10 to 17 (cal / cm 3 ) 1/2 (20.5 to 34.85 (MPa) 1/2 ), and is preferably 12 to 17. (Cal / cm 3 ) 1/2 (24.6 to 34.85 (MPa) 1/2 ) is more preferable.
- polymer compounds examples include phenol novolac resin (SP value: 16.4 (cal / cm 3 ) 1/2 (33.62 (MPa) 1/2 )) and cresol novolac resin (SP value: Phenolic resins such as 15.2 (cal / cm 3 ) 1/2 (31.16 (MPa) 1/2 )), imino-based methylated melamine resins (SP value: 13.8 (cal / cm 3 ) 1 / 2 (28.29 (MPa) 1/2 )), methylol-type methylated melamine resin (SP value: 11.5 (cal / cm 3 ) 1/2 (23.58 (MPa) 1/2 )), Melamine resins such as alkyl-type methylated melamine resins (SP value: 10.5 (cal / cm 3 ) 1/2 (21.53 (MPa) 1/2 )), epoxy resins (SP value: 10.9 (cal)) / Cm 3 ) 1/2 (22.35 (MPa) 1/2 )), nitrocellulose (SP value: 10.1 (cal
- the organic solvent and the polymer compound described in the present specification can be arbitrarily used, and for example, alcohols and novolak resin, Examples include a combination of alcohols and melamine resin. Among them, tripropylene glycol and phenol novolac resin, tripropylene glycol and imino-based methylated melamine resin, dipropylene glycol monobutyl ether and imino-based methylated melamine resin, 3-methyl-3-methoxybutanol and imino-based methylated. A combination of melamine resins is preferred.
- the dyeing solution As the organic solvent contained in the dyeing solution used in the second embodiment of the present invention, the dyeing solution easily permeates the image portion of the lithographic printing plate, the dyeing concentration becomes higher, and the plate inspection property becomes better. Therefore, it is preferable that the SP value is 9.0 to 13.0 (cal / cm 3 ) 1/2 (18.45 to 26.65 (MPa) 1/2 ).
- the organic solvent is preferably ethers and / or alcohols, and more preferably an organic solvent containing at least one of (c) ethers and alcohols described in the first embodiment.
- the dyeing solution used in the second embodiment of the present invention may contain the dye (a) described in the first embodiment.
- the stain used in the second embodiment of the present invention may contain the anionic surfactant described in the first embodiment. More preferably, it contains an anionic surfactant represented by the following general formula (3).
- R 1- X (3) (In the formula, R 1 represents a linear alkyl group having 6 to 10 carbon atoms. X represents SO 3 Na, SO 3 K, COONa, COONH 4 or COOK.) Specific examples of the anionic surfactant include the anionic surfactant represented by the above general formula (1).
- the lithographic printing plate original plate used in the second embodiment of the present invention can be used for both ordinary lithographic printing plates with water and lithographic printing plates without water, but waterless lithographic printing plates are more preferable from the viewpoint of dyeability.
- the waterless lithographic plate used in the second embodiment of the present invention has a substrate. It also has at least a heat sensitive layer and an ink repellent layer on or above the substrate. There may be either a heat-sensitive layer or an ink repellent layer near the substrate, but it is preferable that the substrate, the heat-sensitive layer, and the ink repellent layer are in this order.
- the heat-sensitive layer of the waterless planographic plate contains a polymer compound.
- the polymer compound is the same as the polymer compound contained in the image portion described in the above-mentioned ⁇ Staining solution used in the second embodiment>.
- the polymer compound is preferably contained in the heat-sensitive layer of the waterless planographic plate in an amount of preferably 50% by mass or more, more preferably 70% by mass or more. It is preferable that the polymer compound is contained in an amount of 50% by mass or more because uneven dyeing can be reduced and stable plate inspection can be obtained. Further, the polymer compound is preferably contained in the heat-sensitive layer of the waterless planographic plate in an amount of 95% by mass or less, more preferably 90% by mass or less. When the polymer compound is contained in an amount of 95% by mass or less, it is possible to prevent the dyeing solution from excessively dissolving the image portion and suppress a decrease in the dyeing concentration, which is preferable.
- the method for producing a lithographic printing plate used in the second embodiment is obtained by a method including either the following step (1) or the following step (2) with respect to the lithographic printing plate original plate.
- Steps (1) A step of exposing according to the image (exposure step) Steps (2) After the exposure steps (A), (B) a step of applying physical friction to the exposed planographic printing plate original plate to remove the ink repulsion layer in the exposed portion (development step).
- the obtained lithographic printing plate has an ink repulsion layer corresponding to an exposed portion removed on the surface of the lithographic printing plate original plate.
- the exposure process will be described.
- the lithographic printing plate original plate is exposed according to the image.
- the lithographic printing plate original plate has a protective film, it may be exposed from above the protective film, or the protective film may be peeled off and exposed.
- the light source used in the (A) exposure step include those having an emission wavelength region in the range of 300 nm to 1500 nm. Among these, since it is widely used as the absorption wavelength of the heat-sensitive layer, a semiconductor laser or a YAG laser having an emission wavelength region near the near infrared region is preferably used.
- laser light having wavelengths of 780 nm, 808 nm, 830 nm, and 1064 nm is preferably used for exposure.
- the exposure amount is preferably 150 mJ / cm 2 or more in that the image portion is thermally decomposed, the dyeing solution easily permeates, and the dyeing density is improved.
- the ink repulsion layer of the exposed portion is removed by applying physical friction to the lithographic printing plate original plate after exposure.
- the method of applying physical friction include (i) wiping the plate surface with a non-woven fabric impregnated with a developer, absorbent cotton, cloth, sponge, etc., and (ii) showering tap water after pretreating the plate surface with a developer. While rubbing with a rotating brush, (iii) high-pressure water, hot water, or steam is sprayed onto the plate surface.
- pretreatment may be performed by immersing the lithographic printing plate original plate in the pretreatment liquid for a certain period of time.
- the pretreatment liquid for example, water, a solvent obtained by adding a polar solvent such as alcohol, ketone, ester, or carboxylic acid to water, a solvent containing at least one of aliphatic hydrocarbons, aromatic hydrocarbons, and the like.
- a polar solvent is added to the mixture, or a polar solvent is used.
- a pretreatment liquid for example, as described in Japanese Patent No. 4839987, a pretreatment liquid containing a polyethylene ether diol and a diamine compound having two or more primary amino groups can be used.
- pretreatment liquid examples include PP-1, PP-3, PP-F, PP-FII, PTS-1, CP-1, CP-Y, NP-1, and DP-1 (all of Toray Industries, Inc.). ) Made) and so on.
- the developing solution for example, water, an aqueous solution in which 50% by mass or more of the whole solution is water, alcohol or paraffinic hydrocarbon can be used. Further, a mixture of propylene glycol derivatives such as propylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, and an alkylene oxide adduct to polypropylene glycol and water can also be used. Specific examples of the developing solution include HP-7N and WH-3 (both manufactured by Toray Industries, Inc.). Ordinary surfactants can also be added to the composition of the above developer. As the surfactant, those having a pH of 5 to 8 when made into an aqueous solution are preferable from the viewpoints of safety, cost at the time of disposal, and the like.
- the content of the surfactant is preferably 10% by mass or less of the developer.
- Such a developer is highly safe and is also preferable in terms of economy such as disposal cost.
- the developing solution does not contain an organic solvent so that the exposed portion (image portion) is not dissolved too much and uneven dyeing does not occur.
- the exposed portion (image portion) from which the ink repulsion layer has been removed is dyed with the dyeing solution used in the second embodiment of the present invention.
- the image portion may be dyed with the dyeing solution at the same time as the development, or may be dyed after the development.
- dyeing may be performed while rubbing with a brush or the like.
- a step of drying the dyeing solution on the image part may be included in order to fix the dye and improve the dyeing density. Examples of the drying method include heating and blowing air, but the drying method is not particularly limited.
- a part or all of the above-mentioned developing steps may be automatically performed by an automatic developing machine.
- the following devices can be used as the automatic developing machine.
- Specific examples of such an automatic developing machine are described in TWL-650 series, TWL-860 series, TWL-1160 series (all manufactured by Toray Industries, Inc.), and Japanese Patent Application Laid-Open No. 5-6000.
- an automatic developing machine in which the cradle is dented in a curved shape in order to suppress the occurrence of scratches on the back surface of the plate.
- the dyeing solution of the present invention is introduced into the post-treatment section and used.
- the present invention will be described based on examples, but the present invention is not limited to these examples.
- a solid image and 50% halftone dots were provided at 175 lpi of 2400 dpi on a lithographic printing plate original plate having a length of 560 mm and a width of 335 mm.
- Tap water in the pretreatment tank and developing tank of the automatic developing machine "TWL-1160F" (manufactured by Toray Co., Ltd.), and the dyeing liquids of Examples and Comparative Examples in the post-treatment tank (planographic printing plate dyeing liquid-1 to lithographic printing plate) A total of 1000 planographic printing plates were produced by charging tap water into a printing plate dyeing solution-15) and a washing tank and passing the exposed original plate at a speed of 40 cm / min.
- a solid image and 50% halftone dots were provided at 175 lpi of 2400 dpi on a lithographic printing plate original plate having a length of 560 mm and a width of 335 mm.
- the post-treatment tank was charged with a dyeing solution (lithographic printing plate dyeing solution-16 to lithographic printing plate dyeing solution-21) and tap water in a water washing tank.
- a total of 1000 planographic printing plates were produced by passing the exposed original plate at a speed of 40 cm / min. Further, in Example 20, after the exposed original plate has passed through the post-treatment tank, a hot air generator "HAP3051" (manufactured by Hakkou Denki Co., Ltd.) is used to air volume: 2 m 3 / min and outlet gas temperature: 100 ° C. , Distance to the image part: The post-treatment liquid on the image part was dried with hot air under the condition of 10 cm.
- HAP3051 manufactured by Hakkou Denki Co., Ltd.
- the solid image of the lithographic printing plate obtained on the first sheet is captured by the reflection densitometer "spectro eye” (manufactured by X-rite).
- the measured and obtained reflected light density was taken as the reflected light density of the image portion.
- the non-image part was measured with a reflection densitometer "spectro eye” (manufactured by X-rite), and the obtained value was taken as the reflected light density of the non-image part.
- the reflected light density is measured with cyan, yellow, or magenta filters applied, and the absolute value of the difference between the reflected density of the non-image area and the reflected light density of the image area with each filter applied is calculated.
- the density measurement mode Cyan was selected as the filter in, and the reflection densities of the exposed and unexposed areas were measured. Then, after changing the filter to yellow and magenta, the measurement was performed in the same manner.
- Example 1 The lithographic printing plate dyeing solution-1 was obtained by stirring and mixing the following components at room temperature.
- Dye Rhodamine 6G (xanthene-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.250 parts by mass
- Example 2 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-2.
- the dyeing concentration of the first sheet was 0.61
- the dyeing concentration of the 1000th sheet was 0.47
- the dyeing concentration retention rate was 77.0%.
- the number of dyeing irregularities was 18, and good results were obtained.
- Example 3 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-3.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.250 parts by mass
- the dyeing concentration of the first sheet was 0.55
- the dyeing concentration of the 1000th sheet was 0.42
- the dyeing concentration retention rate was 76.4%.
- the number of dyeing irregularities was 14, and good results were obtained.
- Example 4 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-4.
- the dyeing concentration of the first sheet was 0.52
- the dyeing concentration of the 1000th sheet was 0.40
- the dyeing concentration retention rate was 76.9%.
- the number of dyeing irregularities was 10, and good results were obtained.
- Example 5 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-5.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.250 parts by mass
- Organic solvent: methanol (alcohols, SP value) : ⁇ 13.8 (cal / cm 3 ) 1/2 , steam pressure: 12300 Pa (20 ° C)) (manufactured by Wako Pure Chemical Industry Co., Ltd.): 9.0 parts by mass
- the dyeing concentration of the first sheet was 0.52
- the dyeing concentration of the 1000th sheet was 0.40
- the dyeing concentration retention rate was 76.9%.
- the number of dyeing irregularities was 10, and good results were obtained.
- Example 6 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-6.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.250 parts by mass
- Anionic surfactant Sodium hexanesulfonate (general formula (1))
- R 1 linear alkyl group having 6 carbon atoms
- X SO 3 Na) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.025 parts by mass
- the dyeing concentration of the first sheet was 0.66
- the dyeing concentration of the 1000th sheet was 0.63
- the dyeing concentration retention rate was 95.5%.
- the number of uneven dyeing was 4, and good results were obtained.
- Example 7 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-7.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.250 parts by mass
- Anionic surfactant Sodium hexanesulfonate (general formula (1))
- R 1 linear alkyl group having 6 carbon atoms
- the dyeing concentration of the first sheet was 0.70
- the dyeing concentration of the 1000th sheet was 0.68
- the dyeing concentration retention rate was 97.1%.
- the number of dyeing irregularities was 2, and very good results were obtained.
- Example 8 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-8.
- lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-8.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.500 parts by mass
- Water 90.5 parts by mass
- the dyeing solution for flat plate printing plate The total amount of each component (a) to (d) is 100 parts by mass.
- the dyeing concentration of the first sheet was 1.16
- the dyeing concentration of the 1000th sheet was 1.11
- the dyeing concentration retention rate was 95.7%.
- the number of dyeing irregularities was 2, and very good results were obtained.
- Example 9 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-9.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.250 parts by mass
- Anionic surfactant Sodium hexanesulfonate (general formula (1))
- R 1 linear alkyl group having 6 carbon atoms
- X SO 3 Na) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.025 parts by mass
- the dyeing concentration of the first sheet was 0.66
- the dyeing concentration of the 1000th sheet was 0.65
- the dyeing concentration retention rate was 98.5%.
- the number of dyeing irregularities was 4, and very good results were obtained.
- Example 10 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-10.
- the dyeing concentration of the first sheet was 0.75
- the dyeing concentration of the 1000th sheet was 0.74
- the dyeing concentration retention rate was 98.7%.
- the number of dyeing irregularities was 2, and very good results were obtained.
- the dyeing concentration of the first sheet was 0.19 and the dyeing concentration of the 1000th sheet was 0.00, which was impractical in terms of the dyeing concentration.
- the result was. It is considered that the cause is that the dissolution stability of the dye in the dyeing solution is low and the dyeing concentration is lowered.
- Example 2 The evaluation was carried out in the same manner as in Example 1 except that the lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-12.
- lithographic printing plate dyeing solution-1 was changed to the following lithographic printing plate dyeing solution-12.
- Dye Ethyl violet (triphenylmethane-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.250 parts by mass
- Nonionic surfactant Polyoxyethylene lauryl ether (Wako Pure Chemical Industries, Ltd.
- the dyeing concentration of the first sheet was 0.24
- the dyeing concentration of the 1000th sheet was 0.20
- the dyeing concentration retention rate was 83.3%.
- the number of uneven dyeing was 32, which was not practical in terms of dyeing density and uneven dyeing.
- the dyeing concentration of the first sheet was 0.50
- the dyeing concentration of the 1000th sheet was 0.38
- the dyeing concentration retention rate was 76.0%.
- the number of uneven dyeing was 24, which was not practical due to uneven dyeing.
- the dyeing concentration of the first sheet was 0.49
- the dyeing concentration of the 1000th sheet was 0.37
- the dyeing concentration retention rate was 75.5%.
- the number of uneven dyeing was 25, which was not practical due to uneven dyeing.
- Example 11 (A) Preparation of waterless planographic printing plate original plate-1 The following organic layer composition solution was applied on a degreased aluminum substrate (manufactured by Mitsubishi Aluminum Co., Ltd.) having a thickness of 0.24 mm, and dried at 200 ° C. for 90 seconds. , An organic layer having a thickness of 6.0 ⁇ m was provided. The organic layer composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).
- Image layer composition solution-1 was applied onto the organic layer with a wire bar coater and dried by heating at 140 ° C. for 90 seconds to provide a heat-sensitive layer having a thickness of 2.0 ⁇ m.
- the image layer composition solution-1 was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).
- ⁇ Image layer composition solution-1> Infrared absorbing dye (cyanine dye): NK5559 (manufactured by Hayashihara Co., Ltd., maximum absorption wavelength: 774 nm): 16.0 parts by mass
- Polymer compound: Methacrylic resin "parapet" (SP value: ⁇ 9. 1 (cal / cm 3 ) 1/2 ) (manufactured by Kuraray Co., Ltd.): 84 parts by mass
- Methyl ethyl ketone 900 parts by mass
- the silicone rubber layer composition solution prepared immediately before coating was applied onto the image layer with a wire bar coater, heated at 140 ° C. for 80 seconds, and provided with a silicone rubber layer having an average thickness of 2.0 ⁇ m without water.
- a lithographic printing plate original plate -1 was obtained.
- the silicone rubber layer composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).
- ⁇ Silicone rubber layer composition solution> (A) ⁇ , ⁇ -divinylpolydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 86.26 parts by mass (b) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 (Manufactured by Toray Dow Corning Co., Ltd.): 4.93 parts by mass (c) Vinyltris (methylethylketooxyimino) Silane: 2.64 parts by mass (d) Platinum catalyst SRX212 (manufactured by Toray Dow Corning Co., Ltd., platinum catalyst) Is 6.0% by mass): 6.17 parts by mass (e) "Isopar” E (manufactured by Esso Chemical Co., Ltd.): 900 parts by mass
- lithographic printing plate dyeing solution-16 The lithographic printing plate dyeing solution-16 was obtained by stirring and mixing the following components at room temperature.
- Example 12 Using the waterless lithographic printing plate original plate-2 obtained by changing the image layer composition solution-1 of the waterless lithographic printing plate original plate-1 to the following image layer composition solution-2, the dyeing solution -16 for the lithographic printing plate The evaluation was carried out in the same manner as in Example 11 except that the following lithographic printing plate dyeing solution-17 was used instead.
- Example 13 Using the waterless lithographic printing plate original plate -3 obtained by changing the image layer composition solution -1 of the lithographic printing plate original plate -1 to the following image layer composition solution -3, the dyeing solution -16 for the lithographic printing plate The evaluation was carried out in the same manner as in Example 11 except that the following lithographic printing plate dyeing solution-18 was used instead.
- Example 14 The evaluation was carried out in the same manner as in Example 13 except that the following dyeing solution for lithographic printing plates-19 was used instead of the dyeing solution for lithographic printing plates-18.
- Dye Rhodamine 6G (xanthene-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.50 parts by mass
- Organic solvent: 3-methyl-3-methoxybutanol (alcohols, SP value: ⁇ 10.5 ( cal / cm 3 ) 1/2 ), steam pressure: 67Pa (20 ° C)) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 9.0 parts by mass
- Water 90.45 parts
- Example 15 The evaluation was carried out in the same manner as in Example 13 except that the following dyeing solution for lithographic printing plates-20 was used instead of the dyeing solution for lithographic printing plates-18.
- Dye Rhodamine 6G (xanthene-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.50 parts by mass
- Water 90.45 parts by mass Using the obtained dyeing solution for flat plate
- Example 16 When evaluated by the above method using a waterless lithographic printing plate original plate-2 and a lithographic printing plate dyeing solution-20, the dyeing concentration of the first sheet was 1.00, and the dyeing concentration of the 1000th sheet was 0.95. The result was that the dyeing concentration retention rate was 95.0% and the number of uneven dyeings was 6.
- Example 17 The evaluation was carried out in the same manner as in Example 16 except that the following dyeing solution for lithographic printing plates-21 was used instead of the dyeing solution for lithographic printing plates-20.
- Dye Rhodamine 6G (xanthene-based basic dye) (manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0.50 parts by mass
- Example 18 The evaluation was carried out in the same manner as in Example 17 except that the exposure amount of the waterless planographic printing plate original plate- 2 was changed from 125 mJ / cm 2 to 150 mJ / cm 2 .
- the dyeing density of the first sheet was 1.20
- the dyeing density of the 1000th sheet was 1.18
- the retention rate of the dyeing concentration was 98.3%
- the number of uneven dyeing sheets was 3 sheets, which were very good. It was a good result.
- Example 19 In the development of the waterless planographic printing plate original plate-2, the evaluation was carried out in the same manner as in Example 18 except that the 10% triethylene glycol aqueous solution in the developing tank was changed to tap water.
- the dyeing density of the first sheet was 1.20
- the dyeing density of the 1000th sheet was 1.18
- the retention rate of the dyeing concentration was 98.3%
- the number of uneven dyeing sheets was 1 sheet, which were very good. It was a good result.
- Example 20 Evaluation was carried out in the same manner as in Example 19 except that the exposed waterless planographic printing plate original plate-2 passed through the post-treatment tank and then the post-treatment liquid on the image portion was dried with hot air.
- the dyeing density of the first sheet was 1.30
- the dyeing density of the 1000th sheet was 1.29
- the dyeing concentration retention rate was 99.2%
- the number of uneven dyeing sheets was 0, which were very good. It was a good result.
- Example 6 The same as in Example 11 except that the image layer composition solution-1 of the waterless lithographic printing plate original plate -1 was changed to the following image layer composition solution -4 and the waterless lithographic printing plate original plate -4 was used. And evaluated.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Coloring (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
R1-X (1)
(式中、R1は炭素数3~30の直鎖状のアルキル基または炭素数3~30の直鎖状のアルケニル基を示す。XはSO3Na、SO3K、COONa、COONH4またはCOOKを示す。)
本発明の第1の実施形態に関する平版印刷版用染色液について、以下に説明する。
本発明の第1の実施形態における平版印刷版用染色液とは、平版印刷版原版に対して露光・現像を行って形成された画像部を染色するために用いられ、非画像部の反射光濃度と画像部の反射光濃度との差(染色濃度)により平版印刷版の検版性を向上するものである。
R1-X (1)
(式中、R1は炭素数3~30の直鎖状のアルキル基または炭素数3~30の直鎖状のアルケニル基を示す。XはSO3Na、SO3K、COONa、COONH4またはCOOKを示す。)
R2-(OC3H6)n-OH (2)
(一般式(2)中、R2はCH3、C2H5、C3H7、C4H9、C5H11、およびC6H13のいずれかであり、nは2または3である。また、(OC3H6)は、それぞれ独立して分岐鎖および直鎖のいずれでもよいものとする。)
第1の実施形態に係る平版印刷版用染色液を用いた平版印刷版の染色方法は、平版印刷版原版に対し、現像中もしくは現像後に、本発明の第1の実施形態に係る平版印刷版用染色液を用いて画像部を染色する方法によって得られる。平版印刷版原版、平版印刷版の製造方法、および染色方法は、後述する<第2の実施形態に用いられる平版印刷版原版>、<第2の実施形態に用いられる平版印刷版の製造方法>、および<第2の実施形態に係る平版印刷版の染色方法>と同一である。
本発明の第2の実施形態に用いられる染色液は有機溶剤を含み、平版印刷版に形成された画像部を染色するため、前記画像部に含まれる高分子化合物の溶解度パラメーター(SP値)βと、前記有機溶剤のSP値αは、|β-α|<5(cal/cm3)1/2(|β-α|<10.25(MPa)1/2)の関係を満たす。
R1-X (3)
(式中、R1は炭素数6~10の直鎖状のアルキル基を示す。XはSO3Na、SO3K、COONa、COONH4またはCOOKを示す。)
アニオン性界面活性剤の具体例としては、上述の一般式(1)で示されるアニオン性界面活性剤を挙げることができる。
次に、本発明の第2の実施形態に用いられる平版印刷版原版について説明する。本発明の第2の実施形態に用いられる平版印刷版原版は、通常の水あり平版、水なし平版のいずれにも用いることができるが、染色性の点から、水なし平版がより好ましい。本発明の第2の実施形態に使用する水なし平版は、基板を有する。また、基板の上または上方に少なくとも感熱層およびインキ反発層を有する。基板の近くに感熱層およびインキ反発層のいずれがあってもいいが、基板、感熱層およびインキ反発層の順にあることが好ましい。
第2の実施形態に用いられる平版印刷版の製造方法は、上記平版印刷版原版に対して、下記工程(1)または下記工程(2)のいずれかを含む方法によって得られる。
工程(1)(A)像に従って露光する工程(露光工程)
工程(2)(A)露光工程後に、(B)露光した平版印刷版原版に物理的摩擦を加え、露光部のインキ反発層を除去する工程(現像工程)
得られた平版印刷版は、平版印刷版原版の表面において、露光部に相当するインキ反発層が除去されてなる。
次に、インキ反発層が除去されてなる露光部(画像部)に対して、本発明の第2の実施形態に用いられる染色液により染色が行われる。なお、染色液による画像部の染色は現像と同時に行ってもよいし、現像した後に染色を行ってもよい。また、染色工程では、均染性の向上、現像工程で不完全であった露光部を更に現像することを目的とし、ブラシ等で擦りながら染色してもよい。画像部に染色液が接した後に、染料を定着させ染色濃度を向上させるために、画像部上の染色液を乾燥する工程を含んでいても良い。乾燥方法としては、加熱、送風などが挙げられるが、特に限定されない。
現像処理された平版印刷版を積み重ねて保管する場合に備えて、版面保護の目的で、版と版の間に合紙を挟んでおくことが好ましい。
以下、本発明を実施例に基づいて説明するが、本発明はこれらの実施例に限定されるものではない。
(1-1)実施例1~10および比較例1~5の製版
東レ水なし平版“IMPRIMATM MC”(東レ(株)製、画像部に含まれる高分子化合物:フェノールノボラック樹脂/ポリウレタン=70.6/29.4、高分子化合物のSP値β=14.5(cal/cm3)1/2)に対し、CTP用露光機“PlateRite HD 8900N-E”(大日本スクリーン製造(株)製)を用いて、照射エネルギー:180mJ/cm2(ドラム回転数:140rpm)の条件で露光を行った。縦560mm×横335mmの平版印刷版原版に、2400dpiの175lpiでベタ画像と50%の網点を設けた。自動現像機“TWL-1160F”(東レ(株)製)の前処理槽と現像槽に水道水、後処理槽に各実施例・比較例の染色液(平版印刷版用染色液-1乃至平版印刷版用染色液-15)、水洗槽に水道水を仕込み、露光した原版を速度40cm/分で通して平版印刷版を計1000枚製造した。
所定の高分子化合物を含む画像層を備えた各実施例・比較例に記載されたとおり、水なし平版印刷版原版-1乃至水なし平版印刷版原版-4のいずれかに対し、CTP用露光機“PlateRite HD 8900N-E”(大日本スクリーン製造(株)製)を用いて、照射エネルギー:125mJ/cm2(実施例11~17および比較例6)もしくは150mJ/cm2(実施例18~20)の条件で露光を行った。縦560mm×横335mmの平版印刷版原版に、2400dpiの175lpiでベタ画像と50%の網点を設けた。自動現像機“TWL-1160F”(東レ(株)製)の前処理槽に水道水、現像槽に10%トリエチレングリコール水溶液(実施例11~18および比較例6)もしくは水道水(実施例19および20)、後処理槽に各実施例・比較例に記載されたとおり、染色液(平版印刷版用染色液-16乃至平版印刷版用染色液-21)、水洗槽に水道水を仕込み、露光した原版を速度40cm/分で通して平版印刷版を計1000枚製造した。また、実施例20においては、露光した原版が後処理槽を通過後、熱風発生機“HAP3051”(株式会社八光電機製)を用いて、風量:2m3/min、吹出口気体温度:100℃、画像部までの距離:10cmの条件で、画像部上の後処理液を熱風乾燥した。
反射濃度計“spectro eye”(X-rite社製)の測定コンディションを、内蔵フィルター:No、白色ベース:Auto、光源:D50、観察視野:2°、濃度基準ISO Tに設定後、濃度測定モードでフィルターとしてシアンを選択し、露光部分と未露光部分の反射濃度を測定した。次いで、フィルターをイエロー、マゼンダに変更後、同様に測定を行った。
1枚目の平版印刷版の染色濃度(A)と1000枚目の平版印刷版の染色濃度(B)を、以下の式(I)に代入した値を染色濃度保持率とした。染色濃度保持率が75.0%以上であれば実用上問題なく使用でき、80.0%以上が好ましく、90.0%以上がより好ましく、95.0%以上がさらに好ましく、98.0%以上がさらにより好ましい。
染色濃度保持率(%)= (B)/(A)×100 (I)
(1)染色濃度の評価において作製した計1000枚の平版印刷版の50%網点に対して、“spectro eye”(X-rite製)を用いて画像面積率を測定し、画像面積率が40%以下の箇所が存在する刷版を、染色ムラがある刷版として数を調べた。染色ムラのある刷版の数が20枚以下であれば実用上問題なく使用でき、15枚以下が好ましく、12枚以下がより好ましく、8枚以下がさらに好ましく、4枚以下がさらにより好ましい。
平版印刷版用染色液-1は、下記成分を室温にて撹拌混合することにより得た。
<平版印刷版用染色液-1>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ベヘン酸ナトリウム(一般式(1)において、R1=炭素数21の直鎖状のアルキル基、X=COONa):0.025質量部
(c)有機溶剤:メタノール(アルコール類、SP値:α=13.8(cal/cm3)1/2、蒸気圧:12300Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-1を前記方法で評価したところ、1枚目の染色濃度は0.45、1000枚目の染色濃度は0.35、染色濃度保持率は77.8%、染色ムラの枚数は18枚となり、良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-2に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-2>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ベヘン酸ナトリウム(一般式(1)において、R1=炭素数21の直鎖状のアルキル基、X=COONa):0.025質量部
(c)有機溶剤:メタノール(アルコール類、SP値:α=13.8(cal/cm3)1/2、蒸気圧:12300Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-2を前記方法で評価したところ、1枚目の染色濃度は0.61、1000枚目の染色濃度は0.47、染色濃度保持率は77.0%、染色ムラの枚数は18枚となり、良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-3に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-3>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ステアリン酸ナトリウム(一般式(1)において、R1=炭素数17の直鎖状のアルキル基、X=COONa)(昭和化学(株)製):0.025質量部
(c)有機溶剤:メタノール(アルコール類、SP値:α=13.8(cal/cm3)1/2、蒸気圧:12300Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-3を前記方法で評価したところ、1枚目の染色濃度は0.55、1000枚目の染色濃度は0.42、染色濃度保持率は76.4%、染色ムラの枚数は14枚となり、良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-4に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-4>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:オクタンスルホン酸ナトリウム(一般式(1)において、R1=炭素数8の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:メタノール(アルコール類、SP値:α=13.8(cal/cm3)1/2、蒸気圧:12300Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-4を前記方法で評価したところ、1枚目の染色濃度は0.52、1000枚目の染色濃度は0.40、染色濃度保持率は76.9%、染色ムラの枚数は10枚となり、良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-5に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-5>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:メタノール(アルコール類、SP値:α=13.8(cal/cm3)1/2、蒸気圧:12300Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-5を前記方法で評価したところ、1枚目の染色濃度は0.52、1000枚目の染色濃度は0.40、染色濃度保持率は76.9%、染色ムラの枚数は10枚となり、良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-6に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-6>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:ジプロピレングリコールモノブチルエーテル(エーテル類、一般式(2)において、n=2、R2=C4H9、SP値:α=10.2(cal/cm3)1/2、蒸気圧:5.3Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-6を前記方法で評価したところ、1枚目の染色濃度は0.66、1000枚目の染色濃度は0.63、染色濃度保持率は95.5%、染色ムラの枚数は4枚となり、良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-7に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-7>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:トリプロピレングリコールモノメチルエーテル(エーテル類、一般式(2)において、n=3、R2=CH3、SP値:α=10.3(cal/cm3)1/2、蒸気圧:4Pa(20℃))(東京化成工業(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-7を前記方法で評価したところ、1枚目の染色濃度は0.70、1000枚目の染色濃度は0.68、染色濃度保持率は97.1%、染色ムラの枚数は2枚となり、非常に良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-8に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-8>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.500質量部
(c)有機溶剤:トリプロピレングリコールモノメチルエーテル(エーテル類、一般式(2)において、n=3、R2=CH3、SP値:α=10.3(cal/cm3)1/2、蒸気圧:4Pa(20℃))(東京化成工業(株)製):9.0質量部
(d)水:90.5質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-8を前記方法で評価したところ、1枚目の染色濃度は1.16、1000枚目の染色濃度は1.11、染色濃度保持率は95.7%、染色ムラの枚数は2枚となり、非常に良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-9に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-9>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:トリプロピレングリコール(アルコール類、SP値:α=12.4(cal/cm3)1/2、蒸気圧:140Pa(20℃))(SIGMA-ALDRICH製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-9を前記方法で評価したところ、1枚目の染色濃度は0.66、1000枚目の染色濃度は0.65、染色濃度保持率は98.5%、染色ムラの枚数は4枚となり、非常に良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-10に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-10>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:3-メチル-3-メトキシブタノール(アルコール類、SP値:α=10.5(cal/cm3)1/2、蒸気圧:67Pa(20℃))(東京化成工業(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-10を前記方法で評価したところ、1枚目の染色濃度は0.75、1000枚目の染色濃度は0.74、染色濃度保持率は98.7%、染色ムラの枚数は2枚となり、非常に良好な結果が得られた。
平版印刷版用染色液-1を以下の平版印刷版用染色液-11に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-11>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:酢酸ブチル(エステル類、SP値:α=9.1(cal/cm3)1/2、蒸気圧:1200Pa(20℃))(昭和化学(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-11を前記方法で評価したところ、1枚目の染色濃度は0.19、1000枚目の染色濃度は0.00となり、染色濃度の点から実用不可の結果となった。染色液中での染料の溶解安定性が低く、染色濃度が低下したことが原因と思われる。
平版印刷版用染色液-1を以下の平版印刷版用染色液-12に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-12>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)ノニオン性界面活性剤:ポリオキシエチレンラウリルエーテル(和光純薬(株)製):0.025質量部
(c)有機溶剤:テトラヒドロフラン(エーテル類、SP値:α=9.1(cal/cm3)1/2、蒸気圧:18,900Pa(20℃))(三菱ケミカル(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-12を前記方法で評価したところ、1枚目の染色濃度は0.20、1000枚目の染色濃度は0.14、染色濃度保持率は70.0%、染色ムラの枚数は30枚となり、染色濃度および染色ムラの点から実用不可の結果となった。
平版印刷版用染色液-1を以下の平版印刷版用染色液-13に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-13>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ブチルナフタレンスルホン酸ナトリウム(一般式(1)において、R1=炭素数4の直鎖状のアルキルを有するナフチル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:テトラヒドロフラン(エーテル類、SP値:α=9.1(cal/cm3)1/2、蒸気圧:18,900Pa(20℃))(三菱ケミカル(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-13を前記方法で評価したところ、1枚目の染色濃度は0.24、1000枚目の染色濃度は0.20、染色濃度保持率は83.3%、染色ムラの枚数は32枚となり、染色濃度および染色ムラの点から実用不可の結果となった。
平版印刷版用染色液-1を以下の平版印刷版用染色液-14に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-14>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:2-メチル-2-プロペン-1-スルホン酸 ナトリウム(一般式(1)において、R1=炭素数4の分岐型のアルケニル基、X=SO3Na)(東京化成工業(株)製):0.025質量部
(c)有機溶剤:テトラヒドロフラン(エーテル類、SP値:α=9.1(cal/cm3)1/2、蒸気圧:18,900Pa(20℃))(三菱ケミカル(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-14を前記方法で評価したところ、1枚目の染色濃度は0.50、1000枚目の染色濃度は0.38、染色濃度保持率は76.0%、染色ムラの枚数は24枚となり、染色ムラの点から実用不可の結果となった。
平版印刷版用染色液-1を以下の平版印刷版用染色液-15に変更したこと以外は実施例1と同様にして評価を行った。
<平版印刷版用染色液-15>
(a)染料:エチルバイオレット(トリフェニルメタン系塩基性染料)(東京化成工業(株)製):0.250質量部
(b)アニオン性界面活性剤:ヘキシル硫酸ナトリウム(一般式(1)において、R1=炭素数6の直鎖状のアルキル基、X=SO4Na)(和光純薬(株)製):0.025質量部
(c)有機溶剤:テトラヒドロフラン(エーテル類、SP値:α=9.1(cal/cm3)1/2、蒸気圧:18,900Pa(20℃))(三菱ケミカル(株)製):9.0質量部
(d)水:90.7質量部
なお、上記平版印刷版用染色液の各成分(a)~(d)の配合量の合計が100質量部である。
得られた平版印刷版用染色液-15を前記方法で評価したところ、1枚目の染色濃度は0.49、1000枚目の染色濃度は0.37、染色濃度保持率は75.5%、染色ムラの枚数は25枚となり、染色ムラの点から実用不可の結果となった。
(A)水なし平版印刷版原版-1の作製
厚み0.24mmの脱脂したアルミ基板(三菱アルミ(株)製)上に下記の有機層組成物溶液を塗布し、200℃で90秒間乾燥し、厚み6.0μmの有機層を設けた。なお、有機層組成物溶液は、下記成分を室温(20~28℃)にて撹拌混合することにより得た。
<有機層組成物溶液>
(a)活性水素を有するポリマー:エポキシ樹脂:“エピコート”(登録商標)1010(ジャパンエポキシレジン(株)製):35質量部
(b)活性水素を有するポリマー:ポリウレタン:“サンプレン”(登録商標)LQ-T1331D(三洋化成工業(株)製、固形分濃度:20質量%):375質量部
(c)アルミキレート:アルミキレートALCH-TR(川研ファインケミカル(株)製):10質量部
(d)レベリング剤:“ディスパロン”(登録商標)LC951(楠本化成(株)製、固形分:10質量%):1質量部
(e)酸化チタン:“タイペーク”(登録商標)CR-50(石原産業(株)製)のN,N-ジメチルホルムアミド分散液(酸化チタン50質量%):60質量部
(f)N,N-ジメチルホルムアミド:730質量部
(g)メチルエチルケトン:250質量部
<画像層組成物溶液-1>
(a)赤外線吸収染料(シアニン色素):NK5559(株式会社林原製、最大吸収波長:774nm):16.0質量部
(b)高分子化合物:メタクリル樹脂“パラペット”(SP値:β=9.1(cal/cm3)1/2)(株式会社クラレ製):84質量部
(c)メチルエチルケトン:900質量部
<シリコーンゴム層組成物溶液>
(a)α,ω-ジビニルポリジメチルシロキサン:DMS-V35(重量平均分子量49,500、GELEST Inc.製):86.26質量部
(b)メチルハイドロジェンシロキサン-ジメチルシロキサン共重合体RD-1(東レ・ダウコーニング(株)製):4.93質量部
(c)ビニルトリス(メチルエチルケトオキシイミノ)シラン:2.64質量部
(d)白金触媒SRX212(東レ・ダウコーニング(株)製、白金触媒が6.0質量%):6.17質量部
(e)“アイソパー”E(エッソ化学(株)製):900質量部
平版印刷版用染色液-16は、下記成分を室温にて撹拌混合することにより得た。
<平版印刷版用染色液-16>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.50質量部
(c)有機溶剤:キシレン(SP値:α=8.8(cal/cm3)1/2))(和光純薬(株)製):99.50質量部
得られた水なし平版印刷版原版-1と平版印刷版用染色液-16を用いて、前記方法で評価したところ、1枚目の染色濃度は0.33、1000枚目の染色濃度は0.25、染色濃度保持率は75.8%、染色ムラの枚数は20枚という結果であった。
水なし平版印刷版原版-1の画像層組成物溶液-1を、以下の画像層組成物溶液-2に変更した水なし平版印刷版原版-2を用い、平版印刷版用染色液-16の代わりに以下の平版印刷版用染色液-17を用いた以外は、実施例11と同様にして評価を行った。
<画像層組成物溶液-2>
(a)赤外線吸収染料(シアニン色素):NK5559(株式会社林原製、最大吸収波長:774nm):16.0質量部
(b)高分子化合物:フェノールノボラック樹脂“スミライトレジン”(登録商標)PR53195(SP値:β=16.4(cal/cm3)1/2)(住友ベークライト(株)製):73.05質量部
(c)有機錯化合物:チタニウム-n-ブトキシドビス(アセチルアセトネート):“ナーセム”(登録商標)チタン(日本化学産業(株)製、濃度:73質量%、溶剤としてn-ブタノール:27質量%を含む):15.0質量部
(d)テトラヒドロフラン:895.95質量部。
<平版印刷版用染色液-17>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.50質量部
(b)アニオン性界面活性剤:ベヘン酸ナトリウム(一般式(1)において、R1=炭素数21の直鎖状のアルキル基、X=COONa):0.05質量部
(c)有機溶剤:メタノール(アルコール類、SP値:α=13.8(cal/cm3)1/2)、蒸気圧:12300Pa(20℃))(和光純薬(株)製):9.00質量部
(d)水:90.45質量部
得られた水なし平版印刷版原版-2と平版印刷版用染色液-17を用いて、前記方法で評価したところ、1枚目の染色濃度は0.70、1000枚目の染色濃度は0.64、染色濃度保持率は91.4%、染色ムラの枚数は14枚という結果であった。
水なし平版印刷版原版-1の画像層組成物溶液-1を、以下の画像層組成物溶液-3に変更した水なし平版印刷版原版-3を用い、平版印刷版用染色液-16の代わりに以下の平版印刷版用染色液-18を用いた以外は、実施例11と同様にして評価を行った。
<画像層組成物溶液-3>
(a)赤外線吸収染料(シアニン色素):NK5559(株式会社林原製、最大吸収波長:774nm):16.0質量部
(b)高分子化合物:イミノ基型メチル化メラミン樹脂“サイメル327”(SP値:β=13.8(cal/cm3)1/2))(ALLNEX製):83.0質量部
(c)p-トルエンスルホン酸:1.0質量部
(d)メチルエチルケトン:900質量部
<平版印刷版用染色液-18>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.50質量部
(b)アニオン性界面活性剤:ベヘン酸ナトリウム(一般式(1)において、R1=炭素数21の直鎖状のアルキル基、X=COONa):0.05質量部
(c)有機溶剤:ジプロピレングリコールモノブチルエーテル(エーテル類、一般式(2)において、n=2、R2=C4H9、SP値:α=10.2(cal/cm3)1/2)、蒸気圧:5.3Pa(20℃))(和光純薬(株)製):9.0質量部
(d)水:90.45質量部
得られた水なし平版印刷版原版-3と平版印刷版用染色液-18を用いて、前記方法で評価したところ、1枚目の染色濃度は0.92、1000枚目の染色濃度は0.88、染色濃度保持率は95.7%、染色ムラの枚数は9枚という良好な結果であった。
平版印刷版用染色液-18の代わりに以下の平版印刷版用染色液-19を用いた以外は、実施例13と同様にして評価を行った。
<平版印刷版用染色液-19>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.50質量部
(b)アニオン性界面活性剤:ベヘン酸ナトリウム(一般式(1)において、R1=炭素数21の直鎖状のアルキル基、X=COONa):0.05質量部
(c)有機溶剤:3-メチル-3-メトキシブタノール(アルコール類、SP値:α=10.5(cal/cm3)1/2)、蒸気圧:67Pa(20℃))(東京化成工業(株)製):9.0質量部
(d)水:90.45質量部
得られた平版印刷版用染色液-19を用いて、前記方法で評価したところ、1枚目の染色濃度は1.01、1000枚目の染色濃度は0.96、染色濃度保持率は95.0%、染色ムラの枚数は7枚という良好な結果であった。
平版印刷版用染色液-18の代わりに以下の平版印刷版用染色液-20を用いた以外は、実施例13と同様にして評価を行った。
<平版印刷版用染色液-20>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.50質量部
(b)アニオン性界面活性剤:ベヘン酸ナトリウム(一般式(1)において、R1=炭素数21の直鎖状のアルキル基、X=COONa):0.05質量部
(c)有機溶剤:トリプロピレングリコール(アルコール類、SP値:α=12.4(cal/cm3)1/2)、蒸気圧:140Pa(20℃))(SIGMA-ALDRICH製):9.0質量部
(d)水:90.45質量部
得られた平版印刷版用染色液-20を用いて、前記方法で評価したところ、1枚目の染色濃度は1.02、1000枚目の染色濃度は0.97、染色濃度保持率は95.1%、染色ムラの枚数は7枚という良好な結果であった。
水なし平版印刷版原版-2と平版印刷版用染色液-20を用いて、前記方法で評価したところ、1枚目の染色濃度は1.00、1000枚目の染色濃度は0.95、染色濃度保持率は95.0%、染色ムラの枚数は6枚という結果であった。
平版印刷版用染色液-20の代わりに以下の平版印刷版用染色液-21を用いた以外は、実施例16と同様にして評価を行った。
<平版印刷版用染色液-21>
(a)染料:ローダミン6G(キサンテン系塩基性染料)(東京化成工業(株)製):0.50質量部
(b)アニオン性界面活性剤:ヘキサンスルホン酸ナトリウム(一般式(3)において、R1=炭素数6の直鎖状のアルキル基、X=SO3Na)(東京化成工業(株)製):0.05質量部
(c)有機溶剤:トリプロピレングリコール(アルコール類、SP値:α=12.4(cal/cm3)1/2)、蒸気圧:140Pa(20℃))(SIGMA-ALDRICH製):9.0質量部
(d)水:90.45質量部
得られた平版印刷版用染色液-21を用いて、前記方法で評価したところ、1枚目の染色濃度は1.06、1000枚目の染色濃度は1.01、染色濃度保持率は95.3%、染色ムラの枚数は3枚という非常に良好な結果であった。
水なし平版印刷版原版-2の露光量を125mJ/cm2から150mJ/cm2に変更した以外は、実施例17と同様にして評価を行った。
前記方法で評価したところ、1枚目の染色濃度は1.20、1000枚目の染色濃度は1.18、染色濃度保持率は98.3%、染色ムラの枚数は3枚という非常に良好な結果であった。
水なし平版印刷版原版-2の現像において、現像槽の10%トリエチレングリコール水溶液を水道水に変更した以外は、実施例18と同様にして評価を行った。
前記方法で評価したところ、1枚目の染色濃度は1.20、1000枚目の染色濃度は1.18、染色濃度保持率は98.3%、染色ムラの枚数は1枚という非常に良好な結果であった。
露光した水なし平版印刷版原版-2が後処理槽を通過後、画像部上の後処理液を熱風乾燥した以外は、実施例19と同様にして評価を行った。
前記方法で評価したところ、1枚目の染色濃度は1.30、1000枚目の染色濃度は1.29、染色濃度保持率は99.2%、染色ムラの枚数は0枚という非常に良好な結果であった。
水なし平版印刷版原版-1の画像層組成物溶液-1を、以下の画像層組成物溶液-4に変更した水なし平版印刷版原版-4を用いた以外は、実施例11と同様にして評価を行った。
<画像層組成物溶液-4>
(a)赤外線吸収染料(シアニン色素):NK5559(株式会社林原製、最大吸収波長:774nm):16.0質量部
(b)高分子化合物:カルボキシメチルセルロース(SP値:β=19.5(cal/cm3)1/2))(ダイセルファインケム株式会社製):84質量部
(c)メチルエチルケトン:900質量部
Claims (22)
- 有機溶剤を含有する染色液を用いて、水なし平版印刷版に形成された画像部を染色する方法であって、
前記画像部に高分子化合物が含まれ、前記有機溶剤のSP値αと前記高分子化合物のSP値βが、
|β-α|<5(cal/cm3)1/2の関係を満たす水なし平版印刷版の染色方法。 - 前記有機溶剤のSP値αと前記高分子化合物のSP値βが、1(cal/cm3)1/2<β-α<5(cal/cm3)1/2の関係を満たす請求項1に記載の水なし平版印刷版の染色方法。
- 前記高分子化合物のSP値βが10~17(cal/cm3)1/2である、請求項1または2に記載の水なし平版印刷版の染色方法。
- 前記高分子化合物がフェノール樹脂および/またはメラミン樹脂である、請求項1~3のいずれかに記載の水なし平版印刷版の染色方法。
- 前記有機溶剤のSP値αが9.0~13.0(cal/cm3)1/2である、請求項1~4のいずれかに記載の水なし平版印刷版の染色方法。
- 前記有機溶剤がエーテル類および/またはアルコール類である、請求項1~5のいずれかに記載の水なし平版印刷版の染色方法。
- 前記エーテル類が、下記一般式(2)で示されるジプロピレングリコールモノアルキルエーテルまたはトリプロピレングリコールモノアルキルエーテルである、請求項6に記載の水なし平版印刷版の染色方法。
R2-(OC3H6)n-OH (2)
(式中、R2はCH3、C2H5、C3H7、C4H9、C5H11、またはC6H13、nは2または3である。また、(OC3H6)は、それぞれ独立して分岐鎖および直鎖のいずれでもよいものとする。) - 前記アルコール類が、トリプロピレングリコールまたは3-メチル-3-メトキシブタノールである、請求項6に記載の水なし平版印刷版の染色方法。
- 前記染色液が、さらにアニオン性界面活性剤を含む、請求項1~8のいずれかに記載の水なし平版印刷版の染色方法。
- 前記アニオン性界面活性剤が下記一般式(3)で示される、請求項9に記載の水なし平版印刷版の染色方法。
R1-X (3)
(式中、R1は炭素数6~10の直鎖状のアルキル基を示す。XはSO3Na、SO3K、COONa、COONH4またはCOOKを示す。) - 前記染色液を前記画像部に接した後、前記画像部上の染色液を乾燥する工程を含む、請求項1~10のいずれかに記載の水なし平版印刷版の染色方法。
- 前記水なし平版印刷版原版が少なくとも基材、インキ反発層を有しており、少なくとも水を含む現像液をかけながら摩擦することで、前記インキ反発層を除去した後に、請求項1~11のいずれかに記載の方法で染色する、水なし平版印刷版の染色方法。
- 前記現像液が有機溶剤を含まない、請求項12に記載の水なし平版印刷版の染色方法。
- 前記水なし平版印刷版原版が150mJ/cm2以上の露光量で画像様に露光された後に実施する、請求項1~13のいずれかに記載の水なし平版印刷版の染色方法。
- 平版印刷版原版に形成された画像部を染色するために用いられる染色液であって、
(a)染料、
(b)下記一般式(1)で示されるアニオン性界面活性剤、および
(c)エーテル類およびアルコール類のうち少なくとも1つを含む有機溶剤を含有する平版印刷版用染色液。
R1-X (1)
(式中、R1は炭素数3~30の直鎖状のアルキル基または炭素数3~30の直鎖状のアルケニル基を示す。XはSO3Na、SO3K、COONa、COONH4またはCOOKを示す。) - 前記(a)染料が、塩基性染料である、請求項15に記載の平版印刷版用染色液。
- 前記(a)染料が、トリフェニルメタン系塩基性染料である請求項15または16に記載の平版印刷版用染色液。
- 前記一般式(1)において、R1が炭素数3~20の直鎖状のアルキル基または炭素数3~20の直鎖状のアルケニル基である、請求項15~17のいずれかに記載の平版印刷用染色液。
- 前記エーテル類がアルキレングリコールアルキルエーテルである、請求項15~18のいずれかに記載の平版印刷版用染色液。
- 前記アルコール類およびエーテル類の溶解度パラメーターが9.0~13.0(cal/cm3)1/2である、請求項15~19のいずれかに記載の平版印刷用染色液。
- 前記アルコール類およびエーテル類の20℃における蒸気圧が2000Pa以下である、請求項15~20のいずれかに記載の平版印刷用染色液。
- 平版印刷版原版に対し、現像中もしくは現像後に、請求項15~21のいずれかに記載の平版印刷版用染色液を用いて画像部を染色する、平版印刷版の染色方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20826360.8A EP3988319B1 (en) | 2019-06-20 | 2020-06-15 | Dyeing methods for lithographic printing plates |
JP2020537560A JPWO2020255918A1 (ja) | 2019-06-20 | 2020-06-15 | |
US17/613,233 US20220213327A1 (en) | 2019-06-20 | 2020-06-15 | Waterless planographic printing plate dyeing method and planographic printing dye |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-114381 | 2019-06-20 | ||
JP2019114381 | 2019-06-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020255918A1 true WO2020255918A1 (ja) | 2020-12-24 |
Family
ID=74040769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/023391 WO2020255918A1 (ja) | 2019-06-20 | 2020-06-15 | 水なし平版印刷版の染色方法、および平版印刷版用染色液 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20220213327A1 (ja) |
EP (1) | EP3988319B1 (ja) |
JP (1) | JPWO2020255918A1 (ja) |
WO (1) | WO2020255918A1 (ja) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4839987B1 (ja) | 1970-09-01 | 1973-11-28 | ||
JPH06202313A (ja) * | 1991-03-05 | 1994-07-22 | Mitsubishi Kasei Corp | 湿し水不要感光性平版印刷版 |
JPH0829971A (ja) * | 1994-07-15 | 1996-02-02 | Fuji Photo Film Co Ltd | 水無し感光性平版印刷版用染色液 |
JPH0934132A (ja) | 1995-07-21 | 1997-02-07 | Toray Ind Inc | 水なし平版印刷版の染色液および染色方法 |
JPH1039497A (ja) * | 1996-07-19 | 1998-02-13 | Toray Ind Inc | 直描型水なし平版印刷版原版 |
JP2004233610A (ja) | 2003-01-30 | 2004-08-19 | Toray Ind Inc | 水なし平版印刷版用染色液およびそれを用いた染色方法 |
JP2006248049A (ja) * | 2005-03-10 | 2006-09-21 | Fuji Xerox Co Ltd | インクジェット用処理液、インクジェト用処理液タンク、インクジェット用インクセット、インクジェット用インクタンク、インクジェット記録方法、及びインクジェット記録装置 |
JP2010163534A (ja) * | 2009-01-15 | 2010-07-29 | Fujifilm Corp | インク組成物、インクセットおよびインクジェット画像形成方法 |
JP2013203875A (ja) * | 2012-03-28 | 2013-10-07 | Pentel Corp | ボールペン用油性インキ組成物 |
JP2016102270A (ja) * | 2014-11-27 | 2016-06-02 | Dic株式会社 | 捺染剤及び布帛物 |
JP2018178309A (ja) * | 2017-04-13 | 2018-11-15 | 花王株式会社 | セルロース繊維複合体 |
WO2019039512A1 (ja) * | 2017-08-24 | 2019-02-28 | 東洋紡株式会社 | 伸縮性電極、伸縮性電極の製造方法、生体情報計測用衣服および生体情報計測方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63165466A (ja) * | 1987-11-27 | 1988-07-08 | Seiko Epson Corp | インクジェット記録用速乾性インク |
US6527844B2 (en) * | 2001-02-27 | 2003-03-04 | Eastman Kodak Company | Metal complex for ink jet ink |
CN104893404A (zh) * | 2015-06-10 | 2015-09-09 | 沈阳泉发印刷材料有限公司 | 一种墨水 |
CN105440792A (zh) * | 2015-12-13 | 2016-03-30 | 青岛大方智慧网络科技有限公司 | 一种稳定性高的红色墨水 |
-
2020
- 2020-06-15 JP JP2020537560A patent/JPWO2020255918A1/ja active Pending
- 2020-06-15 EP EP20826360.8A patent/EP3988319B1/en active Active
- 2020-06-15 US US17/613,233 patent/US20220213327A1/en active Pending
- 2020-06-15 WO PCT/JP2020/023391 patent/WO2020255918A1/ja active Application Filing
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4839987B1 (ja) | 1970-09-01 | 1973-11-28 | ||
JPH06202313A (ja) * | 1991-03-05 | 1994-07-22 | Mitsubishi Kasei Corp | 湿し水不要感光性平版印刷版 |
JPH0829971A (ja) * | 1994-07-15 | 1996-02-02 | Fuji Photo Film Co Ltd | 水無し感光性平版印刷版用染色液 |
JPH0934132A (ja) | 1995-07-21 | 1997-02-07 | Toray Ind Inc | 水なし平版印刷版の染色液および染色方法 |
JPH1039497A (ja) * | 1996-07-19 | 1998-02-13 | Toray Ind Inc | 直描型水なし平版印刷版原版 |
JP2004233610A (ja) | 2003-01-30 | 2004-08-19 | Toray Ind Inc | 水なし平版印刷版用染色液およびそれを用いた染色方法 |
JP2006248049A (ja) * | 2005-03-10 | 2006-09-21 | Fuji Xerox Co Ltd | インクジェット用処理液、インクジェト用処理液タンク、インクジェット用インクセット、インクジェット用インクタンク、インクジェット記録方法、及びインクジェット記録装置 |
JP2010163534A (ja) * | 2009-01-15 | 2010-07-29 | Fujifilm Corp | インク組成物、インクセットおよびインクジェット画像形成方法 |
JP2013203875A (ja) * | 2012-03-28 | 2013-10-07 | Pentel Corp | ボールペン用油性インキ組成物 |
JP2016102270A (ja) * | 2014-11-27 | 2016-06-02 | Dic株式会社 | 捺染剤及び布帛物 |
JP2018178309A (ja) * | 2017-04-13 | 2018-11-15 | 花王株式会社 | セルロース繊維複合体 |
WO2019039512A1 (ja) * | 2017-08-24 | 2019-02-28 | 東洋紡株式会社 | 伸縮性電極、伸縮性電極の製造方法、生体情報計測用衣服および生体情報計測方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3988319A4 |
Also Published As
Publication number | Publication date |
---|---|
US20220213327A1 (en) | 2022-07-07 |
EP3988319A1 (en) | 2022-04-27 |
EP3988319A4 (en) | 2023-08-09 |
JPWO2020255918A1 (ja) | 2020-12-24 |
EP3988319B1 (en) | 2024-08-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102483588B (zh) | 用于在平版印版的单步冲洗之后干燥的方法和装置 | |
CN100498523C (zh) | 平版印刷版原版 | |
CN106364209B (zh) | 一种含感热保护层的热敏免处理的平版印刷版材料及应用 | |
CN104827795A (zh) | 一种阳图热敏平版印刷版版材 | |
CN101809504A (zh) | 用于制作平版印刷版的方法 | |
JP2016533541A (ja) | リソグラフ印刷版の提供方法 | |
JP4807472B2 (ja) | 直描型水なし平版印刷版原版およびその製造方法 | |
WO2020255918A1 (ja) | 水なし平版印刷版の染色方法、および平版印刷版用染色液 | |
WO2017204046A1 (ja) | 平版印刷版原版 | |
JP4182775B2 (ja) | 直描型水なし平版印刷版原版 | |
US20190344556A1 (en) | Method for producing lithographic printing plate | |
JP4876423B2 (ja) | 直描型水なし平版印刷版原版の製造方法 | |
JP2006276385A (ja) | 直描型水なし平版印刷版原版 | |
US6368777B1 (en) | Performance of printing plates | |
JP2004334025A (ja) | 直描型水なし平版印刷版原版 | |
JP2019093613A (ja) | 印刷物の製造方法 | |
JPWO2005010613A1 (ja) | 感光性平版印刷版およびその製造方法 | |
JP2019152827A (ja) | 平版印刷版原版 | |
JP2005300586A (ja) | 直描型水なし平版印刷版原版、その製造方法及びそれを用いた印刷版の製造方法 | |
JP3788036B2 (ja) | 感光性平版印刷版及びその製造方法 | |
KR102415539B1 (ko) | 평판 인쇄판 원판, 평판 인쇄판의 제조 방법, 및 그것을 사용한 인쇄물의 제조 방법 | |
JP3829413B2 (ja) | 感光性平版印刷版材料 | |
JP2020026136A (ja) | 平版印刷版原版、平版印刷版の製造方法、およびそれを用いた印刷物の製造方法 | |
WO2005101126A1 (ja) | ネガ型感光性組成物およびネガ型感光性平版印刷版 | |
JP2001242639A (ja) | ポジ画像形成方法及びそれに用いる現像液 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2020537560 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20826360 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2020826360 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2020826360 Country of ref document: EP Effective date: 20220120 |