WO2018082499A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2018082499A1
WO2018082499A1 PCT/CN2017/107840 CN2017107840W WO2018082499A1 WO 2018082499 A1 WO2018082499 A1 WO 2018082499A1 CN 2017107840 W CN2017107840 W CN 2017107840W WO 2018082499 A1 WO2018082499 A1 WO 2018082499A1
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Prior art keywords
heat
printing plate
layer
plate material
lithographic printing
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PCT/CN2017/107840
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English (en)
French (fr)
Inventor
周树云
邹应全
刘金英
邢芳
肖时卓
陈萍
赵建
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中国科学院理化技术研究所
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Application filed by 中国科学院理化技术研究所 filed Critical 中国科学院理化技术研究所
Priority to JP2019520105A priority Critical patent/JP6718020B2/ja
Priority to ES17867568T priority patent/ES2944336T3/es
Priority to PL17867568.2T priority patent/PL3536513T3/pl
Priority to EP17867568.2A priority patent/EP3536513B1/en
Priority to US16/344,526 priority patent/US10926566B2/en
Publication of WO2018082499A1 publication Critical patent/WO2018082499A1/zh

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00Forme preparation
    • B41C1/10Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008Forme 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING 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
    • B41N1/00Printing plates or foils; Materials therefor
    • B41N1/12Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00Forme preparation
    • B41C1/10Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008Forme 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
    • B41C1/1016Forme 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 characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING 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
    • B41N1/00Printing plates or foils; Materials therefor
    • B41N1/04Printing plates or foils; Materials therefor metallic
    • B41N1/08Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02Cover layers; Protective layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04Intermediate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08Developable by water or the fountain solution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING 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
    • B41N2207/00Location or type of the layers in shells for rollers of printing machines
    • B41N2207/14Location or type of the layers in shells for rollers of printing machines characterised by macromolecular organic compounds

Definitions

  • the present invention relates to lithographic printing plate materials; more particularly to a heat-sensitive, process-free lithographic printing plate material and application comprising a thermal protective layer.
  • CTP technology is one of the most popular ones.
  • the CTP technology is a technique for directly producing a printing plate by scanning light with digital image information using a highly directional light such as a laser.
  • plate making defects due to dynamic factors of the developing solution such as fluctuations in pH of the developing solution or accumulation of photosensitive layer components in the developing solution, resulting in deterioration of developability, etc., may be mentioned.
  • the cost of manufacturing the developer the cost of processing the developing waste, and the environmental pollution of the industrial emissions, which have led to an increasing demand for process-free plates.
  • the free-handling CTP plate is mainly divided into three categories: heat sensitive type, photosensitive type and ink jet type.
  • the main problem with inkjet CTP plates is that the image accuracy is not as good as that of the heat sensitive and photosensitive CTP plates.
  • the photosensitive CTP plate is mainly of the microcapsule type, and the main problem is that the protective gel is required to assist development after exposure, and the printing durability is defective due to poor adhesion of the microcapsule to the support.
  • the biggest advantage of the thermal CTP plate is the ability to operate in bright room. Early thermal-free CTP plates were hot ablated and hot melt. The thermal ablation type treatment-free method has been gradually replaced by hot-melt type technology due to the disadvantage that the ablation residue is likely to contaminate the exposure machine.
  • the hot-melt CTP plate requires special glue to remove the unexposed areas after exposure to obtain graphic information, which simplifies the "development” process.
  • On-press development another means of simplifying the development of the plate making process, called “on-press development”, is realized.
  • On-board development means that after the lithographic printing plate is exposed, the original printing plate is directly attached to the printing machine without conventional development, and the dampening solution (exposure zone oleophilic) or ink is used in the early stage of the printing process. The exposed area is hydrophilic) to remove unexposed areas.
  • An on-press development type thermal printing plate material proposed by Fujifilm is characterized in that a layer of a lipophilic heat sensitive layer is applied on a plate, and then a hydrophilic layer and a water-soluble protective layer are coated, and the hydrophilic layer contains Inorganic hydrophilic matrix, the interaction between the oleophilic layer and the hydrophilic layer decreases after exposure, and the non-exposed area of the oleophilic layer is removed by the hydrophilic layer and the hydrophilic substance in the ink during printing, and the exposed area is left to form a graphic Information; also using an adhesive polymer having an alkylene oxide group in the image recording layer, and using a hydroxyalkyl cellulose in the protective layer to promote on-press developability and suppress The inter-layer mixing improves the ink-receiving and printing durability.
  • thermographic layer Another on-board developed thermal printing plate is characterized by thermal imaging on the substrate.
  • the layer, the substrate and the thermographic layer also contain a very thin layer of water-soluble interlayer, but the water-soluble interlayer is extremely thin, does not affect the mechanical interlock between the thermographic layer and the plate, the thermographic layer
  • the upper layer is coated with a water-soluble protective layer.
  • the protective layer acts to block oxygen and prevent oxygen inhibition.
  • the patent publication number is WO 02/21215 A1; the structure of the processing-free thermal plate proposed by Lekai Huaguang Printing Technology Co., Ltd.
  • the water-soluble heat-crosslinking copolymer described herein is a copolymer having an epoxy group, a cyano group and an ether bond in a branched chain, and water development is achieved by changing the water solubility of the copolymer before and after exposure, and the patent publication number is CN105372935A.
  • the structure of the process-free thermal negative plate proposed by Chengdu Core Digital Technology Co., Ltd.
  • thermosensitive negative image forming element comprises a support body and a thermal negative image forming element coated thereon, the heat sensitive negative image forming element comprising a hydrophilic polymer
  • the particles, the hydrophobic polymer particles and the energy conversion material which may be contained, the irradiated portion of the thermosensitive negative image forming element becomes a hydrophobic region, and the unirradiated portion retains its hydrophilic property, so that the dampening can be achieved The development on a liquid machine can be cited as Patent Publication Nos. CN101269564, CN101376305, CN101376306, and CN101376307. These inventions still have room for improvement in meeting the requirements of both the dirty printing (i.e., good developing performance) and high printing durability while satisfying various printing conditions.
  • Another object of the present invention is to provide an application of a heat-sensitive, process-free lithographic printing plate material having a thermal protective layer.
  • the lithographic printing material includes, in order from bottom to top, a support, a hydrophilic layer, a heat sensitive layer, and a thermal protective layer.
  • the support, the hydrophilic layer and the thermosensitive protective layer are hydrophilic; the thermosensitive layer is oleophilic or parental (the parent means both oleophilic and hydrophilic).
  • the support in the present invention is a plate-like body or a film body which can carry a photosensitive layer.
  • the plate-like body capable of supporting the photosensitive layer is an aluminum plate; and the film body capable of supporting the photosensitive layer is various plastic films.
  • the aluminum plate refers to an aluminum plate which is roughened and anodized on the side in contact with the heat sensitive layer;
  • the plastic film is polyethylene terephthalate or polyethylene naphthalate One or more of an alcohol ester, polyethylene, polypropylene, polystyrene, polyvinyl acetal, polycarbonate, cellulose diacetate, and nitrocellulose; still more preferably, the plastic film is a poly Ethylene terephthalate or polyethylene naphthalate.
  • the method of the roughening treatment is a mechanical method or an electrolytic etching method; the mechanical method is not particularly limited, and is preferably a wire brush grinding method; the electrolytic etching method is not particularly limited, and an electrochemical surface is preferably performed in an acidic electrolytic solution. Roughening method.
  • the method of the anodizing treatment is not particularly limited and can be carried out by a known method.
  • the support body may be subjected to a sealing treatment when performing anodizing treatment; the sealing treatment may be performed by hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment It is carried out by a known method such as acetamide treatment.
  • the present invention performs hydrophilization processing on the plastic film on the side in contact with the photosensitive layer; the hydrophilization processing may be performed by corona discharge treatment, flame treatment, plasma treatment. It is carried out by a known method such as ultraviolet irradiation treatment.
  • the hydrophilic layer of the present invention is soluble in an aqueous solution such as a fountain solution, and is mainly composed of a water-soluble resin;
  • the water-soluble resin of the hydrophilic layer is selected from one or more of polyvinyl alcohol, polyvinyl pyrrolidone, aqueous nylon resin, gelatin, and cellulose derivative.
  • the thickness of the hydrophilic layer is sufficiently thin to affect the mechanically interlocking manner between the heat sensitive layer and the support.
  • the heat sensitive layer includes the following components by mass: 10 to 60 parts of the film-forming resin, 30 to 90 parts of the crosslinking agent, 0 to 40 parts of the diluent, 1 to 30 parts of the polymerization initiator, and infrared absorbing dye 1 10 parts and 0.1 to 3 parts of the colored background dye; preferably, the heat sensitive layer comprises the following parts by mass: 20-50 parts of film-forming resin, 50-80 parts of crosslinking agent, 0-30 parts of diluent
  • the polymerization initiator is 1-10 parts
  • the infrared absorbing dye is 1-5 parts
  • the colored background dye is 0.1-5 parts.
  • the film-forming resin is one or more of an oil-soluble polymer having a weight average molecular weight of 20,000 to 100,000 and a water-oil lyotropic polymer having a reactive carbon-carbon double bond having a weight average molecular weight of 10,000 to 200,000.
  • an oil-soluble polymer having a weight average molecular weight of 20,000 to 100,000
  • a water-oil lyotropic polymer having a reactive carbon-carbon double bond having a weight average molecular weight of 10,000 to 200,000.
  • the oil-soluble polymer is selected from one or more of an acrylic resin, an acid anhydride resin, an acrylate resin, a styrene copolymer, and polyvinyl butyral; more preferably, the oil-soluble type
  • the polymer is selected from the group consisting of polystyrene, polybutyl methacrylate, polyethyl methacrylate, polymethyl methacrylate, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, One or more of polybutyl methacrylate, polyisobutyl methacrylate, polyvinyl acetate, polyvinyl chloride, styrene/acrylonitrile copolymer, cellulose acetate butyrate, and polyvinyl butyral .
  • the water-oil solvating polymer is selected from the group consisting of N-vinyl amide copolymers (labeled A1, patent from application number 201310158535.7), modified N-vinylpyrrolidone copolymer (labeled A2, One or more of the modified acrylate copolymer (labeled A3, cited in Japanese Patent Application No. 201410062775.1).
  • N-vinyl amide copolymer (A1) is one or more of the following structural formulas:
  • ratio of moles of x:y is from 50:50 to 99:1;
  • R 1 and R 3 are each independently selected from one of -H and -CH 3 ;
  • R 2 is selected from One of them, where n is an integer from 1 to 4.
  • the ratio of moles of x:y is from 1:99 to 99:1, preferably from 50:50 to 90:10;
  • R 1 , R 2 are independently selected from hydrogen, halogen, cyano, methyl or ethyl;
  • R 3 is selected from one of C1-C3 alkyl groups
  • R 4 is selected from the group consisting of a C1-C6 alkyl group and a terminal hydroxyl-substituted C1-C6 alkyl group;
  • R 5 is selected from a C1-C4 alkyl group, a C3-C10 cycloalkyl group, a C1-C6 alkoxy group or a C6-C10 aryl group; or an ester-bonded C1-C4 alkyl group, C3- a cycloalkyl group of C10, a C1-C6 alkoxy group or a C6-C10 aryl group; or an amide-bonded C1-C4 alkyl group, a C3-C10 cycloalkyl group or a C6-C10 aryl group; Alternatively, it may be selected from a C1-C4 alkyl group bonded to a urethane bond, a C3-C10 cycloalkyl group or a C6-C10 aryl group.
  • the crosslinking agent in the heat sensitive layer is a polyfunctional acrylate compound and a photopolymerizable prepolymer.
  • the polyfunctional acrylate compound is ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethyl diacrylate, dipropylene glycol diacrylate (DEGDA), Triethylene glycol dimethacrylate, tripropylene glycol diacrylate (TPGDA), tripropylene glycol dimethacrylate, polyethylene glycol (200-600) diacrylate, polypropylene glycol (400) diacrylate, poly Propylene glycol (400) dimethacrylate, 1,4-butanediol diacrylate, bisphenol A diacrylate, 1,6-hexanediol diacrylate (HDDA), neopentyl glycol diacrylate, Pentaerythritol triacrylate (PETA), hydroxypropyl glyceryl triacrylate, hydroxyethyl trimethylolpropane triacrylate, pentaerythritol tetraacrylate (PET4A), bis(trimethyl
  • the photopolymerizable prepolymer is an epoxy acrylate and a urethane acrylate; more preferably, the photopolymerizable prepolymer comprises 10 to 30% by weight based on the total mass of the crosslinking agent.
  • a diluent may be added to the heat sensitive layer.
  • the diluent is a low viscosity compound containing a carbon-carbon double bond.
  • the diluent is isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and dipropylene glycol diacrylate.
  • the diluent is isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and dipropylene glycol diacrylate.
  • the diluent is isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and dipropylene glycol diacrylate.
  • the polymerization initiator is an initiator capable of thermally decomposing to generate a radical and a photoinitiator having a wavelength of ⁇ 300 nm of a main peak of ultraviolet absorption.
  • the thermally decomposable free radical generating initiator is persulfate, azobisisobutyronitrile (AIBN), 2,2-azobis(2-amidinopropane) dihydrochloride (ABAH) Azobisisovaleronitrile (AMBN), azobisisoheptanenitrile (ADVN), azobiscyclohexylcarbonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, benzoyl peroxide One or more of tert-butyl ester, lauroyl peroxide and methyl ethyl ketone peroxide.
  • AIBN azobisisobutyronitrile
  • ABAH 2,2-azobis(2-amidinopropane) dihydrochloride
  • AMBN azobisisoheptanenitrile
  • ADVN azobiscyclohexylcarbonitrile
  • benzoyl peroxide benzoyl peroxide
  • benzoyl peroxide
  • the photoinitiator having a wavelength of ⁇ 300 nm of the main peak of ultraviolet absorption is 2-hydroxy-2-methyl-1-phenylacetone (Darocur 1173), 1-hydroxycyclohexyl benzophenone (Irgacure 184), tetramethyl Michler's ketone, tetraethylmethanol ketone, methyl ketone ketone, diphenyl iodonium hexafluorophosphate, hexafluorophosphoric acid-1,6-p-methyldiphenyl iodonium salt, hexafluorophosphate-1 One of 6-p-tert-butyldiphenyliodonium salt, hexafluoroantimony-1,6-p-methyldiphenyliodonium salt, triphenylsulfonium hexafluorophosphate and triazine or A variety.
  • the infrared absorbing dye in the invention mainly functions as energy transfer and can absorb infrared laser
  • the light energy converts the light energy into heat energy to decompose the polymerization initiator.
  • the infrared absorbing dye is a benzofluorene cyanine dye or a step cyanine dye having a maximum absorption wavelength of 750-850 nm, for example, NK-2014, NK-2268, and other companies of the Japanese Linyuan Company. product;
  • the coloring background dye needs to be added to the heat sensitive layer.
  • the colored background dye is selected from the group consisting of Acid Blue BRL, Acid Blue B, Acid Blue 2R, Acid Blue Blue, Acid Blue RLS, Victoria Pure Blue, Indigo Blue, Phthalocyanine Blue, Methyl Violet, Crystal Violet Lactone, One or more of colorless crystal violet lactone, crystal violet lactone and decene.
  • the heat sensitive layer is coated with a heat sensitive protective layer on the heat sensitive layer, and the heat sensitive protective layer is hydrophilic; after exposure, the exposed areas of the heat sensitive protective layer and the heat sensitive layer become oleophilic, and the upper and lower layers are added. Connection; the non-exposed area has the same hydrophilicity and is soluble in water or fountain solution.
  • the function of the thermal protective layer not only increases the image fastness of the exposed area, but also does not affect the water developability of the non-exposed area, thus achieving a double improvement of developability and printing durability.
  • the heat-sensitive protective layer comprises 40-90 parts of a water-soluble resin, 10-60 parts of a hydrophilic crosslinking agent, and 1-30 parts of an acid generator; preferably, the heat-sensitive protective layer comprises a water-soluble resin 60-90 parts, 20-40 parts of hydrophilic cross-linking agent and 1-10 parts of acid generator.
  • the water-soluble resin in the heat-sensitive protective layer is selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, N-vinylpyrrolidone and vinyl acetate copolymer (VA73, VA64, VA55, VA37), N-vinylpyrrolidone and (Meth)acrylate copolymer, N-vinylpyrrolidone and (meth)acrylamide copolymer, N-vinylpyrrolidone and styrene copolymer, N-vinylamide copolymer (labeled A1, cited from the application No.
  • modified N-vinylpyrrolidone copolymer (labeled A2, cited in patent application number 201410182220.0) and modified acrylate copolymer (labeled A3, cited in patent application number 201410062775.1)
  • aqueous nylon resin gelatin and cellulose derivatives.
  • the cellulose derivative may be selected from the group consisting of cellulose nitrate, cellulose acetate, cellulose acetate butyrate and cellulose xanthate, methyl cellulose, carboxymethyl cellulose, ethyl fiber. , hydroxyethyl cellulose, cyanoethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose.
  • the hydrophilic crosslinking agent is selected from an epoxy compound or a vinyl ether monomer containing at least one hydrophilic group; preferably, the hydrophilic group is a hydroxyl group, a carboxyl group, and an ether bond.
  • the hydrophilic crosslinking agent is hydroxyethyl vinyl ether, hydroxybutyl vinyl ether (HBVE), diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl Ether (DVE-3), n-butyl glycidyl ether (BGE), allyl glycidyl ether (AGE), 5-ethylhexyl glycidol Ether (EHAGE), phenyl glycidyl ether (PGE), cresol glycidyl ether (CGE), p-isobutylphenyl glycidyl ether (BPGE), diglycidyl ether (DGE), polyglycol diglycidyl ether (PEGGE), polypropylene glycol diglycidyl ether (PPGGE), butanediol diglycidyl ether (BDGE), trimethylolpropane glycidyl ether (TMP
  • the acid generator is selected from an acid generator having a UV absorption main peak wavelength of ⁇ 300 nm and having self-light safety.
  • the acid generator is one or more of an iodonium salt, a phosphonium salt, and a triazine derivative.
  • the acid generator is diphenyliodonium hexafluorophosphate, 1,6-p-methyldiphenyliodonium hexafluorophosphate, and 1,6-p-tert-butyl hexafluorophosphate.
  • diphenyliodonium salt, hexafluoroantimony-1,6-p-methyldiphenyliodonium salt, triphenylsulfonium hexafluorophosphate and triazine is diphenyliodonium hexafluorophosphate, 1,6-p-methyldiphenyliodonium hexafluorophosphate, and 1,6-p-tert-butyl hexafluorophosphate.
  • the acid generator of the present invention generates cations by thermal cracking under the action of heat, and initiates cationic polymerization of the hydrophilic diluent in the heat sensitive protective layer.
  • a surfactant may be added as a coating property improver in the heat sensitive layer and the heat sensitive protective layer; a resistance may be added to the heat sensitive layer and the heat sensitive protective layer.
  • the polymerization agent acts as a stabilizer.
  • the amount of surfactant added is 5% by weight of the coating solids.
  • the exposed regions undergo cross-linking polymerization to form a dense hardened layer.
  • a method for preparing a heat-sensitive, non-treated lithographic printing plate material containing a heat-sensitive protective layer specifically comprising the following steps:
  • the heat sensitive layer and the heat sensitive protective layer of the present invention can be cured by infrared laser irradiation.
  • the heat sensitive layer undergoes cross-linking polymerization in the exposed region to form a dense hardened layer, which increases the bonding with the upper and lower layers, and the non-exposed area does not change, and is only mechanically coupled with the support.
  • the lock relationship can be removed by external force and aqueous solution.
  • the solvent is pure water, a mixed solvent of pure water and ethanol, or a mixed solvent of pure water and propylene glycol methyl ether.
  • the organic solvent is preferably one or more of an ether, a glycol ether ester, an acyclic ester, a cyclic ester, a ketone, and tetrahydrofuran.
  • the ether is selected from one or more of diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol butyl ether;
  • the glycol ether The ester is selected from one or more of ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, and ethylene glycol methyl ether acetate;
  • the acyclic ester is selected from the group consisting of ethyl lactate, butyl acetate, and pentane acetate.
  • an ester ethyl pyruvate, etc.
  • the cyclic ester is ⁇ -butyrolactone or the like
  • the ketone is selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, and One or more of 2-heptanone.
  • the coating method is not particularly limited and is a coating method of a known lithographic printing plate; preferably, the coating method is an air knife coating method, a blade coating method, a metal bar method, or a blade coating method. Method, dip coating method, gravure coating method, cast coating method, spin coating method, extrusion coating method, or the like.
  • the drying temperature is 80 to 150 ° C; preferably, the drying temperature is 90 to 130 ° C.
  • the hydrophilic layer has a coating dry mass of 0.001-0.1 g/m 2 on the support; the heat-sensitive layer has a coating dry mass on the hydrophilic layer of 0.1-10 g/m 2 ;
  • the dry thermal mass of the thermal protective layer on the heat sensitive layer is from 0.1 to 5 g/m 2 .
  • a use of a thermally sensitive, process-free lithographic printing plate material comprising a thermal protective layer for exposure in a wavelength region from 750 nm to 1200 nm, the source of exposure being from an infrared laser source.
  • the lithographic printing plate material of the present invention can also be used in a CTP-free, process-free lithographic printing plate material.
  • the heat-sensitive protective layer in the lithographic printing plate material can not only isolate oxygen, but also protect the heat-sensitive layer from oxygen inhibition; and can generate polymerization reaction by sensible heat, thereby improving the bonding force with the next layer, so that The printed image provided by the printer has high precision, good developability and high printing durability.
  • a scanning method of infrared laser includes cylindrical outer wall scanning, cylindrical inner wall scanning or plane scanning.
  • the lithographic printing plate material of the invention can be used for exposure in the wavelength region of 750-1200 nm, and can also be used for the CTP-free process-free lithographic printing plate material; the thermal protective layer in the printing plate material can protect the oxygen from being protected.
  • the heat sensitive layer is not affected by oxygen inhibition; the polymerization reaction can be induced by heat, and the bonding force with the next layer is improved, so that the printing plate image provided by the film has high precision, good developability and high printing durability; Therefore, the heat-sensitive protective layer and the heat-sensitive layer of the present invention can be used together to ensure water developability.
  • an on-machine developed lithographic printing plate with good resolution and high printing durability is obtained.
  • a heat-sensitive, process-free lithographic printing plate material comprising a heat-sensitive protective layer comprising, in order from bottom to top, a support, a hydrophilic layer, a heat sensitive layer and a thermal protective layer.
  • Hydrophilic layer a 0.5% by mass aqueous solution of polyvinyl alcohol 2488 was extrusion-coated on the support, and then dried at 100 ° C for 1 minute to obtain a hydrophilic layer having a coating dry mass of 0.02 g/m 2 . .
  • Thermosensitive layer The heat sensitive layer coating liquid was extrusion-coated on the hydrophilic layer prepared as above, and then dried at 100 ° C for 3 minutes to obtain a heat sensitive layer having a coating dry mass of 1.3 g/m 2 .
  • Heat-sensitive protective layer The heat-sensitive protective layer coating liquid was extrusion-coated on the heat-sensitive layer prepared as described above, and then dried at 100 ° C for 3 minutes to obtain a coating dry mass of 1.5 g/m 2 . Thermal protection layer.
  • the thermal protective layer coating liquid formula is the thermal protective layer coating liquid formula:
  • the difference between the embodiment 1-5 and the embodiment 6-20 is that there is no hydrophilic layer between the support of the embodiment 1-5 and the heat sensitive layer, and the thermosensitive coating liquid is directly extrusion-coated on the support. A heat sensitive layer is obtained.
  • the structure of the printing plate is a thermal protective layer, a heat sensitive layer and a support in order from top to bottom, and the formulation of the heat sensitive layer coating liquid and the heat sensitive protective layer coating liquid is as described above.
  • the lithographic printing plate materials of the above examples and comparative examples were exposed using a Kodak Fully Thermal CTP plate-making machine, and the exposure energy was set to 100 mJ/cm 2 .
  • the printing material which has not been developed after the same exposure described above is directly hung on the printing machine, and the ink supply is initially set to zero, and the fountain solution is sufficiently supplied to the layout to start printing, if printing is started from less than 100 sheets.
  • the on-press developability is evaluated as "good”; if the normal print without the dirty plate is obtained from less than 200 sheets, the on-press developability is evaluated as "better”; at 200 sheets The above is evaluated as "poor”.
  • Comparing Table 1 and Table 2 it can be seen that Comparative Examples 1-4 and 7-9 used the same heat sensitive layer, except that the composition of the heat sensitive protective layer was different, and the resin of the heat sensitive protective layer of Comparative Example 1 was used.
  • the film-forming resin described in the heat-sensitive layer does not have water solubility.
  • the water developability of Comparative Example 1 is poor; the hydrophilic cross-linking agent of the heat-sensitive protective layer of Comparative Example 2 is classified.
  • the polyfunctional acrylate described in the heat sensitive layer is subjected to radical polymerization, which is inhibited by oxygen and has a limited degree of polymerization; in Comparative Examples 3 and 4, the acid generating agent of the thermal protective layer is respectively made of a heat sensitive layer.
  • the initiator described in the above generates free radicals after heating, and also occurs in free radical polymerization, which results in a limited degree of polymerization due to oxygen inhibition; similarly, the composition of the thermal protective layer of Comparative Examples 7-8 is incomplete and cannot be The polymerization reaction was carried out, and the infrared laser exposure failed to form a contrast with the non-exposed areas, so it can be seen from Table 3 that the water developability of Comparative Examples 1-4 and 7-9 is acceptable, but the printing durability is greatly reduced, and the resolution is further The rate is not as good as in the case; the thermal protective layer and the actual ratio of 5 and 6 The same embodiment, but the film-forming resin selected thermosensitive layer is not present In the film-forming resin described above, a water-oil-soluble resin having no double bond or an oil-soluble resin having a low weight average molecular weight was used, and as a result, the printing durability was inferior to that of the examples.
  • the above results show that the heat-sensitive protective layer and the heat-sensitive layer of the present invention can be used

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Abstract

一种含感热保护层的热敏免处理的平版印刷版材料,该平版印刷版材料从下到上依次包括:支持体、亲水层、热敏层和感热保护层。其中感热保护层既能起到隔绝氧气、保护热敏层不受氧阻聚的作用,又能感热发生聚合反应,提高与下一层的结合力,使印刷版图像精度高、显影性好、耐印力高。

Description

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 技术领域
本发明涉及平版印刷版材料;更具体地涉及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。
背景技术
近年来,盛行依靠数字技术用计算机电子化地处理、存储和输出图文信息,而CTP技术正是其中备受瞩目的一种。CTP技术是用激光等定向性高的光,按照数字化图像信息进行扫描,直接制造印刷版的技术。另外对于需要显影后处理的传统印刷版来说,可以列举出由于显影液的动态因素而产生的制版缺陷,例如显影液的pH值变动或显影液中感光层成分的蓄积,导致显影性降低等。更不用说制造显影液的成本、处理显影废液的花费以及工业排放对环境的污染,这些均使人们对于免处理版材的期望日益增加。
免处理CTP版材主要分为热敏型、光敏型和喷墨型三大类。喷墨型CTP版材主要问题是图像精度不如热敏型和光敏型CTP版材。光敏型CTP版材主要是微胶囊型的,其主要问题是曝光后需要保护胶辅助显影,而且由于微胶囊与支持体的粘合性差,耐印力存在一定缺陷。热敏型CTP版材的最大优势是能够明室操作。早期的热敏免处理CTP版材有热烧蚀型和热熔融型。热烧蚀型免处理方式,由于会产生烧蚀残渣容易污染曝光机等缺点已经逐步被热熔融型技术所取代。热熔融型CTP版材在曝光后需要特殊的胶水清除未曝光区域才能得到图文信息,相当于简化了“显影”过程。于是另一种简化制版的显影方式,称为“机上显影”的免处理方式得以实现。机上显影,指的是在平版印刷版原版曝光后,在不进行传统显影的情况下,将印刷版原版直接挂上印刷机,在印刷过程早期通过润版液(曝光区亲油)或者油墨(曝光区亲水)清除未曝光区域。富士公司提出的一种机上显影型热敏印刷版材技术特点是在版基上先涂布上一层亲油性热敏层,再涂上亲水层以及水溶性保护层,亲水层中含有无机亲水性基体,曝光后亲油层与亲水层间作用力下降,印刷时亲油层的非曝光区被亲水层和油墨中的亲水性物质裹挟着除去,曝光区留下形成图文信息;还有在图像记录层中使用具有环氧烷基团的粘合性聚合物,在保护层中使用羟烷基纤维素,促进了机上显影性,抑制 了层间混合,提高了上墨性和耐印力,可以列举的专利有JP 2002219881和WO 2012/026265;另一种机上显影型热敏印刷版材技术特点是版基上涂有热敏成像层,版基和热敏成像层之间还含有一层极薄的水溶性夹层,但该水溶性夹层极其薄,不会影响热敏成像层与版基间的机械联锁,热敏成像层上再涂一层水溶性保护层,保护层的作用是隔绝氧,防止氧阻聚,专利公开号为WO 02/21215 A1;乐凯华光印刷科技公司提出的免处理热敏版的结构包括支持体、热敏层和保护层,其中热敏层由水溶性热交联共聚物、交联剂、多官能团单体、热敏引发剂和红外染料组成。其中所述的水溶性热交联共聚物为支链上含有环氧基团、氰基和醚键的共聚物,通过该共聚物曝光前后水溶性的改变来实现水显影,专利公开号为CN105372935A;成都科瑞聚数码科技有限公司提出的免处理热敏阴图版的结构包括支持体以及涂布于上的热敏阴图成像元件,所述的热敏阴图成像元件包括亲水性聚合物微粒、疏水性聚合物微粒和可能含有的能量转换物质构成,该热敏阴图成像元件受到辐照的部分变为疏水区,而未辐照的部分保留其亲水性能,于是能实现润版液机上显影,可以列举的专利公开号为CN101269564、CN101376305、CN101376306、CN101376307。这些发明在同时满足各种印刷条件下防止脏版(即显影性能好)和耐印力高两种要求时仍存在改进空间。
发明内容
本发明的一个目的在于提供一种含感热保护层的热敏免处理的平版印刷版材料。
本发明的另一个目的在于提供一种含感热保护层的热敏免处理的平版印刷版材料的应用。
为达到上述目的,本发明采用下述技术方案:
平版印刷版材料从下到上依次包括:支持体、亲水层、热敏层和感热保护层。
进一步,所述支持体、亲水层和感热保护层是亲水的;所述热敏层是亲油的或双亲的(所述双亲是指既有亲油性又有亲水性)。
进一步,本发明中的支持体为可担载感光层的板状体或膜体。
优选地,所述可担载感光层的板状体为铝板;所述可担载感光层的膜体为各种塑料薄膜。
更优选地,所述铝板是指与热敏层接触的一侧进行粗糙化处理的和阳极氧化处理的铝板;所述塑料薄膜为聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二 醇酯、聚乙烯、聚丙烯、聚苯乙烯、聚乙烯醇缩醛、聚碳酸酯、二醋酸纤维素和硝酸纤维素中的一种或多种;更进一步优选地,所述塑料薄膜为聚对苯二甲酸乙二醇酯或聚萘二甲酸乙二醇酯。
所述粗糙化处理的方法为机械法或电解腐蚀法;所述机械法没有特别限制,优选为钢丝刷研磨法;所述电解腐蚀法没有特别限制,优选在酸性电解液中进行的电化学表面粗糙化的方法。
所述阳极氧化处理的方法没有特别的限制,可使用公知的方法进行。
所述支持体在进行阳极氧化处理时,可进行封孔处理;所述封孔处理可用热水处理、沸水处理、水蒸气处理、硅酸钠处理、重铬酸盐水溶液处理、亚硝酸盐处理或乙酰胺处理等公知的方法进行。
本发明为了提高这些塑料薄膜的亲水性,在与感光层接触的一侧的塑料薄膜上进行亲水化加工;所述亲水化加工,可以采用电晕放电处理、火焰处理、等离子体处理和紫外线照射处理等公知的方法进行。
进一步,本发明的所述亲水层可溶于润版液等水溶液,主要由水溶性树脂构成;
优选地,所述亲水层的水溶性树脂选自聚乙烯醇、聚乙烯吡咯烷酮、水性尼龙树脂、明胶和纤维素衍生物中的一种或多种。
所述亲水层厚度足够薄,不会影响热敏层与支持体之间通过机械连锁的方式结合在一起。
进一步,所述热敏层包括以下质量份的组分:成膜树脂10-60份、交联剂30-90份、稀释剂0-40份、聚合引发剂1-30份、红外吸收染料1-10份和着色背景染料0.1-10份;优选地,所述热敏层包括以下质量份的组分:成膜树脂20-50份、交联剂50-80份、稀释剂0-30份、聚合引发剂1-10份、红外吸收染料1-5份和着色背景染料0.1-5份。
进一步,所述成膜树脂是重均分子量为20000-100000的油溶性聚合物和重均分子量为10000-200000的带有可反应碳碳双键的水油兼溶性聚合物中的一种或多种。
优选地,所述油溶型聚合物选自丙烯酸树脂、酸酐树脂、丙烯酸酯树脂、苯乙烯共聚物和聚乙烯醇缩丁醛中的一种或多种;更优选地,所述油溶型聚合物选自聚苯乙烯、聚丁基异丁烯酸酯、聚乙基异丁烯酸酯、聚甲基异丁烯酸酯、聚甲基丙烯酸酯、聚甲基丙烯酸酯甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸丁酯、聚甲基丙烯酸异丁酯、聚乙酸乙烯酯、聚氯乙烯、苯乙烯/丙烯腈共聚物、乙酸丁酸纤维和聚乙烯醇缩丁醛中的一种或多种。
优选地,所述水油兼溶型聚合物选自N-乙烯基酰胺共聚物(标记为A1、引自申请号为201310158535.7的专利)、改性N-乙烯基吡咯烷酮共聚物(标记为A2,引自申请号为201410182220.0的专利)和改性丙烯酸酯共聚物(标记为A3,引自申请号为201410062775.1的专利)中的一种或多种。
更优选地,所述N-乙烯基酰胺共聚物(A1)为具有下述结构式中的一种或多种:
Figure PCTCN2017107840-appb-000001
Figure PCTCN2017107840-appb-000002
所述改性N-乙烯基吡咯烷酮共聚物的结构如式A2所示:
Figure PCTCN2017107840-appb-000003
式中,x∶y的摩尔数之比为50∶50-99∶1;
R1、R3各自独立地选自-H和-CH3中的一种;
R2选自
Figure PCTCN2017107840-appb-000004
Figure PCTCN2017107840-appb-000005
Figure PCTCN2017107840-appb-000006
中的一种,其中n为1-4的整数。
所述改性丙烯酸酯共聚物的结构如式A3所示:
Figure PCTCN2017107840-appb-000007
式中,n=1-12的整数;
x∶y的摩尔数之比为1∶99~99∶1,优选为50∶50-90∶10;
R1、R2独立地选自氢、卤素、氰基、甲基或乙基;
R3选自C1-C3的烷基中的一种;
R4选自C1-C6的烷基、端羟基取代的C1-C6的烷基中的一种;
R5选自C1-C4的烷基、C3-C10的环烷基、C1-C6的烷氧基或C6-C10的芳基;或者选自酯键连接的C1-C4的烷基、C3-C10的环烷基、C1-C6的烷氧基或C6-C10的芳基;或者选自酰胺键连接的C1-C4的烷基、C3-C10的环烷 基或C6-C10的芳基;或者选自氨基甲酸酯键连接的C1-C4的烷基、C3-C10的环烷基或C6-C10的芳基。
进一步,所述热敏层中的交联剂为多官能度的丙烯酸酯化合物和可光聚合的预聚物。
优选地,所述多官能度的丙烯酸酯化合物为乙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基二丙烯酸酯、二丙二醇二丙烯酸酯(DEGDA)、三乙二醇二甲基丙烯酸酯、三丙二醇二丙烯酸酯(TPGDA)、三丙二醇二甲基丙烯酸酯、聚乙二醇(200-600)二丙烯酸酯、聚丙二醇(400)二丙烯酸酯、聚丙二醇(400)二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、双酚A二丙烯酸酯、1,6-己二醇二丙烯酸酯(HDDA)、新戊二醇二丙烯酸酯、季戊四醇三丙烯酸酯(PETA)、羟丙基甘油基三丙烯酸酯、羟乙基三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯(PET4A)、二(三羟甲基丙烷)四丙烯酸酯和双季戊四醇六丙烯酸酯(DPHA)中的一种或多种;
优选地,所述可光聚合的预聚物为环氧丙烯酸酯类和聚氨酯丙烯酸酯类;更优选地,所述可光聚合的预聚物占交联剂总质量的10-30wt%。
本发明为了调整热敏层的敏度和成像精度,可以在热敏层中加入稀释剂。
进一步,所述稀释剂为低粘度的含有碳碳双键的化合物。
优选地,所述稀释剂为丙烯酸异辛酯、丙烯酸异癸酯、丙烯酸月桂酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸缩水甘油酯和二丙二醇二丙烯酸酯中的一种或多种。
进一步,所述聚合引发剂为可热分解产生自由基的引发剂和紫外吸收主峰的波长≤300nm的光引发剂。
优选地,所述可热分解产生自由基的引发剂为过硫酸盐、偶氮二异丁腈(AIBN)、2,2-偶氮双(2-脒基丙烷)二氢氯化物(ABAH)、偶氮二异戊腈(AMBN)、偶氮二异庚腈(ADVN)、偶氮二环己基甲腈、偶氮二异丁酸二甲酯、过氧化苯甲酰、过氧化苯甲酰叔丁酯、过氧化月桂酰和过氧化甲乙酮中的一种或多种。
优选地,所述紫外吸收主峰的波长≤300nm的光引发剂为2-羟基-2-甲基-1-苯基丙酮(Darocur 1173)、1-羟基环己基苯酮(Irgacure184)、四甲基米蚩酮、四乙基米蚩酮、甲乙基米蚩酮、六氟磷酸二苯基碘鎓盐、六氟磷酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸-1,6-对叔丁基二苯基碘鎓盐、六氟锑酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸三苯基锍鎓盐和三嗪中的一种或多种。
本发明中所述红外吸收染料主要起能量转移的作用,可以吸收红外激光 的光能,并将所述光能转化为热能,使聚合引发剂分解。
进一步,所述红外吸收染料为最大吸收波长在750-850nm的苯并吲哚系菁染料或步花青染料,例如:日本林源公司商品化的NK-2014、NK-2268以及其他公司的同类产品;
本发明为了在曝光后图像颜色反差明显,需在热敏层中加入着色背景染料。
进一步,所述着色背景染料选自酸性蓝BRL、酸性蓝B、酸性蓝2R、酸性艳蓝G、酸性艳蓝RLS、维多利亚纯蓝、靛蓝、酞菁蓝、甲基紫、结晶紫内酯、无色结晶紫内酯、结晶紫内酯内酯和吲哚烯中的一种或多种。
本发明在热敏层上涂有感热保护层,所述感热保护层是亲水的;曝光后,感热保护层和热敏层的曝光区变为亲油的,增加了上下层的连接;非曝光区的亲水性不变,可溶于水或者润版液中。感热保护层的作用既增加了曝光区的图文牢度,又不影响非曝光区的水显影性,于是实现了显影性和耐印力的双重提高。
进一步,所述感热保护层含包括水溶性树脂40-90份、亲水性交联剂10-60份和产酸剂1-30份;优选地,所述感热保护层含包括水溶性树脂60-90份、亲水性交联剂20-40份和产酸剂1-10份。
进一步,所述感热保护层中的水溶性树脂选自聚乙烯醇、聚乙烯吡咯烷酮、N-乙烯基吡咯烷酮与乙酸乙烯酯共聚物(VA73、VA64、VA55、VA37)、N-乙烯基吡咯烷酮与(甲基)丙烯酸酯共聚物、N-乙烯基吡咯烷酮与(甲基)丙烯酰胺共聚物、N-乙烯基吡咯烷酮与苯乙烯共聚物、N-乙烯基酰胺共聚物(标记为A1、引自申请号为201310158535.7的专利)、改性N-乙烯基吡咯烷酮共聚物(标记为A2,引自申请号为201410182220.0的专利)和改性丙烯酸酯共聚物(标记为A3,引自申请号为201410062775.1的专利)、水性尼龙树脂、明胶和纤维素衍生物中的一种或多种。
优选地,所述纤维素衍生物可以选自纤维素硝酸酯、纤维素乙酸酯、纤维素乙酸丁酸酯和纤维素黄酸酯、甲基纤维素、羧甲基纤维素、乙基纤维素、羟乙基纤维素、氰乙基纤维素、羟丙基纤维素或羟丙基甲基纤维素。
进一步,所述亲水性交联剂选自至少含有一个亲水基团的环氧化合物或者乙烯基醚单体;优选地,所述亲水基团为羟基、羧基和醚键。
所述亲水性交联剂为羟乙基乙烯基醚、羟丁基乙烯基醚(HBVE)、二乙二醇单乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚(DVE-3)、正丁基缩水甘油醚(BGE)、烯丙基缩水甘油醚(AGE)、5-乙基己基缩水甘油 醚(EHAGE)、苯基缩水甘油醚(PGE)、甲酚缩水甘油醚(CGE)、对异丁基苯基缩水甘油醚(BPGE)、二缩水甘油醚(DGE)、聚乙醇二缩水甘油醚(PEGGE)、聚丙二醇二缩水甘油醚(PPGGE)、丁二醇二缩水甘油醚(BDGE)、三甲醇基丙烷缩水甘油醚(TMPGE)或丙三醇三缩水甘油醚(GGE)等。
进一步,所述产酸剂选自紫外吸收主峰波长≤300nm、具有自光安全性的产酸剂。
优选地,所述产酸剂为碘鎓盐、锍鎓盐和三嗪衍生物中的一种或多种。
更优选地,所述产酸剂为六氟磷酸二苯基碘鎓盐、六氟磷酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸-1,6-对叔丁基二苯基碘鎓盐、六氟锑酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸三苯基锍鎓盐和三嗪中的一种或多种。
本发明的产酸剂在热作用下会异裂产生阳离子,引发感热保护层中的亲水性稀释剂发生阳离子聚合反应。
在不影响本发明的平版印刷版材料性能的范围内,可在热敏层和感热保护层中添加表面活性剂作为涂布性改善剂;可在热敏层和感热保护层中添加阻聚剂作为稳定剂。优选地,表面活性剂的添加量≤涂层固含量的5%wt。
本发明的平版印刷版材料曝光后,曝光区发生交联聚合反应形成致密的硬化层。
一种含感热保护层的热敏免处理的平版印刷版材料的制备方法,具体包括如下步骤:
1)将构成所述热敏层的各组分溶于有机溶剂,制成热敏层涂布液;
2)将构成所述感热保护层的各种组分溶于溶剂中,剧烈搅拌,制成感热保护层的涂布液;
3)将水溶性树脂溶于水中,制成亲水层涂布液;
4)将所述亲水层涂布液均匀涂布在所述支持体上,然后干燥,得亲水层;将所述热敏层涂布液均匀涂布在所述亲水层上,然后干燥,得热敏层;将所述感热保护层的涂布液均匀涂布在所述热敏层上,然后干燥,即得到含感热保护层的热敏免处理的平版印刷版材料。
本发明的热敏层和感热保护层可在红外线激光照射下进行固化。
本发明的平版印刷版材料曝光后,所述热敏层在曝光区发生交联聚合反应形成致密的硬化层,增加了与上下层的联结,非曝光区不变化,与支持体仅是机械联锁的关系,可以在外力和水溶液的作用下除去。
进一步,所述溶剂为纯水、纯水与乙醇的混合溶剂或纯水与丙二醇甲醚的混合溶剂。
进一步,所述的有机溶剂优选为醚、二醇醚酯、无环酯、环酯、酮、四氢呋喃中的一种或多种。
优选地,所述的醚选自二乙二醇二甲醚、二丙二醇单甲醚、丙二醇甲醚、乙二醇乙醚和丙二醇丁醚等中的一种或多种;所述的二醇醚酯选自乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯和乙二醇甲醚醋酸酯等中的一种或多种;所述的无环酯选自乳酸乙酯、乙酸丁酯、乙酸戊酯和丙酮酸乙酯等中的一种或多种;所述的环酯是γ-丁内酯等;所述的酮选自丙酮、丁酮、环己酮、甲基异丁基酮和2-庚酮中的一种或多种。
进一步,所述涂布方法没有特别限制,为公知的平版印刷版的涂布方法;优选地,所述涂布方法为气刀涂布法、刮板涂布法、金属棒法、刮刀涂布法、浸涂法、凹版涂布法、流延涂布法、旋转涂布法或挤出涂布法等。
进一步,所述干燥的温度为80-150℃;优选地,所述干燥温度为90-130℃。
进一步,所述亲水层在支持体上的涂层干质量为0.001-0.1g/m2;所述热敏层在亲水层上的涂层干质量为0.1-10g/m2;所述感热保护层在热敏层上的涂层干质量为0.1-5g/m2
一种含感热保护层的热敏免处理的平版印刷版材料的应用,该平版印刷版材料用于750nm-1200nm的波长区域曝光,所述曝光的光源来自红外激光光源。
本发明所述平版印刷版材料也能用于CTP方式的免处理型平版印刷版材料。所述平版印刷版材料中的感热保护层既能起到隔绝氧气,保护热敏层不受氧阻聚的作用;又能感热发生聚合反应,提高了与下一层的结合力,使其所提供的印刷版图像精度高、显影性好的同时耐印力高。
作为红外激光的扫描方法,包括圆筒外壁扫描、圆筒内壁扫描或平面扫描等。
在进行图像曝光后,用纯水显影,显影温度为15-25℃。
本发明的有益效果如下:
本发明平版印刷版材料能够用于750-1200nm波长区域曝光,同时也能用于CTP方式的免处理型平版印刷版材料;该印刷版材料中的感热保护层既能起到隔绝氧气,保护热敏层不受氧阻聚的作用;又能感热发生聚合反应,提高了与下一层的结合力,使其所提供的印刷版图像精度高、显影性好的同时耐印力高;因此本发明的感热保护层和热敏层搭配使用能够在保证水显影性 的同时,得到分辨率好、耐印力高的机上显影平版印刷版。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
一种含感热保护层的热敏免处理的平版印刷版材料,该平版印刷版材料从下到上依次包括:支持体、亲水层、热敏层和感热保护层。
支持体:使用预先处理好的并满足下列条件的铝板基:铝板基尺寸:1030mm×800mm;铝板基厚度:0.28-0.3mm;砂目规格:Ra=0.5-0.6μm;Rh=0.3-0.35μm;阳极氧化膜重量:3.0-3.5g/m2
亲水层:在所述支持体上挤压涂布0.5%质量浓度的聚乙烯醇2488水溶液,然后在100℃条件下干燥1分钟,得涂层干质量为0.02g/m2的亲水层。
热敏层:在如上制作的亲水层上挤压涂布热敏层涂布液,然后在100℃条件下中干燥3分钟,得涂层干质量为1.3g/m2的热敏层。
所述热敏层涂布液配方:
Figure PCTCN2017107840-appb-000008
感热保护层:在如上述所制作的热敏层上挤压涂布感热保护层涂布液, 然后在100℃条件下干燥3分钟,得涂层干质量为1.5g/m2的感热保护层。
所述感热保护层涂布液配方:
Figure PCTCN2017107840-appb-000009
实施例1-5与实施例6-20的区别在于,实施例1-5的支持体和热敏层之间没有亲水层,是将热敏涂布液直接挤压涂布于支持体上得到热敏层,印刷版结构组成从上到下依次为感热保护层、热敏层和支持体,热敏层涂布液和感热保护层涂布液的配方如上所述。
曝光实验
利用柯达全胜热敏CTP制版机对上述实施例和对比例的平版印刷版材料进行曝光,曝光能量设定为100mJ/cm2
水显影性实验
1)将曝光完的上述实施例和对比例的平版印刷版材料放至20℃纯水中静置10秒,然后用海绵轻轻擦拭平版印刷版材料,除去未曝光部分,留下曝光区。
2)水显影性的评价:未曝光部分完全除去时评价为“干净”,有少量感光层残留时评价为“较干净”,有显著残膜或显影性不良时评价为“差”。
对水显影性评价为“干净”的情况进行分辨率评价:如果2%网点和20μm细线清楚,则评价为“好”;如果5%网点和40μm以上细线清楚,则评价为“较好”;如果再现性在10%网点以上则评价为“差”。
对水显影性评价为“干净”的情况还进行了耐印力考察。
印刷机上显影试验
使用上述同样的曝光后未显影的印刷版材料直接挂到印刷机上,开始时将墨供给设定为零,润版液充分供给到版面的状态下开始印刷,如果从开始印刷到低于100张时能获得没有脏版的正常印刷物,则机上显影性评价为“好”;如果从低于200张时能获得没有脏版的正常印刷物,则机上显影性评价为“较好”;在200张以上时评价为“差”。
按以上方式评价结果显示于表3中。
表1、热敏层配方
Figure PCTCN2017107840-appb-000010
表2、感热保护层配方
Figure PCTCN2017107840-appb-000011
Figure PCTCN2017107840-appb-000012
表3、水显影热敏CTP版的评价结果
实施例 水显影性 分辨率 耐印力(印) 机上显影性
1 干净 >8万 较好
2 干净 >8万 较好
3 干净 >10万 较好
4 干净 >8万 较好
5 干净 >8万 较好
6 干净 >5万
7 干净 >5万
8 干净 >5万
9 干净 >5万
10 干净 >5万
11 干净 >5万
12 干净 >5万
13 干净 >5万
14 干净 >5万
15 干净 >5万
16 干净 >5万
17 干净 >5万
18 干净 >5万
19 干净 >5万
20 干净 >5万
对比例1 \ \
对比例2 干净 较好 <5千
对比例3 干净 较好 <5千
对比例4 干净 较好 <5千
对比例5 干净 <1万
对比例6 干净 <1万
对比例7 干净 较好 <3千
对比例8 干净 较好 <3千
对比例9 干净 较好 <3千
结论:从实施例1-20可以看出,任何实施例的结果中均显示了好的水显影性、好的机上显影性、好的分辨率和大于5万印的良好的耐印力;
比较表1和表2可以看出,对比例1-4和7-9采用了相同的热敏层,区别在于感热保护层组分的不同,对比例1的感热保护层的树脂采用了热敏层中所述的成膜树脂,不具有水溶性,从表3中可以看出,对比例1的水显影性很差;对比例2的感热保护层的亲水性交联剂采用类热敏层中所述的多官能团丙烯酸酯,发生的是自由基聚合反应,会受氧阻聚,聚合程度有限;对比例3和4,感热保护层的产酸剂分别采用了热敏层中所述的引发剂,受热后产生自由基,同样发生的是自由基聚合反应,由于氧阻聚而导致聚合程度有限;类似地,对比例7-8的感热保护层组成不完整,不能进行聚合反应,红外激光曝光与非曝光区域未能形成反差,所以从表3中可以看出,对比例1-4和7-9水显影性尚可,但耐印力大大降低了,而且分辨率也不如实施例的情况;对比例5和6感热保护层与实施例的一致,但热敏层的成膜树脂没有选用本发 明所述的成膜树脂,而是采用了不带双键的水油兼溶树脂或者采用了重均分子量较低的油溶性树脂,结果显示耐印力不如实施例的情况。综合以上结果说明本发明的感热保护层和热敏层搭配使用能够在保证水显影性的同时,得到分辨率好、耐印力高的机上显影印刷版。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种含感热保护层的热敏免处理的平版印刷版材料,其特征在于,该平版印刷版材料从下到上依次包括:支持体、亲水层、热敏层和感热保护层;
    所述感热保护层包括水溶性树脂40-90份、亲水性交联剂10-60份和产酸剂1-30份;
    所述热敏层包括以下质量份的组分:成膜树脂10-60份、交联剂30-90份、稀释剂0-40份、聚合引发剂1-30份、红外吸收染料1-10份和着色背景染料0.1-10份;
    所述亲水层主要由水溶性树脂构成,亲水层在支持体上的涂层干质量为0.001-0.1g/m2
    所述热敏层中的成膜树脂是重均分子量为20000-100000的油溶性聚合物和重均分子量为10000-200000的水油兼溶性聚合物中的一种或多种。
  2. 根据权利要求1所述的平版印刷版材料,其特征在于,所述热敏层在亲水层上的涂层干质量为0.1-10g/m2;所述感热保护层在热敏层上的涂层干质量为0.1-5g/m2
  3. 根据权利要求1所述的平版印刷版材料,其特征在于,所述亲水层的水溶性树脂选自聚乙烯醇、聚乙烯吡咯烷酮、水性尼龙树脂、明胶和纤维素衍生物中的一种或多种。
  4. 根据权利要求1所述的平版印刷版材料,其特征在于,所述感热保护层中的水溶性树脂选自聚乙烯醇、聚乙烯吡咯烷酮、N-乙烯基吡咯烷酮与乙酸乙烯酯共聚物、N-乙烯基吡咯烷酮与(甲基)丙烯酸酯共聚物、N-乙烯基吡咯烷酮与(甲基)丙烯酰胺共聚物、N-乙烯基吡咯烷酮与苯乙烯共聚物、N-乙烯基酰胺共聚物、改性N-乙烯基吡咯烷酮共聚物、改性丙烯酸酯共聚物、水性尼龙树脂、明胶和纤维素衍生物中的一种或多种。
  5. 根据权利要求1所述的平版印刷版材料,其特征在于,所述亲水性交联剂为羟乙基乙烯基醚、羟丁基乙烯基醚、二乙二醇单乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、正丁基缩水甘油醚、烯丙基缩水甘油醚、5-乙基己基缩水甘油醚、苯基缩水甘油醚、甲酚缩水甘油醚、对异丁基苯基缩水甘油醚、二缩水甘油醚、聚乙醇二缩水甘油醚、聚丙二醇二缩水甘油醚、丁二醇二缩水甘油醚、三甲醇基丙烷缩水甘油醚或丙三醇三缩水甘油醚。
  6. 根据权利要求1所述的平版印刷版材料,其特征在于,所述产酸剂选自紫外吸收主峰波长≤300nm的产酸剂,包括六氟磷酸二苯基碘鎓盐、六氟 磷酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸-1,6-对叔丁基二苯基碘鎓盐、六氟锑酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸三苯基锍鎓盐或三嗪。
  7. 根据权利要求1所述的平版印刷版材料,其特征在于,所述热敏层中的交联剂为多官能度丙烯酸酯化合物和可光聚合的预聚物;其中,所述多官能度丙烯酸酯化合物为乙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基二丙烯酸酯、二丙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、三丙二醇二丙烯酸酯、三丙二醇二甲基丙烯酸酯、聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、聚丙二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、双酚A二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、季戊四醇三丙烯酸酯、羟丙基甘油基三丙烯酸酯、羟乙基三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯和双季戊四醇六丙烯酸酯中的一种或多种;
    所述稀释剂为丙烯酸异辛酯、丙烯酸异癸酯、丙烯酸月桂酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸缩水甘油酯和二丙二醇二丙烯酸酯中的一种或多种;
    所述红外吸收染料为苯并吲哚系菁染料或步花青染料;
    所述着色背景染料为酸性蓝BRL、酸性蓝B、酸性蓝2R、酸性艳蓝G、酸性艳蓝RLS、维多利亚纯蓝、靛蓝、酞菁蓝、甲基紫、结晶紫内酯、无色结晶紫内酯、结晶紫内酯内酯和吲哚烯中的一种或多种;
    所述聚合引发剂为可热分解产生自由基的引发剂和紫外吸收主峰波长≤300nm的光引发剂。
  8. 根据权利要求7所述的平版印刷版材料,其特征在于,优选地,所述油溶型聚合物选自聚苯乙烯、聚丁基异丁烯酸酯、聚乙基异丁烯酸酯、聚甲基异丁烯酸酯、聚甲基丙烯酸酯、聚甲基丙烯酸酯甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸丁酯、聚甲基丙烯酸异丁酯、聚乙酸乙烯酯、聚氯乙烯、苯乙烯/丙烯腈共聚物、乙酸丁酸纤维和聚乙烯醇缩丁醛中的一种或多种;
    所述水油兼溶型聚合物选自N-乙烯基酰胺共聚物、改性N-乙烯基吡咯烷酮共聚物和改性丙烯酸酯共聚物中的一种或多种。
  9. 根据权利要求7所述的平版印刷版材料,其特征在于,优选地,所述可热分解产生自由基的引发剂为过硫酸盐、偶氮二异丁腈、2,2-偶氮双(2-脒基丙烷)二氢氯化物、偶氮二异戊腈、偶氮二异庚腈、偶氮二环己基甲腈、偶氮二异丁酸二甲酯、过氧化苯甲酰、过氧化苯甲酰叔丁酯、过氧化月桂酰或过氧化甲乙酮中的一种或多种;
    所述紫外吸收主峰波长≤300nm的光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯酮、四甲基米蚩酮、四乙基米蚩酮、甲乙基米蚩酮、六氟磷酸二苯基碘鎓盐、六氟磷酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸-1,6-对叔丁基二苯基碘鎓盐、六氟锑酸-1,6-对甲基二苯基碘鎓盐、六氟磷酸三苯基锍鎓盐和三嗪中的一种或多种。
  10. 如权利要求1-9任一所述的平版印刷版材料的应用,其特征在于,该平版印刷版材料用于750nm-1200nm的波长区域曝光,所述曝光的光源来自红外激光光源。
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