WO2022143340A1 - 一种表面自带纹理的平顶网点的柔性树脂版及其制版方法 - Google Patents

一种表面自带纹理的平顶网点的柔性树脂版及其制版方法 Download PDF

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WO2022143340A1
WO2022143340A1 PCT/CN2021/140463 CN2021140463W WO2022143340A1 WO 2022143340 A1 WO2022143340 A1 WO 2022143340A1 CN 2021140463 W CN2021140463 W CN 2021140463W WO 2022143340 A1 WO2022143340 A1 WO 2022143340A1
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layer
flexible resin
resin plate
flat
particles
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PCT/CN2021/140463
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English (en)
French (fr)
Inventor
高英新
王晓阳
黄永山
刘斌
范中会
许文然
王国才
李志勇
王向利
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乐凯华光印刷科技有限公司
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Priority to EP21914077.9A priority Critical patent/EP4269111A4/en
Publication of WO2022143340A1 publication Critical patent/WO2022143340A1/zh

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    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • 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
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C—CHEMISTRY; METALLURGY
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Definitions

  • the invention relates to a preparation method of a flexible resin plate, in particular to a flexible resin plate with flat-top dots with a self-textured surface and a plate-making method thereof.
  • flexo resin plates are widely used in the printing of easily deformed or soft substrates such as cartons, flexible packaging, and labels.
  • a film with a pattern or text is placed on an unexposed flexographic plate containing a photoelastomer, exposed to ultraviolet light, and the transparent part of the film transmits ultraviolet light, and the initiator in the photoelastomer decomposes into free radicals, which initiates crosslinking.
  • the monomer reacts and cures.
  • the cross-linking reaction cannot occur in the areas that do not transmit ultraviolet rays, and the difference in their solubility in the developing solution is used to rinse and develop to obtain a relief image containing a text pattern.
  • the developed plate is dried, detackified, and post-exposed to ensure that the photosensitive layer is fully polymerized.
  • the prepared plate is fixed on the cylinder of the flexo press and is ready for printing.
  • the aforementioned plate-making process requires films with patterns or characters.
  • the films are easily affected by external conditions such as processing, dust, and humidity, causing defects and affecting the restoration of the characters and patterns of the flexible resin plate.
  • external conditions such as processing, dust, and humidity
  • it is easy to bond the film and cause plate-making disadvantages such as light refraction and scattering, resulting in a reduction in the quality of pattern or text reproduction.
  • document information with patterns or text can be converted into digital information, and with the help of computer control, the digital information can be converted into infrared laser, violet laser, etc. and output to flexographic ablation
  • laser ablation imaging is realized, and film imaging is no longer used, thereby eliminating the problem of reducing the quality of image and text reproduction caused by film plate making.
  • Such plates are called digital flexible resin plates.
  • the protective film is removed, the black film is imaged by laser ablation, and then the photosensitive elastomer is exposed with UV-A or UV-LED, rinsed with the developer, dried, and post-processed to make a printing plate. Because the exposure process is carried out in the air, the oxygen in the air inhibits the exposed surface of the photosensitive elastomer, and the dots restored by the plate are bullet-shaped.
  • the bullet dots have low support force during printing, and the friction force with the screen wall of the anilox roller is large, so the printing durability is not high, the printing effect of high-gloss dots is not clear, and the printing effect of high-definition flexo printing 150lpi cannot be achieved.
  • Patent US2009/0186308A1 describes that the oxygen concentration in the exposure machine is best at 100-190ppm. This method requires additional nitrogen making equipment, is bulky, and it is not easy to keep the nitrogen constant every time the plate is made, so it is not a good method for forming flat-top dots.
  • the second is the film coating technology. After conventional laser engraving and ablation of the black film, a film is covered to block the oxygen in the air, and then exposed to the front to form flat dots.
  • the US patent US2017/0297358A1 optimizes the exposure parameters of the film to form flat-top dots, which are suitable for corrugated box printing.
  • the patent adds a process, which is troublesome for the plate making company to use, and dust enters or bubbles are generated during lamination, resulting in waste plates.
  • the third is to immerse the plate with laser engraving and ablation black film, immerse it in water for exposure, block the oxygen in the air, and form flat dots, as described in patent CN107521214A.
  • This patent is cumbersome to use.
  • the fourth is to set an oxygen barrier layer between the laser ablation black film and the photosensitive elastomer, such as patent CN107969149A, the plate structure (A), (B), (C), (D), (E) five layers, in ( An oxygen barrier layer (C) is arranged between B) and (D), and the layer adopts 50-99% by weight of polyvinyl acetate or polyvinyl acetal with a molar hydrolysis degree of 10-75%, and 1-30% alkalinity Polymers such as polyethyleneimine, 0-50% filler SiO2 or silicates.
  • the patent uses an oxygen barrier layer and SiO 2 or silicate particles in the layer to press the surface of the flexible resin plate to form a flat-top halftone plate with its own texture. This layer contains SiO2 or silicate with an average particle size of 2-6 microns, but no organic particles.
  • US8492074B2 oxygen barrier layer using two different resins, such as polyvinylpyrrolidone, purple lacquer, polyvinyl butyral, polyvinylidene chloride or vinyl chloride polymers, can form flat top dots, but can not form the surface of the plate texture.
  • the present invention provides a flexible resin plate with flat top dots on the surface and a plate making method thereof, which can form textures and flat dots on the surface of the plate material, improve the ink transfer ability of the plate material, and improve the quality of the plate. Plate durability.
  • the object of the present invention is achieved in the following manner: a flexible resin plate with flat-top dots with a texture on the surface, the structure of which is, from top to bottom, a laser ablation black film layer, an oxygen barrier layer, and a wool with particles.
  • the oxygen barrier layer provided in the present invention reduces the influence of oxygen on the polymerization of the photosensitive elastomer, and can form flat dots.
  • a protective film may also be provided above the laser ablation black film layer to form a protective film layer for protection.
  • the protective film can be polymer materials such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PE, PVC, etc.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PE polybutylene terephthalate
  • PVC polyvinyl chloride
  • the produced film preferably a PET film, generally has a thickness of 50-150 ⁇ m, preferably 100-135 ⁇ m.
  • the laser ablation black film layer can be the laser ablation black film commonly used in the field, or can be prepared according to the preparation method of the patent ZL201110437989.9.
  • the ablation black film contains nano carbon black, the first polymer polyamide binder, the second polymer binder monoisocyanate modified polyether polyurethane compound, laser ablation dye, super dispersant, Leveling agent, defoaming agent, etc., to prepare ablation black film solution, apply the above components on the support PET or PE by means of scraper, column coating, anilox coating, etc., and use hot air, steam, infrared , microwave and other drying to form a film, for use, the coating thickness is 1-5 ⁇ m, the best coating thickness is 2-4 ⁇ m.
  • the ablation black film obtained by coating can also be coated with other materials such as 8-20 ⁇ m PE or PET, and reserved for future use.
  • the oxygen barrier layer of the present invention is composed of polyamide, acrylic resin containing acrylamide and its derivatives.
  • Acrylic resins containing acrylamide and its derivatives are poly(acrylamide-styrene-methyl methacrylate) resin, poly(N-methylol acrylamide-styrene-methyl methacrylate) resin, poly( N-Hydroxyethylacrylamide-styrene-methyl methacrylate) resin, poly(N-hydroxypropylacrylamide-styrene-methyl methacrylate) resin, polyvinylpyrrolidone, polyvinyl alcohol, gum arabic , at least one of polyvinyl butyral resin. Add leveling agent, defoamer, etc.
  • the oxygen barrier layer of the present invention is preferably a mixture of polyamide and acrylic resin containing acrylamide and its derivatives.
  • a surge temperature as high as about 1000°C will be generated, which will damage the oxygen barrier layer of the present invention, cause cracks or heat the oxygen barrier layer, resulting in uneven thickness.
  • Halogen-free flame retardants or flame retardants need to be added to the oxygen barrier layer, such as DAIGUARD-850, DAIGUARD-880, DAIGUARD-540, DAIGUARD-580 from Japan's Daiba Company, FCX-210 from Teijin Company, and FCX-210 from Kaiping Delhi Company.
  • the above components are coated on the laser ablation black film layer by means of doctor blade, column coating, anilox coating, etc., and are dried by hot air, steam, infrared, microwave, etc. to form a film, and the coating thickness is 1-5 ⁇ m. The best coating thickness is 1-3 ⁇ m.
  • the oxygen barrier layer obtained by coating can also be coated with other materials such as 8-20 ⁇ m PE or PET, and reserved for future use.
  • the organic polymer particles carried by the rough surface layer can be polymethyl methacrylate, polystyrene, polymethacrylate-gelatin dispersed particles, polymethacrylate- Gelatin dispersed particles, vinylidene chloride-methyl methacrylate-acrylic polymer emulsion, vinylidene chloride-styrene-methyl methacrylate-acrylic polymer emulsion, styrene-acrylonitrile-methacrylate polymer emulsion Glycol ether copolymer, styrene-acrylonitrile-polypropylene glycol ether methacrylate copolymer particles, polyvinyl chloride particles, etc.
  • the organic polymer particles of the matte layer can be dispersed in water, polyvinyl alcohol solution , ethylene vinyl acetate copolymer emulsion, polyvinyl pyrrolidone solution, gelatin solution, gum arabic solution, etc. Preference is given to polymethyl methacrylate aqueous dispersion system, polymethacrylate-gelatin dispersion system, polymethacrylate-polyvinyl alcohol dispersion system.
  • vinylidene chloride-methyl methacrylate-acrylic acid polymer emulsion is a copolymer of vinylidene chloride-methyl methacrylate-acrylic acid
  • vinylidene chloride-styrene-methyl methacrylate-acrylic acid is polymerized
  • the polymer emulsion is a copolymer of vinylidene chloride-styrene-methyl methacrylate-acrylic acid.
  • the average particle size of the organic polymer particles carried by the matte layer of the present invention is 0.5-15 ⁇ m, preferably 0.5-10 ⁇ m in average particle size, and more preferably 0.5-8 ⁇ m in average particle size.
  • the organic polymer particles can be coated on the oxygen barrier layer of the patent of the present invention by coating, high-pressure air gun spraying, electrostatic spraying, etc. Drying adopts steam, hot air, infrared electric heating, microwave and other methods, heating temperature 100-140 ° C, heating time In 1-3 minutes, the organic polymer particles are melted and softened by pressure and temperature to form appearance shapes such as hemispherical and elliptical, which are covered on the surface of the oxygen barrier layer of the present invention.
  • texture is generated on the surface of the photo-elastomer.
  • the photosensitive elastomer layer used in the flexible resin plate of the present invention contains at least one thermoplastic polymer material, at least one vinyl unsaturated compound, at least one initiator or initiator system, at least one dye, other auxiliary agents, and the like.
  • the thermoplastic polymeric material in the photoelastomer layer may be a butadiene/styrene copolymer, isoprene/styrene copolymer, acrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer such as polystyrene-polybutadiene-polystyrene triblock copolymer, polystyrene-polyisoprene-polystyrene triblock copolymer, polystyrene Styrene-polyvinylbutylene-polystyrene block copolymer, polystyrene-polyisoprene star copolymer, acrylonitrile/butadiene/styrene copolymer, etc.
  • the ethylenically unsaturated compound in the photoelastomer layer may be a monomer such as 2-(2-ethoxy)ethyl acrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl alcohol acrylate ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, butyl acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate Alkyl ester, octadecyl (meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonaned
  • the initiator or initiating system in the photo-elastomer layer can be benzophenone, mitinone, 4-acetoxy-4'-diethylamine benzophenone, benzoin ether, ⁇ -hydroxyisopropylbenzene Methanone, ⁇ -Hydroxycyclohexyl benzophenone, 2-phenyl-2,2-dimethoxyacetophenone, 2-tert-butylanthraquinone, isopropylthioxanthone, (morpholinobenzene Formyl) 1-hexayl 1,1 (dimethylamino) propane, benzil, benzoin, UV6501, UV6502 of Changsha Xinyu Polymer Technology Co., Ltd., GR-TPO of Hubei Gurun Technology Co., Ltd., GR-L101, GR-ITX, GR-XBPO, GR-TPO-L, GE-DETX, foreign companies such as Ciba-Geigy IGM
  • auxiliary agents such as antioxidants, thermal inhibitors, mold release agents, leveling agents, dyes, etc. may also be added to the photosensitive elastomer layer.
  • the adhesive layer of the present invention may be polyurethane, polyurethane containing 1,2-vinyl in the side chain, polyester, vinylidene chloride copolymer, vinylidene chloride-methacrylate-acrylic acid copolymer, acrylic resin, styrene - Copolymers of acrylates, or mixtures thereof.
  • the above components are prepared into a solution and coated on the support of the present invention with a coating thickness of 1-10 ⁇ m, preferably 1-5 ⁇ m.
  • the support of the present invention can be polyhexylene naphthalene-2,6-dicarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PP film, PVC film, aluminum plate base, steel plate base, magnetic steel base, etc., preferably PET film, with a thickness of 75-200 ⁇ m, preferably 100-175 ⁇ m.
  • the components in the photoelastomer layer are added to the extruder in proportion, heated, mixed, exhausted, etc., mixed at 110-150 ° C for 2-5 minutes, extruded, and obtained through the die to 0.5-6.35
  • a sheet with a thickness of mm is used as the photosensitive elastomer layer, and then the lower surface of the photosensitive elastomer sheet is heated and pressurized to cover the supporting film composed of the support and the adhesive layer of the present invention, and at the same time, the photosensitive elastomer layer is placed on the sheet.
  • the composite film containing the protective film of the present invention, the laser ablation black film layer, the oxygen barrier layer and the rough surface layer with particles is covered by heating and pressing on the top, so as to obtain a flat-topped dot with a self-textured surface of the present invention.
  • Flexible resin version
  • the plate-making method of the flexible resin plate with flat-top dots with textured surface includes: back exposure to form a base; laser engraving and ablation of the black film layer (2); UV-A or UV-LED ultraviolet light front exposure; Washing; heat drying; post-exposure; debonding.
  • the specific plate-making process can be as follows: Now, one side of the support is back-exposed with UV-A or UV-LED to form a base. Then turn the flexible resin plate over, remove the protective film, ablate the black film layer with a 1064-1070nm ND:YAG laser or ablate the black film layer to form an in-situ pattern, which is retained on the photosensitive elastomer layer.
  • the ablated part can transmit ultraviolet light, and the unablated part forms a mask to block the penetration of ultraviolet light.
  • the beneficial effects of the present invention compared with the prior art, provide a flexible resin plate with flat-top dots on the surface and a plate-making method thereof, which can form textures and flat dots on the surface of the plate.
  • the texture on the surface of the plate of the present invention can increase the printing ink transfer on the surface of the plate, improve the ink transfer ability of the plate on the spot and the dot, and the surface of the plate can be transferred to the printing plate.
  • the ink density of the material is higher and the color quality is higher; the flat-top dots formed by the plate of the invention are in contact with the anilox roller, and the flat-top dots are more resistant to abrasion, thereby improving the printing durability of the plate.
  • Fig. 1 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing obtained in Example 1; Wherein: a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and c is 150lpi2% dot profile.
  • FIG. 2 is a surface texture diagram of the solid part of the flexible resin plate obtained in Example 1, and the solid surface texture is clear.
  • Fig. 3 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing that embodiment 2 obtains; Wherein: a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and the c right is 150lpi2% dot profile.
  • Example 4 is a surface texture map of the solid part of the flexible resin plate obtained in Example 2, and the solid surface texture is clear.
  • Fig. 5 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing obtained in Example 3; Wherein: a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and c is 150lpi2% dot profile.
  • FIG. 6 is a surface texture map of the solid part of the flexible resin plate obtained in Example 3, and the solid surface texture is clear.
  • Fig. 7 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing that comparative example 1 obtains; Wherein: a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and c is 150lpi2% dot profile.
  • Fig. 9 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing that comparative example 2 obtains; Wherein: a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and c is 150lpi2% dot profile.
  • FIG. 10 is a solid portion of a flexible resin plate obtained in Comparative Example 2, the surface of which has no texture.
  • Fig. 11 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing that comparative example 3 obtains; Wherein a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and c is 150lpi2% dot profile.
  • Fig. 12 The surface texture map of the solid part of the flexible resin plate obtained in Comparative Example 3, the solid surface texture is clear.
  • Fig. 13 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing obtained in Comparative Example 4; wherein a is the front plan view of 150lpi2% dots, b is the side perspective view of 150lpi2% dots, and c is 150lpi2% dot profile.
  • organic particles and dispersion system used in the present invention are synthesized as follows:
  • the aqueous solution of sodium dodecyl sulfate with a mass fraction of 3% was respectively prepared, and 48 g of purified azobisisobutyronitrile were weighed and dissolved in 2000 ml of methyl methacrylate for later use.
  • a 100-liter dispersion kettle In a 100-liter dispersion kettle, first add 20 liters of deionized water, start stirring, heat up to an internal temperature of 60°C, and add 800 ml of a 3% aqueous sodium dodecyl sulfate solution. Then, pre-dissolved methyl methacrylate-azobisisobutyronitrile solution and 24 ml of m-benzene solution with a mass fraction of 0.5% were added. The dispersion was stirred for 30 minutes, and the stirring was stopped.
  • the above-mentioned 1.15 kilograms of methyl methacrylate particles were added to 18 kilograms of water, stirring was started, and 9 kilograms of 8811 aqueous solutions with a mass fraction of 4% were added.
  • the foaming agent was 130 mm, stirred for 2 hours, and discharged to obtain a polymethyl methacrylate-water dispersion system for later use.
  • the structure of surfactant 8811 is sodium diisooctyl succinate.
  • the aqueous solution of sodium lauryl sulfate with a mass fraction of 3% was respectively prepared, and 48 g of purified benzoyl peroxide were weighed and dissolved in 2000 ml of methyl methacrylate for later use.
  • a 100-liter dispersion kettle In a 100-liter dispersion kettle, first add 20 liters of deionized water, start stirring, heat up to an internal temperature of 60°C, and add 800 ml of a 3% aqueous sodium dodecyl sulfate solution. Then, pre-dissolved methyl methacrylate-benzoyl peroxide solution and 24 ml of m-benzene solution with a mass fraction of 0.5% were added. The dispersion was stirred for 30 minutes, and the stirring was stopped.
  • Synthesis example 3 polymethacrylate-polyvinyl alcohol dispersion system
  • the aqueous solution of sodium dodecyl sulfate with a mass fraction of 3% was respectively prepared, and 60 g of purified benzoyl peroxide was weighed and dissolved in 2000 ml of methyl methacrylate for later use.
  • a 100-liter dispersion kettle In a 100-liter dispersion kettle, first add 20 liters of deionized water, start stirring, heat up to an internal temperature of 60°C, and add 800 ml of a 3% aqueous sodium dodecyl sulfate solution. Then, pre-dissolved methyl methacrylate-benzoyl peroxide solution and 35 ml of m-benzene solution with a mass fraction of 0.5% were added. The dispersion was stirred for 30 minutes, and the stirring was stopped.
  • the protective film is made of polyethylene terephthalate (PET), with a thickness of 100 ⁇ m, produced by Lucky Company; it can also be selected from polyethylene terephthalate-2,6-dicarbonate, polybutylene terephthalate, etc. , thickness 50-150 ⁇ m.
  • PET polyethylene terephthalate
  • the protective film can also be selected from polyethylene terephthalate-2,6-dicarbonate, polybutylene terephthalate, etc. , thickness 50-150 ⁇ m.
  • the laser ablation layer was prepared according to Example 1 of ZL201110437989.9.
  • Oxygen Barrier Layer Polyamide (produced by Henkel, Germany) 4.2g, AS-586 (acrylamide-styrene-methyl methacrylate 35:45:20wt%, Lucky Chemical Co., Ltd.) 0.6g, halogen-free flame retardant DAIGUARD-880 ( 0.2g was dissolved in 95g solvent of benzyl alcohol-n-butanol mass ratio of 30:70, produced by Japan's Daiba Co., Ltd., the solution was coated on the laser ablation layer at a speed of 30 m/min, dried at 70°C for 10 minutes, An adhesive layer with a coating thickness of 2.6 ⁇ m was obtained, and an oxygen barrier layer with a coating dry weight of 2.51 g/m 2 was obtained.
  • the polymethyl methacrylate-water dispersion system of Synthesis Example 1 was sprayed on the above-mentioned oxygen barrier layer with a diaphragm pump with an outlet pressure of 2 kg, and dried at 120° C. for 2 minutes to obtain a rough surface layer with particles.
  • the protective film, the laser ablation layer, the oxygen barrier layer and the rough surface layer with particles form a composite film, which is ready for use.
  • thermoplastic elastomer SIS1107 (Kraton Company), 100 g of plasticizer polybutadiene NissoPB-P2000 (Nippon Soda, Japan), OIL (American CLUMENT) 100g, 1-hydroxycyclohexyl phenyl ketone (Zhangjiagang Free Trade Zone Tianjie International Trade Co., Ltd.) 32g, 2,6-di-tert-butyl-p-cresol (Nanjing Jiulong Chemical Co., Ltd.) 12g, three Methylol propane triacrylate 40g (Tianjin Tianjiao Chemical Co., Ltd.), 1,9-nonanediol diacrylate 15.8g (Tianjin Tianjiao Chemical Co., Ltd.), dye RED 335 (BASF Company) 0.2g were added to the twin-screw extruder. In the machine, knead at 150°C
  • adhesive layer 100 g of methyl ethyl ketone, 50 g of butyl acetate, 40 g of polyurethane vinyl acetate R-317 (produced by Lucky Company), and then 2 g of trimethylolpropane triacrylate (TMPTA, Tianjin Tianjiao Chemical Co., Ltd.), Initiator 1-hydroxycyclohexyl phenyl ketone (commonly known as 184, Zhangjiagang Free Trade Zone Tianjie International Trade Co., Ltd.) 0.5g, 2,6-di-tert-butyl-p-cresol (commonly known as 264, Nanjing Jiulong Chemical Co., Ltd.) 0.2g , 0.05g of FC-4430 (produced by 3M company), stirred in a closed container for 2 hours under the yellow safety light to obtain the coating solution of the cross-linked layer, and coated the solution on the support at a speed of 30 m/min. On the body, it was dried at 60
  • the support was made of polyethylene terephthalate, with a thickness of 125 ⁇ m, produced by Lucky Company. Polyethylene naphthalene-2,6-dicarbonate, polyethylene terephthalate, etc. can also be used, with a thickness of 50-300 ⁇ m.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the upper surface of the sheet of the body layer is heated and pressurized at 120 ° C and 6 MPa, and is covered with a composite film consisting of a protective film, a laser ablation layer, an oxygen barrier layer and a rough surface layer with particles in this embodiment.
  • a flexible resin plate with flat-top dots with a textured surface is obtained.
  • the printing plate made by the above invention without removing the protective film, first UV-A exposure lamp back exposure for 22 seconds (under 365nm, light intensity 18.1mw/cm ), then peel off the protective film, the flexible resin plate of the present invention It was sent to CDI SPARK 2120 plate making machine (produced by ESKO company), under 2540dpi, the imaging speed was set to Optics10.0, the laser dominant wavelength was 1071nm, and the black film 2 of the laser ablation layer was ablated, and the ablation pattern contained 1% at 150lpi, 2%, 3%, 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98% , 100% of the dots, including the field, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent points and independent female points. After laser ablation, the morphology of the oxygen
  • Fig. 1 is the 150lpi2% screen dot perspective view and outline diagram of the flexible resin plate obtained in Example 1; Fig. 1a is the front plan view of the 150lpi2% screen dot, Fig.
  • FIG. 1b is the side perspective view of the 150lpi2% screen dot
  • Fig. 1c is the 150lpi2% screen dot outline diagram, from the screen dot contour diagram Look, the tops of the dots are flat.
  • FIG. 2 is a surface texture diagram of the solid part of the flexible resin plate obtained in Example 1, and the solid surface texture is clear.
  • the protective film can be selected from polyethylene terephthalate-2,6-dicarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc., with a thickness of 50-150 ⁇ m.
  • PET is used as the protective film, with a thickness of 125 ⁇ m, produced by Lucky Company.
  • the laser ablation layer was prepared according to Example 2 of ZL201110437989.9.
  • Oxygen Barrier Layer Polyamide 6900 (manufactured by Henkel, Germany) 4.5g, AS-588 (N-hydroxyethylacrylamide-styrene-methyl methacrylate 30:45:25wt%, Lucky Chemical Co., Ltd.) 0.5g halogen-free flame retardant 0.3 g of agent DAIGUARD-880 (produced by Japan's Daiba Co., Ltd.) was dissolved in 100 g of a solvent with a mass ratio of benzyl alcohol-n-butanol of 30:70, and the solution was coated on the laser ablation layer at a speed of 30 m/min. After drying at °C for 10 minutes, an adhesive layer with a coating thickness of 2.7 ⁇ m was obtained, and the dry weight of the coating was 2.65 g/m 2 , and an oxygen barrier layer was prepared.
  • AS-588 N-hydroxyethylacrylamide-styrene-methyl methacrylate 30:45:25wt%, Lucky Chemical Co., Ltd
  • the protective film, the laser ablation layer, the oxygen barrier layer and the rough surface layer with particles form a composite film, which is ready for use.
  • thermoplastic elastomer SIS1107 (Kraton Company) 700g, plasticizer polybutadiene Nisso PB-P 2000 (Japan Nippon Soda) 100g, OIL (American CLUMENT) 100g, 1-hydroxycyclohexyl phenyl ketone (Zhangjiagang Free Trade Zone Tianjie International Trade Co., Ltd.) 32g, 2,6-di-tert-butyl-p-cresol (Nanjing Jiulong Chemical Co., Ltd.) 12g, three Methylol propane triacrylate 40g (Tianjin Tianjiao Chemical Co., Ltd.), 1,9-nonanediol diacrylate 15.8g (Tianjin Tianjiao Chemical Co., Ltd.), dye RED 335 (BASF Company) 0.2g, added to the twin screw In an extruder, knead at 150° C. for 2 minutes, extru
  • the support body can be selected from polyethylene naphthalene-2,6-dicarbonate, polyethylene terephthalate, polybutylene terephthalate, etc., with a thickness of 50-300 ⁇ m.
  • polyethylene terephthalate was used as the support, with a thickness of 175 ⁇ m (365 nm UV transmittance of 10 ⁇ 2%), produced by Lucky Company.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the upper surface of the sheet of the body layer is heated and pressurized at 120 ° C and 6 MPa, and is covered with a composite film consisting of a protective film, a laser ablation layer, an oxygen barrier layer and a rough surface layer with particles in this embodiment.
  • a flexible resin plate with flat-top dots with a textured surface is obtained.
  • the printing plate made by the above invention was back exposed for 45 seconds (under 365nm, light intensity 18.1mw/cm 2 ), then the protective film was peeled off, and the flexible resin plate of the present invention was sent into CDI SPARK 2120 Plate making machine (produced by ESKO company), under 2540dpi, the imaging speed is set to Optics10.0, the main wavelength of the laser is 1071nm, the laser ablation layer black film 2 is ablated, and the ablation pattern contains 1%, 2%, 3% at 150lpi , 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 100% of the dots , contains solid, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent points and independent female points. After laser ablation, the morphology of the oxygen barrier layer
  • UV-A exposure lamp to expose the plate for 720 seconds (at 365nm, the light intensity is 18.1mw/cm2), wash it with Shanghai Minchen's high-end environmental protection developer for 7 minutes, dry it with hot air at 65°C for 2 hours, and remove the sticking 5- 12 minutes, post-exposure for 5 minutes.
  • 3D microscope and Vipflex334 and other equipment to evaluate whether the solid surface has texture, 2% dot restoration size and dot edge shape, whether it is flat top dots, etc.
  • Fig. 3 is the flexographic resin plate 150lpi2% dots perspective view and outline drawing obtained in Example 2;
  • Fig. 3a is the front plan view of 150lpi2% dots,
  • Fig. 3b is the side perspective view of 150lpi2% dots,
  • Fig. 3c is 150lpi2% dots profile, from the dot profile Look, the tops of the dots are flat.
  • 4 is a surface texture diagram of the solid part of the flexible resin plate obtained in Example 2, and the solid surface texture is clear.
  • the protective film can be selected from polyethylene terephthalate-2,6-dicarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc., with a thickness of 50-150 ⁇ m.
  • PET is used as the protective film, with a thickness of 125 ⁇ m, produced by Lucky Company.
  • the laser ablation layer was prepared according to Example 3 of ZL201110437989.9.
  • Oxygen Barrier Layer Polyamide 6900 (manufactured by Henkel, Germany) 4.2g, AS-586 (acrylamide-styrene-methyl methacrylate 35:45:20wt%, Lucky Chemical Co., Ltd.) 0.6g, halogen-free flame retardant DAIGUARD-880 (produced by Japan's Daiba Co., Ltd.) 0.2g was dissolved in 95g solvent with a mass ratio of benzyl alcohol-n-butanol 30:70, the solution was coated on the laser ablation layer at a speed of 30 m/min, and dried at 70°C for 10 minutes , to obtain an adhesive layer with a coating thickness of 2.6 ⁇ m, and the dry weight of the coating is 2.51 g/m 2 to prepare an oxygen barrier layer.
  • AS-586 acrylamide-styrene-methyl methacrylate 35:45:20wt%, Lucky Chemical Co., Ltd.
  • halogen-free flame retardant DAIGUARD-880 produced by Japan's D
  • the polymethacrylate-polyvinyl alcohol dispersion system of Synthesis Example 3 was sprayed on the above-mentioned oxygen barrier layer with a diaphragm pump with an outlet pressure of 2.6 kg, and dried at 120° C. for 2 minutes to obtain a rough surface layer with particles.
  • the protective film, the laser ablation layer, the oxygen barrier layer and the rough surface layer with particles form a composite film, which is ready for use.
  • thermoplastic elastomer SIS 1107 (Kraton Company) 700g, plasticizer polybutadiene Nisso PB-P 2000 (Japan Nippon Soda) 100g, MIN OIL (American CLUMENT) 100g, 1-Hydroxycyclohexyl phenyl ketone (Zhangjiagang Free Trade Zone Tianjie International Trade Co., Ltd.) 32g, 2,6-di-tert-butyl-p-cresol (Nanjing Jiulong Chemical Co., Ltd.) 12g, 40 g of trimethylolpropane triacrylate (Tianjin Tianjiao Chemical Co., Ltd.), 15.8 g of 1,9-nonanediol diacrylate (Tianjin Tianjiao Chemical Co., Ltd.), 0.2 g of dye RED 335 (BASF Company), In a screw extruder, knead at 150
  • the support body can be selected from polyethylene naphthalene-2,6-dicarbonate, polyethylene terephthalate, polybutylene terephthalate, etc., with a thickness of 50-300 ⁇ m.
  • polyethylene terephthalate was used as the support, with a thickness of 125 ⁇ m, produced by Lucky Company.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the lower surface of the sheet extruded with a photosensitive elastomer layer with a thickness of 2.720 mm in the above-mentioned embodiment was heated and pressed at 120° C. and 6 MPa, and covered with a support film composed of an adhesive layer and a support, and at the same time, the photoelastic
  • the upper surface of the sheet of the body layer is heated and pressurized at 120 ° C and 6 MPa, and is covered with a composite film consisting of a protective film, a laser ablation layer, an oxygen barrier layer and a rough surface layer with particles in this embodiment.
  • a flexible resin plate with flat-top dots with a textured surface is obtained.
  • the ablation pattern contains 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 100% of the outlets, Contains solid, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent points and independent female points. After laser ablation, the morphology of the oxygen barrier layer was observed with a 3D microscope.
  • UV-A exposure lamp to expose the plate for 720 seconds (at 365nm, the light intensity is 18.1mw/cm2), wash it with Shanghai Minchen's high-end environmental protection developer for 7 minutes, dry it with hot air at 65°C for 2 hours, and remove the sticking 5- 12 minutes, post-exposure for 5 minutes.
  • 3D microscope and Vipflex334 and other equipment to evaluate whether the solid surface has texture, 2% dot restoration size and dot edge shape, whether it is flat top dots, etc.
  • Fig. 5 is the 150lpi2% screen dot perspective view and outline drawing of the flexible resin plate obtained in Example 3;
  • Fig. 5a is the front plan view of 150lpi2% screen dot,
  • Fig. 5b is the side perspective view of 150lpi2% screen dot,
  • Fig. 5c is 150lpi2% screen dot outline drawing. From the dot outline, the top of the dot is flat.
  • 6 is a surface texture diagram of the solid part of the flexible resin plate obtained in Example 3, and the solid surface texture is clear.
  • the protective film is the same as in Example 1;
  • the laser ablation layer was prepared according to Example 1 of ZL201110437989.9;
  • oxygen barrier layer without adding halogen-free flame retardant: polyamide 6900 (produced by Henkel, Germany) 4.2g, AS-586 (acrylamide-styrene-methyl methacrylate 35:45:20wt%, Lucky Chemical Co., Ltd.) 0.6g, dissolved in benzyl alcohol n-butanol mass In 95g solvent with a ratio of 30:70, the solution was coated on the laser ablation layer at a speed of 30 m/min, and dried at 70 °C for 10 minutes to obtain a bonding layer with a coating thickness of 2.6 ⁇ m. The dry weight of the coating 2.51g/m2, the oxygen barrier layer was prepared.
  • the protective film, the laser ablation layer, and the oxygen barrier layer form a composite film, which is ready for use.
  • the preparation of the photoelastomer layer is the same as that of Example 1.
  • the support is also Example 1.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the upper surface of the sheet of the bulk layer is heated and pressurized at 120°C and 6MPa, and covered with a composite film consisting of a protective film, a laser ablation layer, and an oxygen barrier layer in this example to obtain a digital flexible resin plate.
  • the printing plate obtained above does not remove the protective film, first back exposure for 22 seconds (under 365nm, light intensity 16.8mw/cm ), then peel off the protective film, the flexible resin plate of the present invention is sent into the CDI SPARK 2120 plate making machine (produced by ESKO), at 2540dpi, the imaging speed is set to Optics10.0, the main laser wavelength is 1071nm, and the black film 2 of the laser ablation layer is ablated, and the ablation pattern contains 1%, 2%, 3%, 4 at 150lpi %, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 100% of the dots, containing Field, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent point and independent female point. After laser ablation, the morphology of the oxygen barrier layer was observed with a 3D
  • UV-A exposure lamp to expose the front for 600 seconds (at 365nm, light intensity 18.1mw/cm 2 ), wash with Shanghai Minchen's high-end environmentally friendly developer for 7 minutes, dry with hot air at 65°C for 2 hours, and remove stickiness for 5-12 minutes , after exposure for 5 min.
  • Fig. 7 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing that the comparative example 1 obtains;
  • Fig. 7a is the front plan view of 150lpi2% dots,
  • Fig. 7b is the side perspective view of 150lpi2% dots,
  • Fig. 7c is 150lpi2% dot outlines. From the outline of the dots, the tops of the dots are in the shape of a rounded tip, not a flat top;
  • Figure 8 is the solid part of the flexible resin plate obtained in Comparative Example 1, and its surface has no texture;
  • the protective film is the same as in Example 1.
  • the laser ablation layer was prepared according to Example 1 of ZL201110437989.9.
  • the preparation of the oxygen barrier layer is the same as that in Example 1.
  • the protective film, the laser ablation layer, and the oxygen barrier layer form a composite film, which is ready for use.
  • the preparation of the photoelastomer layer is the same as that of Example 1.
  • the preparation of the adhesive layer is the same as that in Example 1.
  • the support is the same as in Example 1.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the upper surface of the sheet of the bulk layer is heated and pressurized at 120°C and 6MPa, and covered with a composite film consisting of a protective film, a laser ablation layer, and an oxygen barrier layer in this example to obtain a digital flexible resin plate.
  • the printing plate obtained above does not remove the protective film, first back exposure for 22 seconds (under 365nm, light intensity 16.8mw/cm ), then peel off the protective film, the flexible resin plate of the present invention is sent into the CDI SPARK 2120 plate making machine (produced by ESKO), at 2540dpi, the imaging speed is set to Optics10.0, the main laser wavelength is 1071nm, and the black film 2 of the laser ablation layer is ablated, and the ablation pattern contains 1%, 2%, 3%, 4 at 150lpi %, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 100% of the dots, containing Field, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent point and independent female point. After laser ablation, the morphology of the oxygen barrier layer was observed with a 3D
  • UV-A exposure lamp to expose the front for 600 seconds (at 365nm, the light intensity is 18.1mw/cm2)
  • wash with Shanghai Minchen's high-end environmentally friendly developer for 7 minutes dry it with hot air at 65°C for 2 hours, and remove the sticking for 5-12 minutes.
  • Post-exposure for 5 minutes. Use 3D microscope and Vipflex334 and other equipment to evaluate whether the solid surface has texture, 2% dot restoration size and dot edge shape, whether it is flat top dots, etc.
  • Fig. 9 is the flexographic resin plate 150lpi2% dot perspective view and outline drawing that comparative example 2 obtains;
  • Fig. 9a is the front plan view of 150lpi2% dots,
  • Fig. 9b is the side perspective view of 150lpi2% dots,
  • Fig. 9c is 150lpi2% dot profile. From the outline of the dots, the tops of the dots are flat, but the size is not uniform;
  • Fig. 10 shows the solid part of the flexible resin plate obtained in Comparative Example 2, the surface of which has no texture.
  • the protective film is the same as in Example 2.
  • the laser ablation layer was prepared according to Example 2 of ZL201110437989.9.
  • the preparation of the oxygen barrier layer is the same as that in Example 2, without the halogen-free flame retardant.
  • the matte layer with particles is also Example 2.
  • the protective film, the laser ablation layer, the oxygen barrier layer and the rough surface layer with particles form a composite film, which is ready for use.
  • the preparation of the photoelastomer layer is the same as that of Example 2.
  • the preparation of the adhesive layer is the same as that in Example 2.
  • the support is the same as in Example 2.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the upper surface of the sheet of the body layer is heated and pressurized at 120 ° C and 6 MPa, and is covered with a composite film consisting of a protective film, a laser ablation layer, an oxygen barrier layer and a rough surface layer with particles in this embodiment.
  • a digital flexible resin plate is obtained.
  • the printing plate obtained above does not remove the protective film, first back exposure for 45 seconds (under 365nm, light intensity 18.1mw/cm ), then peel off the protective film, the flexible resin plate of the present invention is sent into the CDI SPARK 2120 plate making machine (produced by ESKO), at 2540dpi, the imaging speed is set to Optics10.0, the main laser wavelength is 1071nm, and the black film 2 of the laser ablation layer is ablated, and the ablation pattern contains 1%, 2%, 3%, 4 at 150lpi %, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 100% of the dots, containing Field, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent point and independent female point. After laser ablation, the morphology of the oxygen barrier layer was observed with a 3D
  • UV-A exposure lamp to expose the plate for 720 seconds (at 365nm, the light intensity is 18.1mw/cm2), wash it with Shanghai Minchen's high-end environmental protection developer for 7 minutes, dry it with hot air at 65°C for 2 hours, and remove the sticking 5- 12 minutes, post-exposure for 5 minutes.
  • 3D microscope and Vipflex334 and other equipment to evaluate whether the solid surface has texture, 2% dot restoration size and dot edge shape, whether it is flat top dots, etc.
  • Figure 11 is a perspective view and outline drawing of the 150lpi2% dots of the flexible resin plate obtained in Comparative Example 3;
  • Figure 11a is a front plan view of the 150lpi2% dots,
  • Figure 11b is a side perspective view of the 150lpi2% dots,
  • Figure 11c is a 150lpi2% dot profile. From the outline of the dots, the tops of the dots are rounded, not flat;
  • Figure 12 shows the solid part of the flexible resin plate obtained in Comparative Example 3, and the ground surface texture is clear.
  • the protective film is the same as in Implementation 2.
  • the laser ablation layer was prepared according to Example 2 of ZL201110437989.9.
  • the preparation of the oxygen barrier layer is the same as that in Example 2.
  • the protective film, the laser ablation layer, and the oxygen barrier layer form a composite film, which is ready for use.
  • the preparation of the photoelastomer layer is the same as that of Example 2.
  • the preparation of the adhesive layer is the same as that in Example 2.
  • the support is the same as in Example 2.
  • the adhesive layer and the support form a support film, which is ready for use.
  • the upper surface of the sheet of the body layer (5) is heated and pressurized at 120° C. and 6 MPa, and covered with a composite film consisting of a protective film, a laser ablation layer, and an oxygen barrier layer in this embodiment to obtain a digital flexible resin. Version.
  • the printing plate obtained above does not remove the protective film, first back exposure for 45 seconds (under 365nm, light intensity 18.1mw/cm ), then peel off the protective film, the flexible resin plate of the present invention is sent into the CDI SPARK 2120 plate making machine (produced by ESKO), at 2540dpi, the imaging speed is set to Optics10.0, the main laser wavelength is 1071nm, and the black film 2 of the laser ablation layer is ablated, and the ablation pattern contains 1%, 2%, 3%, 4 at 150lpi %, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 100% of the dots, containing Field, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent male and female lines, 0.08mm, 0.10mm, 0.15mm, 0.20mm, 0.30mm independent point and independent female point. After laser ablation, the morphology of the oxygen barrier layer was observed with a 3D
  • UV-A exposure lamp to expose the plate for 720 seconds (at 365nm, the light intensity is 18.1mw/cm2), wash it with Shanghai Minchen's high-end environmental protection developer for 7 minutes, dry it with hot air at 65°C for 2 hours, and remove the sticking 5- 12 minutes, post-exposure for 5 minutes.
  • 3D microscope and Vipflex334 and other equipment to evaluate whether the solid surface has texture, 2% dot restoration size and dot edge shape, whether it is flat top dots, etc.
  • Figure 13 is a perspective view and outline drawing of the 150lpi2% dots of the flexible resin plate obtained in Comparative Example 4;
  • Figure 13a is a front plan view of 150lpi2% dots,
  • Figure 13b is a side perspective view of 150lpi2% dots, and
  • Figure 13c is a 150lpi2% dot profile. From the outline of the dots, the tops of the dots are flat;
  • Fig. 14 shows the solid portion of the flexible resin version obtained in Comparative Example 4, the surface of which has no texture.

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Abstract

一种表面自带纹理的平顶网点的柔性树脂版及其制版方法。柔性树脂版的结构自上而下依次为激光烧蚀黑膜层、阻氧层、带有颗粒的毛面层、感光弹性体层、粘结层和支持体；毛面层带有的颗粒为有机聚合物颗粒，有机聚合物颗粒的平均直径为0.5-15μm；当带有有机聚合物颗粒的毛面层与感光弹性体层覆合在一起时，有机聚合物颗粒形成的砂目转移到感光弹性体的表面，形成纹理，提高柔性树脂版的传墨性能。该柔性树脂版设置了阻氧层，减少了氧气对感光弹性体聚合的影响，可以形成平顶网点，提高了版材的耐印率。

Description

一种表面自带纹理的平顶网点的柔性树脂版及其制版方法 技术领域
本发明涉及一种柔性树脂版制备方法，尤其是涉及一种表面自带纹理的平顶网点的柔性树脂版及其制版方法。
背景技术
目前，柔性树脂版广泛用于纸箱、软包装、标签等容易变形或较软承印物的印刷。
通常，将具有图案或文字的胶片放置在含有感光弹性体的未曝光的柔性版上，紫外线曝光，胶片透明的地方透过紫外光，感光弹性体内的引发剂分解成自由基，引发可交联单体反应而固化。未透过紫外线的区域不能发生交联反应，利用它们在显影液中溶解度的差异，冲洗显影得到含有文字图案的浮雕影像。显影后的版材干燥，去粘，后曝光，确保感光层完全聚合。制好的版材固定在柔印机的滚筒上，可以准备印刷。
前述制版过程需要具有图案或文字的胶片，胶片很容易受冲洗加工、灰尘、潮湿等外部条件影响，造成弊病，影响柔性树脂版版材文字、图案等的还原，同时软片贴附在柔性版防粘层制版时，容易粘接软片和引起光的折射、散射等制版弊病，造成图案或文字还原质量降低。
随着计算机技术和印前文档处理技术的发展，带有图案或文字等的文档信息可以转化为数字信息，借助计算机控制，将数字信息转换为红外激光、紫激光等输出到柔性版的烧蚀黑膜上，实现激光烧蚀成像，不再用胶片成像，从而消除了使用胶片制版造成的版材图文还原质量降低问题。这样的版材称之为数码柔性树脂版。
常规的数码柔版，揭去保护膜，用激光烧蚀黑膜成像，然后用UV-A或者UV-LED曝光感光弹性体，显影液冲洗，干燥，后处理制成印版。因为曝光过程在空气中进行，空气中的氧气抑制了曝光的感光弹性体表面，版材还原的网点为子弹头形状。子弹头网点在印刷时支撑力小，与网纹辊的网墙摩擦力大，因此耐印力不高，高光网点印刷效果不清晰，达不到高清柔印150lpi的印刷效果。
研究发现，为实现高清柔印需要平顶网点，同时感光弹性体层上需要自带纹理，提高油墨转移，提升版材耐印率。
为实现柔性树脂版表面自带纹理并实现平顶网点，研究人员寻找了各种解决方案。
一是在曝光机里的光罩里充氮气，氮气由机器外制氮机或氮气瓶提供，当氮气达到一定浓度后，曝光常规版材，形成平顶网点。专利US2009/0186308A1描述了曝光机内氧气浓度在100-190ppm最好。这种方法需要额外的制氮设备，体积庞大，且氮气每次制版保持恒定并 不容易，故不是形成平顶网点的好方法。
二是覆膜技术，在常规激光雕刻烧蚀黑膜后，覆上一层薄膜，阻断空气中的氧气，然后再正面曝光，形成平点网点。美国专利US2017/0297358A1，优化覆膜的曝光参数，形成平顶网点，该网点还原适合瓦楞纸箱印刷。该专利增加一道工序，对于制版公司使用起来操作麻烦，在覆膜时有灰尘进入或有气泡产生，造成废版。
三是将激光雕刻烧蚀黑膜好的版材，浸没在水中曝光，阻断空气中的氧气，形成平点网点，如专利CN107521214A所述。该专利使用起来较麻烦。
四是在激光烧蚀黑膜和感光弹性体之间设置阻氧层，如专利CN107969149A，版材结构(A)、(B)、(C)、(D)、(E)五层，在(B)和(D)之间设置阻氧层(C)，该层采用50-99％重量的10-75％摩尔水解度的聚乙酸乙烯脂或聚乙烯缩醛，1-30％的碱性聚合物如聚乙烯亚胺，0-50％的填料SiO 2或硅酸盐。该专利借助阻氧层和该层内的SiO 2或硅酸盐颗粒压到柔性树脂版表面，形成自带纹理的平顶网点版材。该层含有平均粒径2-6微米的SiO 2或硅酸盐，但不含有机颗粒。
US8492074B2阻氧层，采用两种不同的树脂，如聚乙烯吡咯烷酮、紫漆、聚乙烯醇缩丁醛、聚偏氯乙烯或氯乙烯类聚合物，能形成平顶网点，但形不成版材表面纹理。
五是通过感光弹性体的化学组分改变，形成平顶网点，但不能在表面形成纹理。如专利US8808968所示。
发明内容
为解决上述问题，本发明提供一种表面自带纹理的平顶网点的柔性树脂版及其制版方法，可以在版材表面形成纹理且形成平点网点，提高版材的传墨能力，并提高版材耐印率。
本发明的目的是以下述方式实现的：一种表面自带纹理的平顶网点的柔性树脂版，其结构自上而下依次为激光烧蚀黑膜层、阻氧层、带有颗粒的毛面层、感光弹性体层、粘结层、支持体；毛面层带有的颗粒为有机聚合物颗粒，有机聚合物颗粒的平均直径为0.5-15μm；当带有有机聚合物颗粒的毛面层与感光弹性体层覆合在一起时，有机聚合物颗粒形成的砂目转移到在感光弹性体的表面，形成纹理，提高柔性树脂版的传墨性能。本发明设置的阻氧层，减少了氧气对感光弹性体聚合的影响，可以形成平点网点。
激光烧蚀黑膜层上方还可以设有保护膜形成保护膜层进行保护。保护膜可以是聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、PE、PVC等高分子材料制作的薄膜，优选PET膜，厚度一般50-150μm，最好100-135μm。
激光烧蚀黑膜层可以为本领域中常用的激光烧蚀黑膜，也可以按专利ZL201110437989.9 制备方法制备。烧蚀黑膜中含有纳米炭黑、第一聚合物聚酰胺粘合剂、第二聚合物粘合剂单异腈酸酯改性的聚醚型聚氨酯化合物、激光烧蚀染料、超级分散剂、流平剂、消泡剂等，制得烧蚀黑膜溶液，通过刮刀、柱涂、网纹辊涂布等方式将上述组分涂布在支持体PET或PE上，利用热风、蒸汽、红外、微波等干燥成膜，备用，涂层厚度1-5μm，最好涂层厚度2-4μm。为了保护烧蚀黑膜刮伤，也可以将涂布得到的烧蚀黑膜，用8-20μm的PE或PET等其它材料覆上膜，留待备用。
本发明的阻氧层，组分是聚酰胺、含有丙烯酰胺及其衍生物的丙烯酸树脂。含有丙烯酰胺及其衍生物的丙烯酸树脂为聚(丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂、聚(N-羟甲基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂、聚(N-羟乙基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂、聚(N-羟丙基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂、聚乙烯吡咯烷酮、聚乙烯醇、阿拉伯树胶、聚乙烯缩丁醛树脂中的至少一种。阻氧层必要时添加流平剂、消泡剂等。本发明阻氧层优选聚酰胺和含有丙烯酰胺及其衍生物的丙烯酸树脂的混合物。当激光作用在激光烧蚀黑膜层时，会产生高达1000℃左右的刺波温度，对本发明阻氧层产生破坏，发生裂纹或对阻氧层加热，造成厚度不均匀，为解决该问题，阻氧层中需要添加无卤阻燃剂或难燃剤，如日本大八公司的DAIGUARD-850、DAIGUARD-880、DAIGUARD-540、DAIGUARD-580，帝人公司的难燃剤FCX-210，开平德里公司的FB-BN880无卤阻燃剂等。通过刮刀、柱涂、网纹辊涂布等方式将上述组分涂布在激光烧蚀黑膜层上，利用热风、蒸汽、红外、微波等干燥成膜，备用，涂层厚度1-5μm，最好涂层厚度1-3μm。为了保护阻氧层，也可以将涂布得到的阻氧层，用8-20μm的PE或PET等其它材料覆上膜，留待备用。
本发明带有颗粒的毛面层，该毛面层带有的有机聚合物颗粒可以是聚甲基丙烯酸甲酯、聚苯乙烯、聚甲基丙烯酸酯-明胶分散粒、聚甲基丙烯酸酯-明胶分散粒、偏二氯乙烯-甲基丙烯酸甲酯-丙烯酸聚合物乳液，偏二氯乙烯-苯乙烯-甲基丙烯酸甲酯-丙烯酸聚合物乳液、苯乙烯-丙烯腈-甲基丙烯酸酯聚乙二醇醚的共聚物、苯乙烯-丙烯腈-甲基丙烯酸聚丙二醇醚酯的共聚物颗粒、聚氯乙烯颗粒等，该毛面层的有机聚合物颗粒可以分散在水中、聚乙烯醇溶液、乙烯醋酸乙烯共聚物乳液、聚乙烯基吡咯烷酮溶液、明胶溶液、阿拉伯树胶溶液等。优选聚甲基丙烯酸甲酯水分散体系、聚甲基丙烯酸酯-明胶分散体系、聚甲基丙烯酸酯-聚乙烯醇分散体系。这里，偏二氯乙烯-甲基丙烯酸甲酯-丙烯酸聚合物乳液是偏二氯乙烯-甲基丙烯酸甲酯-丙烯酸的共聚物，偏二氯乙烯-苯乙烯-甲基丙烯酸甲酯-丙烯酸聚合物乳液是偏二氯乙烯-苯乙烯-甲基丙烯酸甲酯-丙烯酸的共聚物。
本发明毛面层带有的有机聚合物颗粒的平均粒径为0.5-15μm，优选平均粒径0.5-10μ m，更优选平均粒径为0.5-8μm。有机聚合物颗粒可以采用涂布、高压气枪喷涂、静电喷涂等涂在本发明专利的阻氧层上，干燥采用蒸汽、热风、红外电加热、微波等方式，加热温度100-140℃，加热时间1-3分钟，有机聚合物颗粒通过压力、温度熔融软化等工艺，形成半球状、椭圆形等外观形态覆在本发明的阻氧层表面。当本发明的颗粒毛面层覆在感光弹性体层上，在感光弹性体的表面产生纹理。
本发明的柔性树脂版所用的感光弹性体层中，至少含有一种热塑性聚合材料、至少一种乙烯基不饱和化合物、至少一种引发剂或引发体系、至少一种染料、其他助剂等。
感光弹性体层中的热塑性聚合材料可以是丁二烯/苯乙烯的共聚物、异戊二烯/苯乙烯的共聚物、丙烯腈/苯乙烯共聚物、丙烯腈/丁二烯/苯乙烯共聚物、聚氨酯、聚乙烯等，这样的例子如聚苯乙烯-聚丁二烯-聚苯乙烯三嵌段共聚物、聚苯乙烯-聚异戊二烯-聚苯乙烯三嵌段共聚物、聚苯乙烯-聚乙烯丁烯-聚苯乙烯嵌段共聚物、聚苯乙烯-聚异戊二烯的星型共聚物、丙烯腈/丁二烯/苯乙烯共聚物等。
感光弹性体层中的乙烯基不饱和化合物可以是这样的单体，如2-(2乙氧基)乙基丙烯酸酯、异冰片丙烯酸酯、2-苯氧乙基丙烯酸酯、四氢糠醇丙烯酸酯、(甲基)丙烯酸-2-羟乙酯、丙烯酸-2-羟乙酯、(甲基)丙烯酸羟丙酯、丙烯酸丁酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十八酯、1，3-丙二醇二(甲基)丙烯酸酯、1，4-丁二醇二(甲基)丙烯酸酯、1，5-戊二醇二(甲基)丙烯酸酯、1，6-己二醇二(甲基)丙烯酸酯、1，9-壬二醇二(甲基)丙烯酸酯、三缩乙二醇二(甲基)丙烯酸酯、四缩乙二醇二(甲基)丙烯酸酯、五缩乙二醇二(甲基)丙烯酸酯、二丙二醇二丙烯酸酯、三缩丙二醇二(甲基)丙烯酸酯、四缩丙二醇二(甲基)丙烯酸酯、新戊二醇二丙烯酸酯、邻苯二甲酸二乙二醇二丙烯酸酯、邻苯二甲酸三丙二醇二丙烯酸酯、乙氧基化双酚A二丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧化甘油三丙烯酸酯、2，2-二(对羟基苯基)-丙烷二(甲基)丙烯酸酯、二羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯等等。
感光弹性体层中的引发剂或引发体系可以是二苯甲酮、米嗤酮、4-乙酰氧基-4’-二乙基胺二苯甲酮、安息香乙醚、α－羟基异丙基苯甲酮、α－羟基环己基苯甲酮、2-苯基-2，2-二甲氧基乙酰苯酮、2-特丁基蒽醌、异丙基硫杂蒽酮、(吗啉基苯甲酰基)1－六基1，1(二甲胺基)丙烷、苯偶酰、苯偶姻、长沙新宇高分子科技有限公司的UV6501、UV6502，湖北固润科技股份有限公司的GR-TPO、GR-L101、GR-ITX、GR-XBPO、GR-TPO-L、GE-DETX，国 外公司如汽巴嘉基
Figure PCTCN2021140463-appb-000001
IGM的
Figure PCTCN2021140463-appb-000002
等等。
感光弹性体层中还可以添加抗氧剂、热抑制剂、脱模剂、流平剂、染料等其他助剂。
本发明的粘结层，可以是聚氨酯、侧链含有1,2-乙烯基的聚氨酯、聚酯、二氯乙烯共聚物、偏氯乙烯-甲基丙烯酸酯-丙烯酸共聚物、丙烯酸树脂、苯乙烯-丙烯酸酯的共聚物、或者它们的混合物。上述组分配制成溶液，涂布在本发明的支持体上，涂层厚度1-10μm，最好1-5μm。
本发明的支持体，可以是聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、PP膜、PVC膜、铝板基、钢板基、磁性钢基等，优选PET膜，厚度为75-200μm，优选100-175μm。
感光弹性体层中的各组分按比例加入到挤出机中，加热、混炼、排气等，在110-150℃混炼2-5分钟，挤出，经模头制得0.5-6.35mm厚度的片材作为感光弹性体层，然后将感光弹性体片材下表面加热、加压覆上由本发明支持体和粘结层组成的支撑膜上，同时再在感光弹性体层的片材上面加热加压覆上含有本发明保护膜、激光烧蚀黑膜层、阻氧层和带有颗粒的毛面层的复合膜，便得到本发明的一种表面自带纹理的平顶网点的柔性树脂版。
所述的表面自带纹理的平顶网点的柔性树脂版的制版方法，包括：背曝光形成底基；激光雕刻烧蚀黑膜层(2)；UV-A或UV-LED紫外光正面曝光；洗版；加热干燥；后曝光；去粘。
具体制版过程可以如下：现在支持体一面用UV-A或UV-LED背曝光，形成底基。然后把是柔性树脂版翻转过来，揭去保护膜，用1064-1070nm的ND:YAG激光等烧蚀或气化激光烧蚀黑膜层，形成原位图案，保留在感光弹性体层上，激光烧蚀的部分可以透过紫外光，未烧蚀的部分形成掩膜，阻挡紫外光的穿透。接着正面UV-A或UV-LED曝光，激光烧蚀的部分，紫外光透过使感光弹性体交联聚合，激光未烧蚀的部分形成掩膜，紫外光不能透过，该部分感光弹性体不能交联聚合，然后在四氯乙烯/正丁醇的有机溶剂或含有萜烯或市售的上海敏晨高端环保显影液等环保显影液中显影，移去未烧蚀的激光烧蚀层部分和未交联的感光弹性体，形成有凸起的图案，随后60-70℃烘干1.5-2小时、后曝光、去粘，即得到表面带有纹理的平顶网点的可以上机印刷的柔性树脂版。
本发明的有益效果，相对于现有技术，本发明提供一种表面自带纹理的平顶网点的柔性树脂版及其制版方法，可以在版材表面形成纹理且形成平点网点。相比传统数码柔性树脂版的“子弹头”网点，本发明版材表面自带的纹理，可以增加版材表面印刷传墨，提高版材的实地和网点传墨能力，印版表面转移到承印物的油墨密度更高，色彩质量更高；本发明版材 形成的平顶网点，与网纹辊接触，平顶网点更耐磨损，从而提高了版材耐印率。
附图说明
图1是实施例1获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中：a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c是150lpi2％网点轮廓图。
图2是实施例1获得的柔性树脂版实地部分的表面纹理图，实地表面纹理清晰。
图3是实施例2获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中：a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c右是150lpi2％网点轮廓图。
图4是实施例2获得的柔性树脂版实地部分表面纹理图，实地表面纹理清晰。
图5是实施例3获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中：a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c是150lpi2％网点轮廓图。
图6是实施例3获得的柔性树脂版实地部分表面纹理图，实地表面纹理清晰。
图7是比较例1获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中：a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c是150lpi2％网点轮廓图。
图8是比较例1获得的柔性树脂版实地部分，其表面无纹理。
图9是比较例2获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中：a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c是150lpi2％网点轮廓图。
图10是比较例2获得的柔性树脂版实地部分，其表面无纹理。
图11是比较例3获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c是150lpi2％网点轮廓图。
图12比较例3获得的柔性树脂版实地部分的表面纹理图，实地表面纹理清晰。
图13是比较例4获得的柔性树脂版150lpi2％网点立体图和轮廓图；其中a是150lpi2％网点的正面俯视图，b是150lpi2％网点的侧面立体图，c是150lpi2％网点轮廓图。
图14是比较例4获得的柔性树脂版实地部分，其表面无纹理。
具体实施方式
下面结合具体实施例对本发明进行具体描述，有必要在此指出的是本实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整。
一、本发明所用的有机颗粒及分散体系，合成如下：
合成例1.聚甲基丙烯酸甲酯-水分散体系合成
分别配制质量分数为3％的十二烷基硫酸钠水溶液、称取48g精制的偶氮二异丁腈，并溶解于2000ml甲基丙烯酸甲酯中，备用。
在100升分散釜中，先加入20升的去离子水，启动搅拌，升温加热至内温60℃，加入800ml质量分数为3％的十二烷基硫酸钠水溶液。然后，再加入预先溶解好的甲基丙烯酸甲酯－偶氮二异丁腈溶液和质量分数为0.5％的间苯溶液24毫升。分散搅拌30分钟，停止搅拌。
把分散好的物料分放在50升的不锈钢桶中，加盖后立即放置于60℃±1℃的恒温水槽中，保温聚合20小时。
把聚合物从恒温水槽中取出，倒出上层清水，再添加8L去离子水。搅拌均匀后用尼龙布过滤，聚合物料放置在50升的不锈钢桶中，加30L去离子水，搅拌均匀，静置24小时，倒掉上层液体，沉于桶底的白色固体即为聚甲基丙烯酸甲酯颗粒成品。得产品1.15kg。平均粒径6.6微米。
将上述1.15公斤的甲基丙烯酸甲酯颗粒，加入18公斤水中，开启搅拌，加入质量分数为4％的8811水溶液9公斤，加入十六醇和正丁醇按质量比为1:3组成的混合消泡剂130mm，搅拌2小时，出料，得到聚甲基丙烯酸甲酯-水分散体系备用。表面活性剂8811的结构为丁二酸二异辛基磺酸钠。
合成2：聚甲基丙烯酸酯-明胶分散体系
分别配制质量分数为3％的十二烷基硫酸钠水溶液、称取48g精制的过氧化苯甲酰，并溶解于2000ml甲基丙烯酸甲酯中，备用。
在100升分散釜中，先加入20升的去离子水，启动搅拌，升温加热至内温60℃，加入800ml质量分数为3％的十二烷基硫酸钠水溶液。然后，再加入预先溶解好的甲基丙烯酸甲酯－过氧化苯甲酰溶液和质量分数为0.5％的间苯溶液24毫升。分散搅拌30分钟，停止搅拌。
把分散好的物料分放在50升的不锈钢桶中，加盖后立即放置于54℃±1℃的恒温水槽中，保温聚合20小时。
把聚合物从恒温水槽中取出，倒出上层清水，再添加8L去离子水。搅拌均匀后用尼龙布过滤，聚合物料放置在50升的不锈钢桶中，加30L去离子水，搅拌均匀，静置24小时，倒掉上层液体，沉于桶底的白色固体即为聚甲基丙烯酸甲酯颗粒成品。得产品1.2kg。平均粒径7.8微米。
将上述1.2公斤的甲基丙烯酸甲酯颗粒，加入8公斤质量分数为4.8％的明胶水溶液，质量分数为4％的氯化钠水溶液8公斤，开启搅拌，加入十六醇和正丁醇按质量比为1:3组成的混合消泡剂135mm，搅拌2小时，出料，得到聚甲基丙烯酸甲酯-明胶分散体系备用。
合成例3：聚甲基丙烯酸酯—聚乙烯醇分散体系
分别配制质量分数为3％的十二烷基硫酸钠水溶液、称取60g精制的过氧化苯甲酰，并溶解于2000ml甲基丙烯酸甲酯中，备用。
在100升分散釜中，先加入20升的去离子水，启动搅拌，升温加热至内温60℃，加入800ml质量分数为3％的十二烷基硫酸钠水溶液。然后，再加入预先溶解好的甲基丙烯酸甲酯－过氧化苯甲酰溶液和质量分数为0.5％的间苯溶液35毫升。分散搅拌30分钟，停止搅拌。
把分散好的物料分放在50升的不锈钢桶中，加盖后立即放置于57℃±1℃的恒温水槽中，保温聚合20小时。
把聚合物从恒温水槽中取出，倒出上层清水，再添加8L去离子水。搅拌均匀后用尼龙布过滤，聚合物料放置在50升的不锈钢桶中，加30L去离子水，搅拌均匀，静置24小时，倒掉上层液体，沉于桶底的白色固体即为聚甲基丙烯酸甲酯颗粒成品。得产品1.05kg。平均粒径4.8微米。
将上述1.05公斤的甲基丙烯酸甲酯颗粒，加入质量分数为5.1％的PVA水溶液16公斤，开启搅拌，加入十六醇和正丁醇按质量比为1:3组成的混合消泡剂120mm，搅拌2小时，出料，得到聚甲基丙烯酸甲酯-聚乙烯醇分散体系备用。
二、表面自带纹理的平顶网点柔性树脂版的具体实施例如下：
实施例1
保护膜选用聚对苯二甲酸乙二醇酯(PET)，厚度100μm，乐凯公司生产；也可选用聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸丁二醇酯等，厚度50-150μm。
激光烧蚀层按ZL201110437989.9实施例1制备。
阻氧层的制备：聚酰胺
Figure PCTCN2021140463-appb-000003
(德国Henkel公司生产)4.2g，AS-586(丙烯酰胺-苯乙烯-甲基丙烯酸甲酯35:45:20wt％，乐凯化学品有限公司)0.6g，无卤阻燃剂DAIGUARD-880(日本大八公司生产)0.2g溶解在苯甲醇正丁醇质量比30：70的95g溶剂中，将此溶液以30米/分钟的速度涂布在激光烧蚀层上，70℃干燥10分钟，得到涂层厚度为2.6μm的粘结层，涂层干重2.51g/m 2的阻氧层。
将合成例1聚甲基丙烯酸甲酯-水分散体系用隔膜泵，出口压力2公斤，喷涂在上述阻氧层，120℃干燥2分钟，制得带有颗粒的毛面层。
保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成了复合膜，备用。
感光弹性体层的制备：将热塑性弹性体SIS1107(科腾公司)700g、增塑剂聚丁二烯NissoPB-P2000(日本Nippon Soda)100g、
Figure PCTCN2021140463-appb-000004
OIL(美国CLUMENT)100g、1-羟 基环已基苯基甲酮(张家港保税区天捷国际贸易有限公司)32g、2,6-二特丁基对甲酚(南京九龙化工有限公司)12g、三羟甲基丙烷三丙烯酸酯40g(天津天骄化工有限公司)，1，9-壬二醇二丙烯酸酯15.8g(天津天骄化工有限公司)、染料RED 335(BASF公司)0.2g加入到双螺杆挤出机中，150℃混炼2分钟，挤出厚度为1.585mm的感光弹性体层，备用。
粘结层的制备：甲乙酮100g、醋酸丁酯50g、聚氨酯醋酸乙烯酯R-317(乐凯公司生产)40g，然后加入三羟甲基丙烷三丙烯酸酯(TMPTA，天津天骄化工有限公司)2g、引发剂1-羟基环己基苯基甲酮(俗称184，张家港保税区天捷国际贸易有限公司)0.5g、2，6-二特丁基对甲酚(俗称264，南京九龙化工有限公司)0.2g、FC-4430(3M公司生产)0.05g，在黄色安全灯下，在密闭的容器中搅拌2小时，得到交联层的涂布溶液，将此溶液以30米/分钟的速度涂布在支持体上，60℃干燥10分钟，得到涂层厚度为2.9μm的粘结层，涂层干重2.86g/m 2，制备得到的支撑膜，收卷备用。
支持体采用聚对苯二甲酸乙二醇酯，厚度125μm，乐凯公司生产。也可选用聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯等，厚度50-300μm。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为1.585mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成的复合膜，便得到表面自带纹理的平顶网点的柔性树脂版。
上述发明制得的印版，不揭去保护膜，先UV-A曝光灯管背曝光22秒(365nm下，光强18.1mw/cm2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光600秒(365nm下，光强18.1mw/cm2)，上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。具体结果见如图1和图2。图1是实施例1获得的柔性树脂版150lpi2％网点立体图和轮廓图；图1a是150lpi2％网点的正面俯视图，图1b150lpi2％网点的侧面立体图、图1c 是150lpi2％网点轮廓图，从网点轮廓图看，网点的顶部是平的。图2是实施例1获得的柔性树脂版实地部分的表面纹理图，实地表面纹理清晰。
实施例2
保护膜可选用聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯等(PBT)等，厚度50-150μm。本实施例采用PET作为保护膜，厚度125μm，乐凯公司生产。
激光烧蚀层按ZL201110437989.9实施例2制备.
阻氧层的制备：聚酰胺
Figure PCTCN2021140463-appb-000005
6900(德国Henkel公司生产)4.5g，AS-588(N-羟乙基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯30:45:25wt％，乐凯化学品有限公司)0.5g无卤阻燃剂DAIGUARD-880(日本大八公司生产)0.3g溶解在苯甲醇正丁醇质量比30：70的100g溶剂中，将此溶液以30米/分钟的速度涂布在激光烧蚀层上，70℃干燥10分钟，得到涂层厚度为2.7μm的粘结层，涂层干重2.65g/m 2，制备得到阻氧层。
将合成2聚甲基丙烯酸酯—明胶分散体系用隔膜泵，出口压力3.1公斤，喷涂在上述阻氧层，120℃干燥2分钟，制得带有颗粒的毛面层。
保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成了复合膜，备用。
感光弹性体层的制备：将热塑性弹性体SIS1107(科腾公司)700g、增塑剂聚丁二烯Nisso PB-P 2000(日本Nippon Soda)100g、
Figure PCTCN2021140463-appb-000006
OIL(美国CLUMENT)100g、1-羟基环已基苯基甲酮(张家港保税区天捷国际贸易有限公司)32g、2,6-二特丁基对甲酚(南京九龙化工有限公司)12g、三羟甲基丙烷三丙烯酸酯40g(天津天骄化工有限公司)、1，9-壬二醇二丙烯酸酯15.8g(天津天骄化工有限公司)、染料RED 335(BASF公司)0.2g、加入到双螺杆挤出机中，150℃混炼2分钟，挤出厚度为0.970mm的感光弹性体层，备用。
粘结层的制备：甲乙酮100g、醋酸丁酯50g、聚氨酯醋酸乙烯酯R-317(乐凯公司生产)40g，然后加入三羟甲基丙烷三丙烯酸酯(TMPTA，天津天骄化工有限公司)2克、引发剂1-羟基环己基苯基甲酮(俗称184，张家港保税区天捷国际贸易有限公司)0.5g、2，6-二特丁基对甲酚(俗称264，南京九龙化工有限公司)0.2g、FC-4430(3M公司生产)0.05g，在黄色安全灯下，在密闭的容器中搅拌2小时，得到交联层的涂布溶液，将此溶液以30米/分钟的速度涂布在支持体上，60℃干燥10分钟，得到涂层厚度为2.9μm的粘结层，涂层干重2.86g/m 2，制备得到的支撑膜，收卷备用。
支持体可选用聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等，厚度50-300μm。本实施例采用聚对苯二甲酸乙二醇酯作为支持体，厚度175μm(365nmUV透过率10±2％)，乐凯公司生产。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为0.970mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成的复合膜，便得到表面自带纹理的平顶网点的柔性树脂版。
上述发明制得的印版，不揭去保护膜，先背曝光45秒(365nm下，光强18.1mw/cm 2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光版材720秒(365nm下，光强18.1mw/cm2)，用上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。
具体结果见如图3和图4。图3是实施例2获得的柔性树脂版150lpi2％网点立体图和轮廓图；图3a是150lpi2％网点的正面俯视图，图3b150lpi2％网点的侧面立体图、图3c是150lpi2％网点轮廓图，从网点轮廓图看，网点的顶部是平的。图4是实施例2获得的柔性树脂版实地部分的表面纹理图，实地表面纹理清晰。
实施例3
保护膜可选用聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯等(PBT)等，厚度50-150μm。本实施例采用PET作为保护膜，厚度125μm，乐凯公司生产。
激光烧蚀层按ZL201110437989.9实施例3制备。
阻氧层的制备：聚酰胺
Figure PCTCN2021140463-appb-000007
6900(德国Henkel公司生产)4.2g，AS-586(丙烯酰胺-苯乙烯-甲基丙烯酸甲酯35:45:20wt％，乐凯化学品有限公司)0.6g,无卤阻燃剂 DAIGUARD-880(日本大八公司生产)0.2g溶解在苯甲醇正丁醇质量比30：70的95g溶剂中，将此溶液以30米/分钟的速度涂布在激光烧蚀层上，70℃干燥10分钟，得到涂层厚度为2.6μm的粘结层，涂层干重2.51g/m 2，制备得到阻氧层。
将合成例3聚甲基丙烯酸酯—聚乙烯醇分散体系用隔膜泵，出口压力2.6公斤，喷涂在上述阻氧层，120℃干燥2分钟，制得带有颗粒的毛面层。
保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成了复合膜，备用。
感光弹性体层的制备：将热塑性弹性体SIS 1107(科腾公司)700g、增塑剂聚丁二烯Nisso PB-P 2000(日本Nippon Soda)100g、
Figure PCTCN2021140463-appb-000008
MIN OIL(美国CLUMENT)100g、1-羟基环已基苯基甲酮(张家港保税区天捷国际贸易有限公司)32g、2,6-二特丁基对甲酚(南京九龙化工有限公司)12g、三羟甲基丙烷三丙烯酸酯40g(天津天骄化工有限公司)，1，9-壬二醇二丙烯酸酯15.8g(天津天骄化工有限公司)、染料RED 335(BASF公司)0.2g、加入到双螺杆挤出机中，150℃混炼2分钟，挤出厚度为2.720mm的感光弹性体层，备用。
粘结层的制备：甲乙酮100g、醋酸丁酯50g、聚氨酯醋酸乙烯酯R-317(乐凯公司生产)40g，然后加入三羟甲基丙烷三丙烯酸酯(TMPTA，天津天骄化工有限公司)2克、引发剂1-羟基环己基苯基甲酮(俗称184，张家港保税区天捷国际贸易有限公司)0.5g、2，6-二特丁基对甲酚(俗称264，南京九龙化工有限公司)0.2g、FC-4430(3M公司生产)0.05g，在黄色安全灯下，在密闭的容器中搅拌2小时，得到交联层的涂布溶液，将此溶液以30米/分钟的速度涂布在支持体上，60℃干燥10分钟，得到涂层厚度为2.9μm的粘结层，涂层干重2.86g/m 2，制备得到的支撑膜，收卷备用。
支持体可选用聚已撑萘-2，6-二碳酸酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等，厚度50-300μm。本实施例采用聚对苯二甲酸乙二醇酯作为支持体，厚度125μm，乐凯公司生产。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为2.720mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成的复合膜，便得到表面自带纹理的平顶网点的柔性树脂版。
上述发明制得的印版，不揭去保护膜，先背曝光22秒(365nm下，光强16.8mw/cm2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧 蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光版材720秒(365nm下，光强18.1mw/cm2)，用上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。
具体结果见如图5和图6。图5是实施例3获得的柔性树脂版150lpi2％网点立体图和轮廓图；图5a是150lpi2％网点的正面俯视图，图5b150lpi2％网点的侧面立体图、图5c是150lpi2％网点轮廓图。从网点轮廓图看，网点的顶部是平的。图6是实施例3获得的柔性树脂版实地部分的表面纹理图，实地表面纹理清晰。
比较例1
保护膜同实施例1；
激光烧蚀层按ZL201110437989.9实施例1制备；
阻氧层的制备，不添加无卤素阻燃剂：聚酰胺
Figure PCTCN2021140463-appb-000009
6900(德国Henkel公司生产)4.2g，AS-586(丙烯酰胺-苯乙烯-甲基丙烯酸甲酯35:45:20wt％，乐凯化学品有限公司)0.6g,溶解在苯甲醇正丁醇质量比30：70的95g溶剂中，将此溶液以30米/分钟的速度涂布在激光烧蚀层上，70℃干燥10分钟，得到涂层厚度为2.6μm的粘结层，涂层干重2.51g/m2，制备得到阻氧层。
不设置带有颗粒的毛面层。
保护膜、激光烧蚀层、阻氧层组成了复合膜，备用。
感光弹性体层的制备同实施例1。
粘结层的制备：同实施例1。
支持体同时实施例1。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为1.585mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层组成的复合膜，便得到数码柔性树脂版。
上述制得的印版，不揭去保护膜，先背曝光22秒(365nm下，光强16.8mw/cm2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光600秒(365nm下，光强18.1mw/cm 2)，上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。
具体结果见图7和图8。图7是比较例1获得的柔性树脂版150lpi2％网点立体图和轮廓图；图7a是150lpi2％网点的正面俯视图，图7b150lpi2％网点的侧面立体图、图7c是150lpi2％网点轮廓图。从网点轮廓图看，网点的顶部是圆尖形状，不是平顶形状；图8是比较例1获得的柔性树脂版实地部分，其表面无纹理；
比较例2
保护膜同实施例1。
激光烧蚀层按ZL201110437989.9实施例1制备。
阻氧层的制备同实施例1。
不设置带有颗粒的毛面层。
保护膜、激光烧蚀层、阻氧层组成了复合膜，备用。
感光弹性体层的制备同实施例1。
粘结层的制备同实施例1。
支持体同实施例1。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为1.585mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层组成的复合膜，便得到数码柔性树脂版。
上述制得的印版，不揭去保护膜，先背曝光22秒(365nm下，光强16.8mw/cm2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光600秒(365nm下，光强18.1mw/cm2)，上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。
具体结果见图9和图10。图9是比较例2获得的柔性树脂版150lpi2％网点立体图和轮廓图；图9a是150lpi2％网点的正面俯视图，图9b150lpi2％网点的侧面立体图、图9c是150lpi2％网点轮廓图。从网点轮廓图看，网点的顶是平的，但大小不均匀；图10是比较例2获得的柔性树脂版实地部分，其表面无纹理。
比较例3
保护膜同实施例2。
激光烧蚀层按ZL201110437989.9实施例2制备。
阻氧层的制备，同实施例2，不含无卤阻燃剂。
带有颗粒的毛面层同时实施例2。
保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成了复合膜，备用。
感光弹性体层的制备同实施例2。
粘结层的制备同实施例2。
支持体同实施例2。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为0.970mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层和带有颗粒的毛面层组成的复合膜，便得到数码柔性树脂版。
上述制得的印版，不揭去保护膜，先背曝光45秒(365nm下，光强18.1mw/cm2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光版材720秒(365nm下，光强18.1mw/cm2)，用上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。
具体结果见图11和图12。图11是比较例3获得的柔性树脂版150lpi2％网点立体图和轮廓图；图11a是150lpi2％网点的正面俯视图，图11b150lpi2％网点的侧面立体图、图11c是150lpi2％网点轮廓图。从网点轮廓图看，网点的顶部是圆尖形状，不是平顶形状；图12是比较例3获得的柔性树脂版实地部分，其实地表面纹理清晰。
比较例4
保护膜同实施2。
激光烧蚀层按ZL201110437989.9实施例2制备.
阻氧层的制备同实施例2。
不设置带有颗粒的毛面层。
保护膜、激光烧蚀层、阻氧层组成了复合膜，备用。
感光弹性体层的制备同实施例2。
粘结层的制备同实施例2。
支持体同实施例2。
粘结层和支持体组成了支撑膜，备用。
将上述实施例中挤出厚度为0.970mm的感光弹性体层的片材的下表面，在120℃和6MPa加热加压下，覆上粘结层和支持体组成的支撑膜，同时在感光弹性体层(5)的片材的上表面，在120℃和6MPa加热加压下，覆上本实施例中含有保护膜、激光烧蚀层、阻氧层组成的复合膜，便得到数码柔性树脂版。
上述制得的印版，不揭去保护膜，先背曝光45秒(365nm下，光强18.1mw/cm2)，然后剥去保护膜，将本发明的柔性树脂版送入CDI SPARK 2120制版机(ESKO公司生产)，2540dpi下，成像速度设定为Optics10.0，激光主波长1071nm，烧蚀激光烧蚀层黑膜2，该烧蚀图案含有150lpi下1％、2％、3％、4％、5％、10％、20％、30％、40％、50％、60％、70％、80％、90％、95％、96％、97％、98％、100％的网点，含有实地，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm的独立阳线和阴线，0.08mm、0.10mm、0.15mm、0.20mm、0.30mm独立点和独立阴点。激光烧蚀后，用3D显微镜观察阻氧层的形态。
然后用UV-A曝光灯管正面曝光版材720秒(365nm下，光强18.1mw/cm2)，用上海敏晨的高端环保显影液洗7分钟，65℃热风干燥2小时，去粘5-12分钟，后曝光5分钟。用3D显微镜和Vipflex334等设备，评测实地表面有无纹理、2％网点还原大小和网点边沿形状、是否平顶网点等。
具体结果见图13和图14。图13是比较例4获得的柔性树脂版150lpi2％网点立体图和轮廓图；图13a是150lpi2％网点的正面俯视图，图13b150lpi2％网点的侧面立体图、图13c是150lpi2％网点轮廓图。从网点轮廓图看，网点的顶部是平顶；图14是比较例4获得的柔性树脂版实地部分，其表面无纹理。
实施例1-3和比较例1-4的评测结果见表1。
表1实施例1-3和比较例1-4的评测结果
Figure PCTCN2021140463-appb-000010
Figure PCTCN2021140463-appb-000011
从表1看出，采用本发明技术可以得到表面自带纹理的平顶网点柔性树脂版。
以上实施例为典型的表面自带纹理的平顶网点柔性树脂版制备方法，是为了让读者较好的理解本发明，但本发明的保护范围并不局限于此，应当指出，对于本领域的及任何熟悉本技术领域的技术人员来说，在不脱离本发明整体构思前提下，根据本发明的技术方案及其发明构思加以等同替换或改变，及作出的若干改变和改进，这些也应该视为本发明的保护范围。

Claims (10)

  1. 一种表面自带纹理的平顶网点的柔性树脂版，其特征在于：包括自上而下的激光烧蚀黑膜、阻氧层、带有颗粒的毛面层、感光弹性体层、粘结层、支持体；毛面层带有的颗粒为有机聚合物颗粒，有机聚合物颗粒的平均直径为0.5-15μm；当带有有机聚合物颗粒的毛面层与感光弹性体层覆合在一起时，有机聚合物颗粒形成的砂目转移到在感光弹性体的表面，形成纹理。
  2. 根据权利要求1所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：毛面层带有的有机聚合物颗粒是聚甲基丙烯酸甲酯、聚苯乙烯、聚甲基丙烯酸酯-明胶分散粒、聚甲基丙烯酸酯-明胶分散粒、偏二氯乙烯-甲基丙烯酸甲酯-丙烯酸聚合物乳液，偏二氯乙烯-苯乙烯-甲基丙烯酸甲酯-丙烯酸聚合物乳液苯乙烯-丙烯腈-甲基丙烯酸酯聚乙二醇醚的共聚物、苯乙烯-丙烯腈-甲基丙烯酸聚丙二醇醚酯的共聚物颗粒、聚氯乙烯颗粒中的至少一种。
  3. 根据权利要求2所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：毛面层带有的有机聚合物颗粒可以分散在水中、聚乙烯醇溶液、乙烯醋酸乙烯共聚物乳液、聚乙烯基吡咯烷酮溶液、明胶溶液、或阿拉伯树胶溶液中。
  4. 根据权利要求3所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：毛面层带有的有机聚合物颗粒的平均直径为0.5-10μm；毛面层带有的有机聚合物颗粒的分散体系是聚甲基丙烯酸甲酯水分散体系、聚甲基丙烯酸酯-明胶分散体系、聚甲基丙烯酸酯-聚乙烯醇分散体系中的至少一种。
  5. 根据权利要求1所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：毛面层带有的有机聚合物颗粒的平均直径为0.5-8μm。
  6. 根据权利要求1所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：毛面层带有的有机聚合物颗粒以半球状或椭圆形的外观形态覆在阻氧层表面。
  7. 根据权利要求1所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：阻氧层含有聚酰胺，含有丙烯酰胺及其衍生物的丙烯酸树脂，含有无卤阻燃剂或者难燃剤。
  8. 根据权利要求2所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：阻氧层含有的丙烯酰胺及其衍生物的丙烯酸树脂是聚(丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂、聚(N-羟甲基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂、聚(N-羟乙基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂或聚(N-羟丙基丙烯酰胺-苯乙烯-甲基丙烯酸甲酯)树脂中的至少一种；阻氧层厚度为1-3μm。
  9. 根据权利要求1所述的表面自带纹理的平顶网点的柔性树脂版，其特征在于：激光烧蚀黑膜层上方设有保护膜。
  10. 权利要求1-9任意一项所述的表面自带纹理的平顶网点的柔性树脂版的制版方法，其特征在于：包括：背曝光形成底基；激光雕刻烧蚀黑膜层；UV-A或UV-LED紫外光正面曝光；洗版；加热干燥；后曝光；去粘。
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