WO2021102610A1 - 一种多涂层辐射固化预涂装膜及其制备方法 - Google Patents

一种多涂层辐射固化预涂装膜及其制备方法 Download PDF

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WO2021102610A1
WO2021102610A1 PCT/CN2019/120508 CN2019120508W WO2021102610A1 WO 2021102610 A1 WO2021102610 A1 WO 2021102610A1 CN 2019120508 W CN2019120508 W CN 2019120508W WO 2021102610 A1 WO2021102610 A1 WO 2021102610A1
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layer
radiation
acrylate
parts
radiation curing
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PCT/CN2019/120508
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English (en)
French (fr)
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李新雄
龙贺年
李辉
张冬明
李时珍
邓秀琳
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邦弗特新材料股份有限公司
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Priority to PCT/CN2019/120508 priority Critical patent/WO2021102610A1/zh
Priority to US17/027,821 priority patent/US11597844B2/en
Publication of WO2021102610A1 publication Critical patent/WO2021102610A1/zh

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
    • 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
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
    • C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • 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
    • C09D151/003—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 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D151/08—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 grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/586—No clear coat specified each layer being cured, at least partially, separately

Definitions

  • the present invention relates to the technical field of floor surface decoration materials. More specifically, the present invention provides a multi-layer radiation curing pre-coating film and a preparation method thereof.
  • the first aspect of the present invention provides a multi-coat radiation curing pre-coating film, which includes a flexible transparent film layer 1 and a radiation curing coating 3 from bottom to top.
  • the top layer includes a radiation-cured elastic primer layer 31 and a radiation-cured wear-resistant topcoat layer 32 in turn.
  • the radiation-curable elastic primer layer 31 and the radiation-cured wear-resistant topcoat layer 32 are each provided with at least one layer.
  • the lacquer layer 31 includes a radiation curing elastic wear-resistant primer layer 312 and a radiation curing elastic matte/bright primer layer 313 from bottom to top.
  • a pretreatment layer 2 for pretreatment of the surface of the flexible transparent film layer 1 is provided between the flexible transparent film layer 1 and the radiation curing coating 3.
  • the bottom layer of the radiation curing elastic wear-resistant primer layer 312 is provided with a radiation curing elastic adhesion primer layer 311.
  • the raw materials for preparing the pretreatment layer 2 include 2-10 parts of bifunctional polyurethane acrylate resin, 0-5 parts of vinyl acetate resin, and 30-40 parts of two parts. Functional acrylate monomer, 30-50 parts solvent and 0-1 part initiator.
  • the raw materials for preparing the radiation-curable elastic adhesion primer layer 311 include 30-60 parts of bifunctional urethane acrylate resin and 20-40 parts of bifunctional acrylate. Monomer, 10-15 parts of monofunctional acrylate and 0-5 parts of initiator.
  • the monofunctional acrylate is selected from isobornyl acrylate, acryloyl morpholine, hydroxyethyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate , N-butyl acrylate, lauryl acrylate, stearate acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, ethoxyethyl Any one or a combination of multiple acrylates.
  • the relative molecular weight of the bifunctional polyurethane acrylate resin is greater than 3000; preferably, the raw materials for preparing the bifunctional polyurethane acrylate resin include polyols, isocyanates and hydroxyl-containing acrylate monomers ; Among them, the molar ratio of polyol and isocyanate is 1:2-5.
  • the polyol includes a component A polyol and a component B polyol, the relative molecular weight of the A component is 500 to 10,000; the relative molecular weight of the B component is 450 to 30; preferably In particular, the molar ratio of component A to component B is (1-3):1.
  • the molecular formula of the A component polyol is OH-R 3 -COO-R 1 -COO-R 2 -OH, and R 3 , R 1 , and R 2 are selected from any group Group;
  • the B component polyol is selected from 1,4-butanediol, 1,4-cyclohexanedimethanol, hydroxyethylated bisphenol A, ethylene glycol, propylene glycol, hexanediol, p-benzene Any one or a combination of diol, neopentyl glycol, and diethylene glycol.
  • the second aspect of the present invention provides a composite material containing the multi-layer radiation curing pre-coating film.
  • the present invention provides a multi-layer coating coating scheme, which greatly improves wear resistance and scratch resistance, and the radiation-cured coating of the multi-layer radiation-cured pre-coating film has excellent elasticity
  • the adhesion bottom layer and the elastic bottom layer to match the flexible film material
  • the adhesion of the pre-coated film layer on the substrate surface is improved, and at the same time, it is beneficial to maintain a better processing type under high temperature conditions, and will not be in the processing process.
  • the problem of whitening or cracking provides a favorable material basis for simplifying the processing and production of traditional PVC composite materials.
  • Figure 1 Schematic diagram of the structure of the coating radiation curing pre-coated film
  • 1-flexible transparent film layer 2-pretreatment layer; 3-radiation curing coating; 31-radiation curing elastic primer layer; 32-radiation curing wear-resistant topcoat layer; 311-radiation curing elastic adhesion primer layer; 312 -Radiation curing elastic wear-resistant primer layer; 313-radiation curing elastic matte/gloss primer layer.
  • the first aspect of the present invention provides a multi-coat radiation curing pre-coating film, which includes a flexible transparent film layer 1 and a radiation curing coating 3 from bottom to top.
  • the top layer includes a radiation-cured elastic primer layer 31 and a radiation-cured wear-resistant topcoat layer 32 in turn.
  • the radiation-curable elastic primer layer 31 and the radiation-cured wear-resistant topcoat layer 32 are each provided with at least one layer.
  • the lacquer layer 31 includes a radiation curing elastic wear-resistant primer layer 312 and a radiation curing elastic matte/bright primer layer 313 from bottom to top.
  • a pretreatment layer 2 for pretreatment of the surface of the flexible transparent film layer 1 is provided between the flexible transparent film layer 1 and the radiation curing coating 3.
  • the bottom layer of the radiation curing elastic wear-resistant primer layer 312 is provided with a radiation curing elastic adhesion primer layer 311.
  • the thickness of the flexible transparent film layer is 50 ⁇ m-1 mm; preferably, the thickness of the flexible transparent film layer is 200 ⁇ m-500 ⁇ m; more preferably, the thickness of the flexible transparent film layer is 350 ⁇ m .
  • the radiation-curable elastic primer layer is 1-3 layers; preferably, the radiation-curable elastic primer layer is 1-2 layers; more preferably, the radiation-curable elastic primer layer For 1 layer.
  • the radiation-curable wear-resistant topcoat layer is 1-3 layers; preferably, the radiation-cured wear-resistant topcoat layer is 1-2 layers; more preferably, the radiation-cured wear-resistant topcoat layer is 1-2 layers;
  • the top paint layer is 1 layer.
  • the raw materials for preparing the pretreatment layer 2 include 2-10 parts of bifunctional urethane acrylate resin, 0-5 parts of vinyl acetate resin, and 30-40 parts of bifunctional acrylate monomer.
  • the preparation raw materials include 4-8 parts bifunctional urethane acrylate resin, 1-4 parts vinyl ester resin, and 33-38 parts bifunctional acrylate Monomers, 35-45 parts solvent and 0.2-0.8 parts initiator; more preferably, the preparation raw materials include 6 parts bifunctional urethane acrylate resin, 3 parts vinyl resin, 35 parts bifunctional acrylate monomer, 40 parts Parts solvent and 0.5 part initiator.
  • the raw materials for preparing the radiation-curable elastic adhesion primer layer 311 include 30-60 parts of bifunctional urethane acrylate resin, 20-40 parts of bifunctional acrylate monomer, 10 ⁇ 15 parts of monofunctional acrylate and 0-5 parts of initiator; preferably, the preparation raw materials include 40-50 parts of bifunctional urethane acrylate resin, 25-35 parts of bifunctional acrylate monomer, and 11-14 parts of monofunctional acrylate monomer. Functional acrylate and 1 to 4 parts of initiator; more preferably, the preparation raw materials include 45 parts of bifunctional urethane acrylate resin, 30 parts of bifunctional acrylate monomer, 13 parts of monofunctional acrylate and 3 parts of initiator Agent.
  • the bifunctional acrylate monomer is selected from any one of 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate.
  • a combination of one or more; preferably, the bifunctional acrylate monomer is 1, 6-hexanediol diacrylate.
  • the vinyl chloride resin is a binary vinyl chloride resin and/or a ternary vinyl chloride resin.
  • the vinyl chloride resin is purchased from Dongguan Yifan Resin Co., Ltd., vinyl chloride resin 14-50.
  • the solvent is selected from any of ethyl acetate, butyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, methanol, n-butanol, and ethanol. One or more combinations.
  • the monofunctional acrylate is selected from isobornyl acrylate, acryloyl morpholine, hydroxyethyl methacrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, stearate acrylate , Isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and ethoxyethyl acrylate; preferably Specifically, the monofunctional acrylate is isobornyl acrylate and acryloyl morpholine; further preferably, the weight ratio of isobornyl acrylate to acryloyl morpholine is 1: (0.3 to 0.8); more preferably, isobornyl acrylate The weight ratio of ester to acryloylmorpholine is 1:0.5.
  • the initiator is selected from 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2-phenylbenzyl -2-Dimethylamine-1-(4-morpholinebenzylphenyl)butanone (369), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), (2 ,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO) one or more; preferably, the initiator is (2,4,6-trimethylbenzoyl)diphenyl Phosphine oxide (TPO).
  • the relative molecular weight of the two-functional polyurethane acrylate resin is greater than 3000; preferably, the raw materials for the preparation of the two-functional polyurethane acrylate resin include polyols, isocyanates, and hydroxyl-containing acrylate monomers; wherein the molar ratio of polyols to isocyanates is 1 : 2-5; Preferably, the molar ratio of polyol to isocyanate is 1:3.5.
  • the hydroxyl-containing acrylate monomer content is used to completely block the isocyanate.
  • the polyol includes a component A polyol and a component B polyol.
  • the relative molecular weight of the A component is 500 to 10,000; the relative molecular weight of the B component is 450 to 30.
  • the molar ratio of component A to component B is (1-3):1; more preferably, the molar ratio of component A to component B is 2:1.
  • the molecular formula of the A component polyol is OH-R 3 -COO-R 1 -COO-R 2 -OH, and R 3 , R 1 , and R 2 are selected from any group; preferably,
  • the A-component polyol is selected from polycaprolactone diol, polyneopentyl adipate diol, polycarbonate diol, poly-1,4-butanediol adipate diol , Polyhexamethylene glycol-propylene glycol ester diol, polybutylene succinate diol, poly adipate neopentyl glycol-1,4-butanediol ester diol, polypropylene glycol ether two Alcohol, any one or a combination of polytetrahydrofuran ether glycol, poly-1,6-hexamethylene adipate diol, and polyphthalate propylene glycol ester diol; preferably Particularly, the A-
  • the weight average molecular weight of the polycaprolactone diol is 1000-3000; preferably, the weight average molecular weight of the polycaprolactone diol is 2000-2500.
  • the weight average molecular weight of the poly(neopentyl glycol adipate) diol is 2000-4000; preferably, the weight average molecular weight of the polycaprolactone diol is 3000-3500.
  • the weight average molecular weight of the polycarbonate diol is 2000-4000; preferably, the weight average molecular weight of the polycarbonate diol is 3000-3500.
  • the present invention does not specifically limit the purchasers of polycaprolactone diol, polyneopentyl adipate diol and polycarbonate diol.
  • the polycaprolactone diol Alcohol, polyneopentyl adipate diol, and polycarbonate diol were purchased from Asahikawa Chemical.
  • the B-component polyol is selected from 1,4-butanediol, 1,4-cyclohexanedimethanol, hydroxyethylated bisphenol A, ethylene glycol, propylene glycol, hexanediol, Any one or a combination of p-phenylene glycol, neopentyl glycol, and diethylene glycol; preferably, the B component polyol is selected from 1,4-butanediol, 1,4-cyclohexane Any one or a combination of dimethanol and hydroxyethylated bisphenol A; further preferably, the B component polyol includes 1,4-butanediol, 1,4-cyclohexanedimethanol, and hydroxy Ethylated bisphenol A; further preferably, the weight ratio of 1,4-butanediol, 1,4-cyclohexanedimethanol and hydroxyethylated bisphenol A is 1:(0.3 ⁇ 0.5):(
  • the hydroxyl-containing acrylate monomer is selected from any one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, methyl hydroxyacrylate, and hydroxypropyl methacrylate.
  • hydroxyethyl acrylate hydroxyethyl methacrylate
  • hydroxybutyl acrylate methyl hydroxyacrylate
  • hydroxypropyl methacrylate hydroxypropyl methacrylate
  • the isocyanate is selected from any of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate. One or more combinations.
  • the flexible transparent film layer material can be selected from any of PVC film, PET film, PETG film, PP film, PC film, PMMA film, and PA film, preferably PVC film; the present invention is transparent to PVC
  • the source of the film layer is not particularly limited.
  • the PVC transparent film layer is purchased from Jiangsu Green Smith Barney.
  • the preparation method of the multi-layer radiation curing pre-coating film is as follows:
  • the coating amount of the radiation curable elastic adhesion primer layer is 2-20 g/m 2 , and the coating amount of the radiation curable elastic wear-resistant primer layer is 10-100 g/m 2 ,
  • the coating amount of the radiation curing elastic matte/bright primer layer is 4-20g/m 2
  • the coating amount of the radiation curing wear-resistant topcoat layer is 4-20g/m 2
  • the radiation curing elasticity is controlled
  • the total coating amount of the adhesion primer layer, the radiation curing elastic wear-resistant primer layer, the radiation curing elastic matte/bright primer layer and the radiation curing wear-resistant topcoat layer is 20-150g/m 2 ; preferably, the The coating amount of the radiation curing elastic adhesion primer layer is 5-15g/m 2 , the coating amount of the radiation curing elastic wear-resistant primer layer is 20-80g/m 2 , the radiation curing elastic matte/bright gloss
  • the coating amount of the primer layer is 10-15g/m 2
  • the total coating amount of the ground primer layer, the radiation curing elastic matte/bright primer layer and the radiation curing wear-resistant topcoat layer is 60-100 g/m 2 ; more preferably, the radiation curing elastic adhesion primer layer
  • the coating amount is 10g/m 2
  • the coating amount of the radiation curable elastic wear-resistant primer layer is 50g/m 2
  • the coating amount of the radiation curable elastic matte/bright primer layer is 12g/m 2
  • the coating amount of the radiation curable wear-resistant topcoat layer is 13 g/m 2 .
  • the amount of pre-coating layer is 2 4 ⁇ 10g / m 2; more preferably, the pretreatment layer 2 The coating amount is 4g/m 2 .
  • the wavelength of the LED light source in step (2) is 200-800nm, and the energy intensity of the light source is greater than 7W/cm 2 ; preferably, the wavelength of the LED light source in step (2) is selected from 365nm, 385nm, 395nm, and the The source energy intensity is 10-12W/cm 2 .
  • the wavelength of the LED light source in step (3) is 200-800nm, and the energy intensity of the light source is greater than 7W/cm 2 ; preferably, the wavelength of the LED light source in step (3) is selected from 365nm, 385nm, 395nm, and the The source energy intensity is 10-12W/cm 2 .
  • the wavelength of the LED light source in step (4) is 200-800nm, and the energy intensity of the light source is greater than 7W/cm 2 ; preferably, the wavelength of the LED light source in step (4) is selected from 365nm, 385nm, 395nm, and The source energy intensity is 10-12W/cm 2 .
  • the wavelength of the LED light source in step (5) is 200-800nm, and the energy intensity of the light source is greater than 7W/cm 2 ; preferably, the wavelength of the LED light source in step (5) is selected from 365nm, 385nm, 395nm, and the light The source energy intensity is 10-12W/cm 2 .
  • the second aspect of the present invention provides a composite material containing the multi-layer radiation curing pre-coating film.
  • the PVC bottom plate and the PVC film are pressed and formed at high temperature to obtain the PVC board substrate, and then UV curing coating is applied to the PVC board substrate to obtain the finished PVC floor.
  • the PVC floor coating obtained by this process has poor adhesion, and the paint is easily peeled off locally, which affects the appearance of the PVC floor; in addition, the PVC floor produced by some grained PVC floor sometimes tends to show uneven gloss; this application tried to pass
  • To prepare a pre-coated film with a multi-layer structure it can be directly pressed with the substrate to form a material, but it is not just that you can get a qualified PVC pre-coating film by simply painting on the PVC film.
  • the PVC pre-coating film has winding cracking, Subsequent pressing and forming of PVC flooring will have various problems such as whitening, cracking, and yellowing.
  • the multi-layer pre-coating film layer material provided in the present application is used, the above-mentioned problems can be better avoided. Perhaps due to the multi-layer coating scheme, the wear resistance and scratch resistance are greatly improved.
  • the radiation-cured coating of the multi-coat radiation-cured pre-coating film has excellent elasticity, so it has good flexibility and can solve the warpage problem of the multi-coating film, so that the composite of the multi-coat radiation-curing pre-coating film
  • the material has good wear resistance, scratch resistance and dimensional stability; in addition, when the flexible film material is treated with a specific treatment layer and an elastic adhesion primer layer is provided, the use performance of the composite material can be further improved.
  • the vinyl chloride resin is similar in polarity to the vinyl chloride in the PVC film structure, which can greatly improve the adhesion of the coating to the PVC film.
  • a small amount in the pretreatment layer The bifunctional urethane acrylate has the effect of bridging the connection between the PVC film and the elastic primer coating.
  • the elastic adhesion primer coating uses a high proportion of bifunctional urethane acrylate. This bifunctional urethane acrylate is extremely polymerized.
  • the functional layer and topcoat layer of the subsequent coating can use conventional and ordinary paint to avoid the above-mentioned cracking , Whitening and yellowing problems.
  • the source of the radiation-curable elastic wear-resistant primer layer 312, the radiation-curable elastic matte primer layer 313, and the radiation-curable wear-resistant topcoat layer 32 is not particularly limited in the present invention, and they can be purchased directly or prepared by themselves; In one embodiment, the radiation-cured elastic wear-resistant primer layer 312, the radiation-cured elastic matte primer layer 313, and the radiation-cured wear-resistant topcoat layer 32 were purchased from Hunan Bangforte New Material Technology Co., Ltd., the models are: BMZ322H , BMZ-3331H, BMZ-1052A.
  • Embodiment 1 of the present invention provides a multi-coat radiation curing pre-coating film, which includes a flexible transparent film layer 1 and a radiation curing coating 3 from bottom to top, and the radiation curing coating 3 includes radiation curing from bottom to top.
  • An elastic primer layer 31 and a radiation-cured wear-resistant topcoat layer 32, the radiation-cured elastic primer layer 31 and the radiation-cured wear-resistant topcoat layer 32 are both provided with at least one layer, and the radiation-cured elastic primer layer 31 consists of
  • the top layer includes radiation curing elastic wear-resistant primer layer 312 and radiation curing elastic matte primer layer 313;
  • a pretreatment layer 2 for pretreatment of the surface of the flexible transparent film layer 1 is provided between the flexible transparent film layer 1 and the radiation curable coating layer 3, and the bottom layer of the radiation curable elastic wear-resistant primer layer 312 is provided There is a radiation curing elastic adhesion primer layer 311; the thickness of the flexible transparent film layer is 350 ⁇ m;
  • the radiation curable elastic primer layer is one layer, and the radiation curable wear-resistant topcoat layer is one layer;
  • the raw materials for preparing the pretreatment layer 2 include 6 parts of bifunctional urethane acrylate resin, 3 parts of vinyl acetate resin, 35 parts of bifunctional acrylate monomer, 40 parts of solvent, and 0.5 part of initiator;
  • the raw materials for the preparation of the radiation-curable elastic adhesion primer layer 311 include 45 parts of bifunctional urethane acrylate resin, 30 parts of bifunctional acrylate monomer, 13 parts of monofunctional acrylate, and 3 parts of initiator;
  • the bifunctional acrylate monomer is 1,6-hexanediol diacrylate, and the vinyl acetate resin is purchased from Dongguan Yifan Resin Co., Ltd., vinyl acetate resin 14-50;
  • the solvent is butyl acetate
  • Monofunctional acrylate is isobornyl acrylate and acryloyl morpholine, and the weight ratio of isobornyl acrylate to acryloyl morpholine is 1:0.5;
  • the initiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO);
  • the raw materials for the preparation of the two-functional polyurethane acrylate resin include polyol, isocyanate and hydroxyl-containing acrylate monomer.
  • the molar ratio of polyol to isocyanate is 1:3.5; the content of hydroxyl-containing acrylate monomer is used to completely block the isocyanate;
  • the hydroxyl-containing acrylate monomer content is used to completely block the isocyanate
  • Polyols include component A polyols and component B polyols, and the molar ratio of component A to component B is 2:1;
  • the A-component polyols include polycaprolactone diol, polyneopentyl adipate diol and polycarbonate diol, polycaprolactone diol, polyneopentyl adipate diol
  • the weight ratio of ester diol and polycarbonate diol is 1:1:0.6;
  • the weight average molecular weight of polycaprolactone diol is 2000-2500, the weight average molecular weight of polycaprolactone diol is 3000-3500, and the weight average molecular weight of polycarbonate diol is 3000-3500;
  • B-component polyols include 1,4-butanediol, 1,4-cyclohexanedimethanol and hydroxyethylated bisphenol A, 1,4-butanediol, 1,4-cyclohexanedimethanol, and The weight ratio of hydroxyethylated bisphenol A is 1:0.45:0.2;
  • the hydroxyl-containing acrylate monomer is methyl hydroxyacrylate; the isocyanate is hexamethylene diisocyanate;
  • the flexible transparent film layer material is PVC film
  • the preparation method of the multi-coat radiation curing pre-coating film is as follows:
  • the coating amount of the radiation curing elastic adhesion primer layer is 10g/m 2
  • the coating amount of the radiation curing elastic wear-resistant primer layer is 50g/m 2
  • the radiation curing elastic matte primer layer The coating amount is 12g/m 2
  • the coating amount of the radiation curable wear-resistant topcoat layer is 13g/m 2 ;
  • the coating amount of the pretreatment layer 2 is 4 g/m 2 .
  • Embodiment 2 of the present invention provides a multi-coat radiation curing pre-coating film, which includes a flexible transparent film layer 1 and a radiation curing coating 3 from bottom to top, and the radiation curing coating 3 includes radiation curing from bottom to top.
  • An elastic primer layer 31 and a radiation-cured wear-resistant topcoat layer 32, the radiation-cured elastic primer layer 31 and the radiation-cured wear-resistant topcoat layer 32 are both provided with at least one layer, and the radiation-cured elastic primer layer 31 consists of
  • the top layer includes radiation curing elastic wear-resistant primer layer 312 and radiation curing elastic matte primer layer 313;
  • a pretreatment layer 2 for pretreatment of the surface of the flexible transparent film layer 1 is provided between the flexible transparent film layer 1 and the radiation curable coating layer 3, and the bottom layer of the radiation curable elastic wear-resistant primer layer 312 is provided There is a radiation curing elastic adhesion primer layer 311; the thickness of the flexible transparent film layer is 500 ⁇ m;
  • the radiation curing elastic primer layer has 3 layers, and the radiation curing wear-resistant top paint layer has 3 layers;
  • the raw materials for preparing the pretreatment layer 2 include 10 parts of bifunctional urethane acrylate resin, 5 parts of vinyl acetate resin, 40 parts of bifunctional acrylate monomer, 50 parts of solvent and 1 part of initiator;
  • the raw materials for preparing the radiation-curable elastic adhesion primer layer 311 include 60 parts of bifunctional urethane acrylate resin, 40 parts of bifunctional acrylate monomer, 15 parts of monofunctional acrylate, and 5 parts of initiator;
  • the bifunctional acrylate monomer is 1,6-hexanediol diacrylate, and the vinyl acetate resin is purchased from Dongguan Yifan Resin Co., Ltd., vinyl acetate resin 14-50;
  • the solvent is butyl acetate
  • Monofunctional acrylate is isobornyl acrylate and acryloyl morpholine, and the weight ratio of isobornyl acrylate to acryloyl morpholine is 1:0.8;
  • the initiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO);
  • the raw materials for the preparation of the two-functional polyurethane acrylate resin include polyol, isocyanate and hydroxyl-containing acrylate monomer; the molar ratio of polyol to isocyanate is 1:5; the content of hydroxyl-containing acrylate monomer is used to completely block the isocyanate;
  • Polyols include component A polyols and component B polyols, and the molar ratio of component A to component B is 3:1;
  • the A-component polyols include polycaprolactone diol, polyneopentyl adipate diol and polycarbonate diol, polycaprolactone diol, polyneopentyl adipate diol
  • the weight ratio of ester diol and polycarbonate diol is 1:1.5:1.5;
  • the weight average molecular weight of polycaprolactone diol is 2000-2500, the weight average molecular weight of polycaprolactone diol is 3000-3500, and the weight average molecular weight of polycarbonate diol is 3000-3500;
  • B-component polyols include 1,4-butanediol, 1,4-cyclohexanedimethanol and hydroxyethylated bisphenol A, 1,4-butanediol, 1,4-cyclohexanedimethanol, and The weight ratio of hydroxyethylated bisphenol A is 1:0.5:0.3;
  • the hydroxyl-containing acrylate monomer is methyl hydroxyacrylate; the isocyanate is hexamethylene diisocyanate;
  • the flexible transparent film layer material is PVC film
  • the preparation method of the multi-coat radiation curing pre-coating film is as follows:
  • the coating amount of the radiation curing elastic adhesion primer layer is 10g/m 2
  • the coating amount of the radiation curing elastic wear-resistant primer layer is 50g/m 2
  • the radiation curing elastic matte primer layer The coating amount is 12g/m 2
  • the coating amount of the radiation curable wear-resistant topcoat layer is 13g/m 2 ;
  • the coating amount of the pretreatment layer 2 is 4 g/m 2 .
  • Embodiment 3 of the present invention provides a multi-coat radiation curing pre-coating film, which includes a flexible transparent film layer 1 and a radiation curing coating 3 from bottom to top, and the radiation curing coating 3 includes radiation curing from bottom to top.
  • An elastic primer layer 31 and a radiation-cured wear-resistant topcoat layer 32, the radiation-cured elastic primer layer 31 and the radiation-cured wear-resistant topcoat layer 32 are both provided with at least one layer, and the radiation-cured elastic primer layer 31 consists of
  • the top layer includes radiation curing elastic wear-resistant primer layer 312 and radiation curing elastic matte primer layer 313;
  • a pretreatment layer 2 for pretreatment of the surface of the flexible transparent film layer 1 is provided between the flexible transparent film layer 1 and the radiation curable coating layer 3, and the bottom layer of the radiation curable elastic wear-resistant primer layer 312 is provided There is a radiation curing elastic adhesion primer layer 311; the thickness of the flexible transparent film layer is 200 ⁇ m;
  • the radiation curable elastic primer layer is one layer, and the radiation curable wear-resistant topcoat layer is one layer;
  • the raw materials for preparing the pretreatment layer 2 include 2 parts of bifunctional urethane acrylate resin, 1 part of vinyl acetate resin, 30 parts of bifunctional acrylate monomer, 30 parts of solvent and 0.1 part of initiator;
  • the raw materials for preparing the radiation-curable elastic adhesion primer layer 311 include 30 parts of bifunctional urethane acrylate resin, 20 parts of bifunctional acrylate monomer, 10 parts of monofunctional acrylate and 1 part of initiator;
  • the bifunctional acrylate monomer is 1,6-hexanediol diacrylate, and the vinyl acetate resin is purchased from Dongguan Yifan Resin Co., Ltd., vinyl acetate resin 14-50;
  • the solvent is butyl acetate
  • Monofunctional acrylate is isobornyl acrylate and acryloyl morpholine, and the weight ratio of isobornyl acrylate to acryloyl morpholine is 1:0.3;
  • the initiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO);
  • the raw materials for the preparation of the two-functional polyurethane acrylate resin include polyol, isocyanate and hydroxyl-containing acrylate monomer; the molar ratio of polyol to isocyanate is 1:3; the content of hydroxyl-containing acrylate monomer is used to completely block the isocyanate;
  • Polyols include component A polyols and component B polyols, and the molar ratio of component A to component B is 1.5:1;
  • the A-component polyols include polycaprolactone diol, polyneopentyl adipate diol and polycarbonate diol, polycaprolactone diol, polyneopentyl adipate diol
  • the weight ratio of ester diol and polycarbonate diol is 1:0.5:0.5;
  • the weight average molecular weight of polycaprolactone diol is 2000-2500, the weight average molecular weight of polycaprolactone diol is 3000-3500, and the weight average molecular weight of polycarbonate diol is 3000-3500;
  • Small molecule diols include 1,4-butanediol, 1,4-cyclohexanedimethanol and hydroxyethylated bisphenol A, 1,4-butanediol, 1,4-cyclohexanedimethanol and The weight ratio of hydroxyethylated bisphenol A is 1:0.3:0.1;
  • the hydroxyl-containing acrylate monomer is methyl hydroxyacrylate; the isocyanate is hexamethylene diisocyanate;
  • the flexible transparent film layer material is PVC film
  • the preparation method of the multi-coat radiation curing pre-coating film is the same as that of Example 1.
  • Example 4 of the present invention provides a multi-coat radiation curing pre-coating film.
  • the specific implementation is the same as that of Example 1, except that there is no arrangement between the flexible transparent film layer 1 and the radiation curing coating 3 A pretreatment layer 2 for pretreatment of the surface of the flexible transparent film layer 1.
  • Example 5 of the present invention provides a multi-coat radiation curing pre-coated film.
  • the specific implementation is the same as that of Example 1, except that the raw material for the pretreatment layer 2 includes 0 parts of a bifunctional polyurethane acrylate resin. , 3 parts of vinyl acetate resin, 35 parts of bifunctional acrylate monomer, 40 parts of solvent and 0.5 parts of initiator.
  • Example 6 of the present invention provides a multi-coat radiation curing pre-coated film.
  • the specific implementation is the same as that of Example 1, except that the raw material for preparing the pretreatment layer 2 includes 25 parts of a bifunctional polyurethane acrylate resin. , 3 parts of vinyl acetate resin, 35 parts of bifunctional acrylate monomer, 40 parts of solvent and 0.5 parts of initiator.
  • Example 7 of the present invention provides a multi-coat radiation curing pre-coated film.
  • the specific implementation is the same as that of Example 1.
  • the difference is that, in parts by weight, the raw material for preparing the pretreatment layer 2 includes 6 parts of bifunctional Polyurethane acrylate resin, 0 parts vinyl resin, 35 parts bifunctional acrylate monomer, 40 parts solvent and 0.5 parts initiator.
  • Example 8 of the present invention provides a multi-coat radiation curing pre-coating film.
  • the specific implementation is the same as that of Example 1, except that the bottom layer of the radiation curing elastic wear-resistant primer layer 312 is not provided with radiation curing.
  • the primer layer 311 is elastically attached.
  • Example 9 of the present invention provides a multi-coat radiation curing pre-coating film.
  • the specific implementation is the same as that of Example 1.
  • the difference is that the raw materials for preparing the radiation curing elastic adhesion primer layer 311 include 0 parts of bifunctionality.
  • Example 10 of the present invention provides a multi-layer radiation curing pre-coating film.
  • the specific implementation is the same as that of Example 1.
  • the difference is that the raw materials for preparing the radiation curing elastic adhesion primer layer 311 include 15 parts of bifunctionality.
  • the pre-coated film material and the SPC substrate obtained in the examples were heated to 175° C., rolled by steel for 5 seconds, and cooled to form a composite material.
  • Adhesion test The composite material prepared with the pre-coated film obtained in Examples 1 to 10 was used to measure the adhesive force of the material in accordance with ASTM D3359. The test results are shown in Table 1;
  • PVC pre-coating film processing performance test observe whether the PVC pre-coating film cracks during the preparation of the composite material prepared by the pre-coating film obtained in Examples 1-10. Each example corresponds to 100 samples, and the probability of cracking is calculated , The test results are shown in Table 1.
  • Example 3 5B 1 Example 4 2B 42
  • Example 5 Example 5 4B 36
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 4B 12
  • the present invention uses the adhesion bottom layer and the elastic bottom layer to match the PVC flexible film material to improve the adhesion of the PVC pre-coated film layer on the surface of the substrate, and at the same time, it is beneficial to maintain a better processing type under high temperature conditions. Will not cause whitening, cracking, yellowing and other problems.

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Abstract

本发明涉及地板表面装饰材料的技术领域，更具体地，本发明提供一种多涂层辐射固化预涂装膜及其制备方法。本发明第一方面提供一种多涂层辐射固化预涂装膜，由下至上依次包括柔性透明膜层1与辐射固化涂层3，所述辐射固化涂层3由下至上依次包括辐射固化弹性底漆层31和辐射固化耐磨面漆层32，所述辐射固化弹性底漆层31和辐射固化耐磨面漆层32均至少设置一层，所述辐射固化弹性底漆层31由下至上依次包括辐射固化弹性耐磨底漆层312和辐射固化弹性哑光/亮光底漆层313。本发明提供了多道涂层的涂装方案，大幅提高了耐磨、耐刮伤性，且多涂层辐射固化预涂装膜的辐射固化涂层具有优异的弹性，同时避免涂层脱落、翘曲等问题。

Description

一种多涂层辐射固化预涂装膜及其制备方法 技术领域
本发明涉及地板表面装饰材料的技术领域，更具体地，本发明提供一种多涂层辐射固化预涂装膜及其制备方法。
背景技术
随着环保法规的日益严格、环保呼声的日益提高，消费者对地板反复的涂装、安装方式提高了更好的要求，开发出新的施工方式迫在眉睫。常规的覆膜(又称贴塑)具有施工简单、绿色环保的特性，覆膜后的产品具有一定的防水、防褪色、耐污作用，提高了基材质感和档次，但是强度差，不具备耐磨、耐刮伤作用，目前仅使用在对耐磨、耐刮、强度等性能要求不高的印刷品市场及各类包装品市场，在地板、家具等涂装领域尚未得到应用。
此外，在实际使用过程中，为满足消费者对地板表面耐磨、耐刮伤、强度等不同性能的要求，经常于地板表面添加各种功能性涂层以满足不同消费者对不同类型地板的需求，但在实现多样化地板生产的同时，制备得到的地板容易出现各种问题，例如地板与涂层结合力较差，涂层不耐用，容易脱落，造成地板寿命降低；此外，部分有纹路的PVC地板，生产成的PVC地板有时容易呈现光泽不均匀，地板之间的差异化较大。
发明内容
为解决上述技术问题，本发明第一方面提供一种多涂层辐射固化预涂装膜，由下至上依次包括柔性透明膜层1与辐射固化涂层3，所述辐射固化涂层3由下至上依次包括辐射固化弹性底漆层31和辐射固化耐磨面漆层32，所述辐射固化弹性底漆层31和辐射固化耐磨面漆层32均至少设置一层，所述辐射固化弹性底漆层31由下至上依次包括辐射固化弹性耐磨底漆层312和辐射固化弹性哑光/亮光底漆层313。
作为本发明的一种优选技术方案，其中，所述柔性透明膜层1与辐射固化涂层3之间设有一层用于对柔性透明膜层1表面进行预处理的预处理层2。
作为本发明的一种优选技术方案，其中，所述辐射固化弹性耐磨底漆层312的底层设有辐射固化弹性附着底漆层311。
作为本发明的一种优选技术方案，其中，按重量份计，预处理层2的制备原 料包括2～10份两官能度聚氨酯丙烯酸酯树脂、0～5份氯醋树脂、30～40份两官能度丙烯酸酯单体、30～50份溶剂以及0-1份引发剂。
作为本发明的一种优选技术方案，其中，按重量份计，辐射固化弹性附着底漆层311的制备原料包括30～60份两官能度聚氨酯丙烯酸酯树脂、20～40份两官能度丙烯酸酯单体、10～15份单官能度丙烯酸酯以及0～5份引发剂。
作为本发明的一种优选技术方案，其中，单官能度丙烯酸酯选自丙烯酸异冰片酯、丙烯酰吗啉，甲基丙烯酸羟乙酯、丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸月桂酯、丙烯酸硬脂酸酯、丙烯酸异丙酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、乙氧基乙基丙烯酸酯中的任一种或多种的组合。
作为本发明的一种优选技术方案，其中，两官能度聚氨酯丙烯酸酯树脂的相对分子量大于3000；优选地，两官能度聚氨酯丙烯酸酯树脂的制备原料包括多元醇、异氰酸酯以及含羟基丙烯酸酯单体；其中，多元醇与异氰酸酯的摩尔比为1：2～5。
作为本发明的一种优选技术方案，其中，多元醇包括A组分多元醇与B组分多元醇，A组分的相对分子量为500～10000；B组分的相对分子量为450～30；优选地，A组分与B组分的摩尔比为(1～3)：1。
作为本发明的一种优选技术方案，其中，A组分多元醇的分子式为OH-R 3-COO-R 1-COO-R 2-OH，且R 3、R 1、R 2选自任意基团；优选地，B组分多元醇选自1,4-丁二醇、1,4-环己烷二甲醇、羟乙基化双酚A、乙二醇、丙二醇、己二醇、对苯二醇、新戊二醇、二乙二醇中的任一种或多种的组合。
本发明的第二方面提供一种含有所述多涂层辐射固化预涂装膜的复合材料。
与现有技术相比，本发明提供了多道涂层的涂装方案，大幅提高了耐磨、耐刮伤性，且多涂层辐射固化预涂装膜的辐射固化涂层具有优异的弹性，此外，通过利用附着底层以及弹性底层以配合柔性膜材料，提高预涂装膜层在基板表面的附着力，同时有利于在高温条件下也可保持较好的加工型，不会在加工过程中发白或开裂的问题，从而为简化传统PVC复合材料的加工生产提供了有利的材料基础。
附图说明
图1：涂层辐射固化预涂装膜的结构示意图；
1-柔性透明膜层；2-预处理层；3-辐射固化涂层；31-辐射固化弹性底漆层；32-辐射固化耐磨面漆层；311-辐射固化弹性附着底漆层；312-辐射固化弹性耐磨底漆层；313-辐射固化弹性哑光/亮光底漆层。
具体实施方式
除非另有说明、从上下文暗示或属于现有技术的惯例，否则本申请中所有的份数和百分比都基于重量，且所用的测试和表征方法都是与本申请的提交日期同步的。如果现有技术中披露的具体术语的定义与本申请中提供的任何定义不一致，则以本申请中提供的术语定义为准。
下面结合具体实施方式对本发明提供技术方案中的技术特征作进一步清楚、完整的描述，并非对其保护范围的限制。
本发明中的词语“优选的”、“优选地”、“更优选的”等是指，在某些情况下可提供某些有益效果的本发明实施方案。然而，在相同的情况下或其他情况下，其他实施方案也可能是优选的。此外，对一个或多个优选实施方案的表述并不暗示其他实施方案不可用，也并非旨在将其他实施方案排除在本发明的范围之外。本发明中未提及的组分的来源均为市售。
为解决上述技术问题，本发明第一方面提供一种多涂层辐射固化预涂装膜，由下至上依次包括柔性透明膜层1与辐射固化涂层3，所述辐射固化涂层3由下至上依次包括辐射固化弹性底漆层31和辐射固化耐磨面漆层32，所述辐射固化弹性底漆层31和辐射固化耐磨面漆层32均至少设置一层，所述辐射固化弹性底漆层31由下至上依次包括辐射固化弹性耐磨底漆层312和辐射固化弹性哑光/亮光底漆层313。
在一种实施方式中，所述柔性透明膜层1与辐射固化涂层3之间设有一层用于对柔性透明膜层1表面进行预处理的预处理层2。
在一种实施方式中，所述辐射固化弹性耐磨底漆层312的底层设有辐射固化弹性附着底漆层311。
在一种实施方式中，所述柔性透明膜层的厚度为50μm-1mm；优选地，所述柔性透明膜层的厚度为200μm-500μm；更优选地，所述柔性透明膜层的厚度为350μm。
在一种实施方式中，所述辐射固化弹性底漆层为1-3层；优选地，所述辐射固化弹性底漆层为1-2层；更优选地，所述辐射固化弹性底漆层为1层。
在一种实施方式中，所述辐射固化耐磨面漆层为1-3层；优选地，所述辐射固化耐磨面漆层为1-2层；更优选地，所述辐射固化耐磨面漆层为1层。
在一种实施方式中，按重量份计，预处理层2的制备原料包括2～10份两官能度聚氨酯丙烯酸酯树脂、0～5份氯醋树脂、30～40份两官能度丙烯酸酯单体、30～50份溶剂以及0～1份引发剂；优选地，制备原料包括4～8份两官能度聚氨酯丙烯酸酯树脂、1～4份氯醋树脂、33～38份两官能度丙烯酸酯单体、35～45份溶剂以及0.2～0.8份引发剂；更优选地，制备原料包括6份两官能度聚氨酯丙烯酸酯树脂、3份氯醋树脂、35份两官能度丙烯酸酯单体、40份溶剂以及0.5份引发剂。
在一种实施方式中，按重量份计，辐射固化弹性附着底漆层311的制备原料包括30～60份两官能度聚氨酯丙烯酸酯树脂、20～40份两官能度丙烯酸酯单体、10～15份单官能度丙烯酸酯以及0～5份引发剂；优选地，制备原料包括40～50份两官能度聚氨酯丙烯酸酯树脂、25～35份两官能度丙烯酸酯单体、11～14份单官能度丙烯酸酯以及1～4份引发剂；更优选地，制备原料包括45份两官能度聚氨酯丙烯酸酯树脂、30份两官能度丙烯酸酯单体、13份单官能度丙烯酸酯以及3份引发剂。
在一种实施方式中，两官能度丙烯酸酯单体选自1、6-已二醇二丙烯酸酯、新戊二醇二丙烯酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯中的任一种或多种的组合；优选地，两官能度丙烯酸酯单体为1、6-已二醇二丙烯酸酯。
在一种实施方式中，氯醋树脂为二元氯醋树脂和\或三元氯醋树脂。
本发明对购买厂家不做特别限制，一种实施方式中，氯醋树脂购自东莞市一帆树脂有限公司，氯醋树脂14-50。
在一种实施方式中，溶剂选自乙酸乙酯、醋酸丁酯、丁二酸二甲酯、戊二酸二甲酯、已二酸二甲酯、甲醇、正丁醇、乙醇中的任一种或多种的组合。
在一种实施方式中，单官能度丙烯酸酯选自丙烯酸异冰片酯、丙烯酰吗啉，甲基丙烯酸羟乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸月桂酯、丙烯酸硬脂酸酯、丙烯酸异丙酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸羟乙酯、丙烯酸羟 丙酯、丙烯酸羟丁酯、乙氧基乙基丙烯酸酯中的任一种或多种的组合；优选地，单官能度丙烯酸酯为丙烯酸异冰片酯与丙烯酰吗啉；进一步优选地，丙烯酸异冰片酯与丙烯酰吗啉的重量比为1：(0.3～0.8)；更优选地，丙烯酸异冰片酯与丙烯酰吗啉的重量比为1：0.5。
在一种实施方式中，引发剂选自1-羟基环己基苯基甲酮(184)、2-羟基-2-甲基-1-苯基-1-丙酮(1173)、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮(369)、苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)、(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)中的一种或几种；优选地，引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)。
两官能度聚氨酯丙烯酸酯树脂的相对分子量大于3000；优选地，两官能度聚氨酯丙烯酸酯树脂的制备原料包括多元醇、异氰酸酯以及含羟基丙烯酸酯单体；其中，多元醇与异氰酸酯的摩尔比为1：2～5；优选地，多元醇与异氰酸酯的摩尔比为1：3.5。
在一种实施方式中，含羟基丙烯酸酯单体含量用于完全封闭异氰酸酯。
在一种实施方式中，多元醇包括A组分多元醇与B组分多元醇，A组分的相对分子量为500～10000；B组分的相对分子量为450～30。
在一种实施方式中，A组分与B组分的摩尔比为(1～3)：1；更优选地，A组分与B组分的摩尔比为2：1。
在一种实施方式中，A组分多元醇的分子式为OH-R 3-COO-R 1-COO-R 2-OH，且R 3、R 1、R 2选自任意基团；优选地，A组分多元醇选自聚己内酯二元醇、聚己二酸新戊二醇酯二元醇、聚碳酸酯二元醇、聚己二酸-1，4一丁二醇酯二醇、聚己二酯乙二醇-丙二醇酯二醇、聚丁二酸丁二醇酯二元醇、聚己二酸新戊二醇-1，4-丁二醇酯二醇、聚丙二醇醚二醇，聚四氢喃喃醚二醇、聚已二酸-1,6已二醇酯二元醇、聚邻苯二甲酯丙二醇酯二元醇中的任一种或多种的组合；优选地，A组分多元醇包括聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇；进一步优选地，聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇的重量比为1：(0.5～1.5)：(0.5～1.5)；更优选地，聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇的重量比为1：1：0.6。
在一种实施方式中，聚己内酯二元醇的重均分子量为1000～3000；优选地， 聚己内酯二元醇的重均分子量为2000～2500。
在一种实施方式中，聚己二酸新戊二醇酯二元醇的重均分子量为2000～4000；优选地，聚己内酯二元醇的重均分子量为3000～3500。
在一种实施方式中，聚碳酸酯二元醇的重均分子量为2000～4000；优选地，聚碳酸酯二元醇的重均分子量为3000～3500。
本发明对聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇的购买厂家不做特别限制，一种实施方式中，聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇分别购自旭川化学。
在一种实施方式中，B组分多元醇选自1,4-丁二醇、1,4-环己烷二甲醇、羟乙基化双酚A、乙二醇、丙二醇、己二醇、对苯二醇、新戊二醇、二乙二醇中的任一种或多种的组合；优选地，B组分多元醇选自1,4-丁二醇、1,4-环己烷二甲醇、羟乙基化双酚A中的任一种或多种的组合；进一步优选地，B组分多元醇包括1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A；进一步优选地，1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A的重量比为1：(0.3～0.5)：(0.1～0.3)；更优选地，1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A的重量比为1：0.45：0.2。
在一种实施方式中，含羟基丙烯酸酯单体选自丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丁酯、羟基丙烯酸甲酯、甲基丙烯酸羟丙酯中的任一种或多种的组合。
在一种实施方式中，异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯中的任一种或多种的组合。
在一种实施方式中，柔性透明膜层材料可选用PVC膜、PET膜、PETG膜、PP膜、PC膜、PMMA膜、PA膜中的任一种，优选采用PVC膜；本发明对PVC透明膜层的来源不做特别限制，一种实施方式中，PVC透明膜层购自江苏绿色美邦。
在一种实施方式中，所述多涂层辐射固化预涂装膜的制备方法如下：
(1)将预处理层2与辐射固化弹性附着底漆层311的制备原料分别用分散釜搅拌均匀；
(2)于柔性透明膜层1表面用辊轮将预处理层2涂布均匀，进行LED固化；
(3)于预处理层2表面用辊轮将辐射固化弹性附着底漆层311涂布均匀，进行LED固化；
(4)于辐射固化弹性附着底漆层311表面用辊轮将辐射固化弹性耐磨底漆层312涂布均匀，进行LED固化；
(5)于辐射固化弹性耐磨底漆层312表面用辊轮将辐射固化弹性哑光底漆层313涂布均匀，进行LED固化；
(6)于辐射固化弹性哑光底漆层313表面用辊轮将辐射固化耐磨面漆层32涂布均匀，进行汞灯固化；即得多涂层辐射固化预涂装膜。
在一种实施方式中，所述辐射固化弹性附着底漆层的涂布量为2-20g/m 2，所述辐射固化弹性耐磨底漆层的涂布量为10-100g/m 2，所述辐射固化弹性哑光/亮光底漆层的涂布量为4-20g/m 2，所述辐射固化耐磨面漆层的涂布量为4-20g/m 2，并控制辐射固化弹性附着底漆层、辐射固化弹性耐磨底漆层、辐射固化弹性哑光/亮光底漆层和辐射固化耐磨面漆层的总涂布量为20-150g/m 2；优选地，所述辐射固化弹性附着底漆层的涂布量为5-15g/m 2，所述辐射固化弹性耐磨底漆层的涂布量为20-80g/m 2，所述辐射固化弹性哑光/亮光底漆层的涂布量为10-15g/m 2，所述辐射固化耐磨面漆层的涂布量为10-15g/m 2，并控制辐射固化弹性附着底漆层、辐射固化弹性耐磨底漆层、辐射固化弹性哑光/亮光底漆层和辐射固化耐磨面漆层的总涂布量为60-100g/m 2；更优选地，所述辐射固化弹性附着底漆层的涂布量为10g/m 2，所述辐射固化弹性耐磨底漆层的涂布量为50g/m 2，所述辐射固化弹性哑光/亮光底漆层的涂布量为12g/m 2，所述辐射固化耐磨面漆层的涂布量为13g/m 2。
在一种实施方式中，预处理层2的涂布量为3～20g/m2；优选地，预处理层2的涂布量为4～10g/m 2；更优选地，预处理层2的涂布量为4g/m 2。
在一种实施方式中，步骤(2)中LED光源波长为200-800nm，灯源能量强度大于7W/cm 2；优选地，步骤(2)中LED光源波长选自365nm、385nm、395nm，灯源能量强度为10～12W/cm 2。
在一种实施方式中，步骤(3)中LED光源波长为200-800nm，灯源能量强度大于7W/cm 2；优选地，步骤(3)中LED光源波长选自365nm、385nm、395nm， 灯源能量强度为10～12W/cm 2。
在一种实施方式中，步骤(4)中LED光源波长为200-800nm，灯源能量强度大于7W/cm 2；优选地，步骤(4)中LED光源波长选自365nm、385nm、395nm，灯源能量强度为10～12W/cm 2。
在一种实施方式中，步骤(5)中LED光源波长为200-800nm，灯源能量强度大于7W/cm 2；优选地，步骤(5)中LED光源波长选自365nm、385nm、395nm，灯源能量强度为10～12W/cm 2。
本发明的第二方面提供一种含有所述多涂层辐射固化预涂装膜的复合材料。
传统的PVC地板复合材料的制备过程中，是通过PVC底板与PVC膜高温压贴成型，得到PVC板基材，然后在PVC板基材做紫外光固化涂料，得到PVC地板成品。按这种工艺得到的PVC地板涂层附着力差，油漆局部容易脱落，影响PVC地板的美观；此外，部分有纹路的PVC地板，生产成的PVC地板有时容易呈现光泽不均匀；本申请尝试通过制备多层结构的预涂装膜层，其可以直接与基板压合，形成材料，但并不是随便在PVC膜上做油漆均可以得到合格PVC预涂膜，PVC预涂膜存在收卷开裂，后续压贴成型PVC地板会出现发白、开裂、变黄等多种问题。
申请人发现当采用本申请提供的多层预涂装膜层材料时，可以较好的避免上述问题，可能由于采用多道涂层的涂装方案，大幅提高了耐磨、耐刮伤性，且多涂层辐射固化预涂装膜的辐射固化涂层具有优异的弹性，因此柔韧性好，能解决多涂漆膜的翘曲难题，使应用该多涂层辐射固化预涂装膜的复合材料的具有良好的耐磨、耐刮及尺寸稳定性；此外，当采用特定处理层对柔性膜材料进行处理时，且设置有弹性附着底漆层时，可以进一步提高复合材料的使用性能，可能由于预处理层通过使用对PVC膜有咬蚀使用的单体和溶剂，氯醋树脂与PVC膜结构中氯乙烯极性相似，可以大大提高涂层对PVC膜的附着力，预处理层中少量的两官能聚氨酯丙烯酸酯对PVC膜和弹性底漆涂层之间起来驾桥连接作用，弹性附着底漆涂层中的使用高比例的两官聚氨酯丙烯酸酯，此两官聚氨酯丙烯酸酯聚有极好的韧性和伸长率，抗黄变性好，通过附着底漆层和弹性底漆层的优化测试，后续涂装的功能层、面漆层就可以使用常规、普通的油漆，从而避免上述的开裂、发白、黄变问题。
本发明对辐射固化弹性耐磨底漆层312、辐射固化弹性哑光底漆层313、辐射固化耐磨面漆层32的来源不做特别限制，可以直接购买得到，也可以自己制备得到；一种实施方式中，辐射固化弹性耐磨底漆层312、辐射固化弹性哑光底漆层313、辐射固化耐磨面漆层32购自湖南邦弗特新材料技术有限公司，型号分别为：BMZ322H、BMZ-3331H、BMZ-1052A。
为了更好的理解上述技术方案，下面将结合具体的实施例对上述技术方案进行详细的说明。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。其中，辐射固化弹性耐磨底漆层312、辐射固化弹性哑光底漆层313、辐射固化耐磨面漆层32购自湖南邦弗特新材料技术有限公司，型号分别为：BMZ322H、BMZ-3331H、BMZ-1052A。
实施例1
本发明的实施例1提供一种多涂层辐射固化预涂装膜，由下至上依次包括柔性透明膜层1与辐射固化涂层3，所述辐射固化涂层3由下至上依次包括辐射固化弹性底漆层31和辐射固化耐磨面漆层32，所述辐射固化弹性底漆层31和辐射固化耐磨面漆层32均至少设置一层，所述辐射固化弹性底漆层31由下至上依次包括辐射固化弹性耐磨底漆层312和辐射固化弹性哑光底漆层313；
所述柔性透明膜层1与辐射固化涂层3之间设有一层用于对柔性透明膜层1表面进行预处理的预处理层2，所述辐射固化弹性耐磨底漆层312的底层设有辐射固化弹性附着底漆层311；所述柔性透明膜层的厚度为350μm；
所述辐射固化弹性底漆层为1层，所述辐射固化耐磨面漆层为1层；
按重量份计，预处理层2的制备原料包括6份两官能度聚氨酯丙烯酸酯树脂、3份氯醋树脂、35份两官能度丙烯酸酯单体、40份溶剂以及0.5份引发剂；
按重量份计，辐射固化弹性附着底漆层311的制备原料包括45份两官能度聚氨酯丙烯酸酯树脂、30份两官能度丙烯酸酯单体、13份单官能度丙烯酸酯以及3份引发剂；
两官能度丙烯酸酯单体为1、6-已二醇二丙烯酸酯，氯醋树脂购自东莞市一帆树脂有限公司，氯醋树脂14-50；
溶剂为醋酸丁酯；
单官能度丙烯酸酯为丙烯酸异冰片酯与丙烯酰吗啉，丙烯酸异冰片酯与丙烯酰吗啉的重量比为1：0.5；
引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)；
两官能度聚氨酯丙烯酸酯树脂的制备原料包括多元醇、异氰酸酯以及含羟基丙烯酸酯单体，多元醇与异氰酸酯的摩尔比为1：3.5；含羟基丙烯酸酯单体含量用于完全封闭异氰酸酯；
含羟基丙烯酸酯单体含量用于完全封闭异氰酸酯，
多元醇包括A组分多元醇与B组分多元醇，A组分与B组分的摩尔比为2：1；
A组分多元醇包括聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇，聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇的重量比为1：1：0.6；
聚己内酯二元醇的重均分子量为2000～2500，聚己内酯二元醇的重均分子量为3000～3500，聚碳酸酯二元醇的重均分子量为3000～3500；
B组分多元醇包括1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A，1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A的重量比为1：0.45：0.2；
含羟基丙烯酸酯单体为羟基丙烯酸甲酯；异氰酸酯为六亚甲基二异氰酸酯；
柔性透明膜层材料为PVC膜；
所述多涂层辐射固化预涂装膜的制备方法如下：
(1)将预处理层2与辐射固化弹性附着底漆层311的制备原料分别用分散釜搅拌均匀；
(2)于柔性透明膜层1表面用辊轮将预处理层2涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(3)于预处理层2表面用辊轮将辐射固化弹性附着底漆层311涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(4)于辐射固化弹性附着底漆层311表面用辊轮将辐射固化弹性耐磨底漆层312涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(5)于辐射固化弹性耐磨底漆层312表面用辊轮将辐射固化弹性哑光底漆层313涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(6)于辐射固化弹性哑光底漆层313表面用辊轮将辐射固化耐磨面漆层32涂布均匀，进行汞灯固化；即得多涂层辐射固化预涂装膜；
所述辐射固化弹性附着底漆层的涂布量为10g/m 2，所述辐射固化弹性耐磨底漆层的涂布量为50g/m 2，所述辐射固化弹性哑光底漆层的涂布量为12g/m 2，所述辐射固化耐磨面漆层的涂布量为13g/m 2；
预处理层2的涂布量为4g/m 2。
实施例2
本发明的实施例2提供一种多涂层辐射固化预涂装膜，由下至上依次包括柔性透明膜层1与辐射固化涂层3，所述辐射固化涂层3由下至上依次包括辐射固化弹性底漆层31和辐射固化耐磨面漆层32，所述辐射固化弹性底漆层31和辐射固化耐磨面漆层32均至少设置一层，所述辐射固化弹性底漆层31由下至上依次包括辐射固化弹性耐磨底漆层312和辐射固化弹性哑光底漆层313；
所述柔性透明膜层1与辐射固化涂层3之间设有一层用于对柔性透明膜层1表面进行预处理的预处理层2，所述辐射固化弹性耐磨底漆层312的底层设有辐射固化弹性附着底漆层311；所述柔性透明膜层的厚度为500μm；
所述辐射固化弹性底漆层为3层，所述辐射固化耐磨面漆层为3层；
按重量份计，预处理层2的制备原料包括10份两官能度聚氨酯丙烯酸酯树脂、5份氯醋树脂、40份两官能度丙烯酸酯单体、50份溶剂以及1份引发剂；
按重量份计，辐射固化弹性附着底漆层311的制备原料包括60份两官能度聚氨酯丙烯酸酯树脂、40份两官能度丙烯酸酯单体、15份单官能度丙烯酸酯以及5份引发剂；
两官能度丙烯酸酯单体为1、6-已二醇二丙烯酸酯，氯醋树脂购自东莞市一帆树脂有限公司，氯醋树脂14-50；
溶剂为醋酸丁酯；
单官能度丙烯酸酯为丙烯酸异冰片酯与丙烯酰吗啉，丙烯酸异冰片酯与丙烯酰吗啉的重量比为1：0.8；
引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)；
两官能度聚氨酯丙烯酸酯树脂的制备原料包括多元醇、异氰酸酯以及含羟基丙烯酸酯单体；多元醇与异氰酸酯的摩尔比为1：5；含羟基丙烯酸酯单体含量用于完全封闭异氰酸酯；
多元醇包括A组分多元醇与B组分多元醇，A组分与B组分的摩尔比为3：1；
A组分多元醇包括聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇，聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇的重量比为1：1.5：1.5；
聚己内酯二元醇的重均分子量为2000～2500，聚己内酯二元醇的重均分子量为3000～3500，聚碳酸酯二元醇的重均分子量为3000～3500；
B组分多元醇包括1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A，1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A的重量比为1：0.5：0.3；
含羟基丙烯酸酯单体为羟基丙烯酸甲酯；异氰酸酯为六亚甲基二异氰酸酯；
柔性透明膜层材料为PVC膜；
所述多涂层辐射固化预涂装膜的制备方法如下：
(1)将预处理层2与辐射固化弹性附着底漆层311的制备原料分别用分散釜搅拌均匀；
(2)于柔性透明膜层1表面用辊轮将预处理层2涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(3)于预处理层2表面用辊轮将辐射固化弹性附着底漆层311涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(4)于辐射固化弹性附着底漆层311表面用辊轮将辐射固化弹性耐磨底漆层312涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(5)于辐射固化弹性耐磨底漆层312表面用辊轮将辐射固化弹性哑光底漆层313涂布均匀，进行LED固化，LED光源波长为395nm，灯源能量强度为10W/cm 2；
(6)于辐射固化弹性哑光底漆层313表面用辊轮将辐射固化耐磨面漆层32 涂布均匀，进行汞灯固化；即得多涂层辐射固化预涂装膜；
所述辐射固化弹性附着底漆层的涂布量为10g/m 2，所述辐射固化弹性耐磨底漆层的涂布量为50g/m 2，所述辐射固化弹性哑光底漆层的涂布量为12g/m 2，所述辐射固化耐磨面漆层的涂布量为13g/m 2；
预处理层2的涂布量为4g/m 2。
实施例3
本发明的实施例3提供一种多涂层辐射固化预涂装膜，由下至上依次包括柔性透明膜层1与辐射固化涂层3，所述辐射固化涂层3由下至上依次包括辐射固化弹性底漆层31和辐射固化耐磨面漆层32，所述辐射固化弹性底漆层31和辐射固化耐磨面漆层32均至少设置一层，所述辐射固化弹性底漆层31由下至上依次包括辐射固化弹性耐磨底漆层312和辐射固化弹性哑光底漆层313；
所述柔性透明膜层1与辐射固化涂层3之间设有一层用于对柔性透明膜层1表面进行预处理的预处理层2，所述辐射固化弹性耐磨底漆层312的底层设有辐射固化弹性附着底漆层311；所述柔性透明膜层的厚度为200μm；
所述辐射固化弹性底漆层为1层，所述辐射固化耐磨面漆层为1层；
按重量份计，预处理层2的制备原料包括2份两官能度聚氨酯丙烯酸酯树脂、1份氯醋树脂、30份两官能度丙烯酸酯单体、30份溶剂以及0.1份引发剂；
按重量份计，辐射固化弹性附着底漆层311的制备原料包括30份两官能度聚氨酯丙烯酸酯树脂、20份两官能度丙烯酸酯单体、10份单官能度丙烯酸酯以及1份引发剂；
两官能度丙烯酸酯单体为1、6-已二醇二丙烯酸酯，氯醋树脂购自东莞市一帆树脂有限公司，氯醋树脂14-50；
溶剂为醋酸丁酯；
单官能度丙烯酸酯为丙烯酸异冰片酯与丙烯酰吗啉，丙烯酸异冰片酯与丙烯酰吗啉的重量比为1：0.3；
引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)；
两官能度聚氨酯丙烯酸酯树脂的制备原料包括多元醇、异氰酸酯以及含羟基丙烯酸酯单体；多元醇与异氰酸酯的摩尔比为1：3；含羟基丙烯酸酯单体含量用于完全封闭异氰酸酯；
多元醇包括A组分多元醇与B组分多元醇，A组分与B组分的摩尔比为1.5：1；
A组分多元醇包括聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇，聚己内酯二元醇、聚己二酸新戊二醇酯二元醇以及聚碳酸酯二元醇的重量比为1：0.5：0.5；
聚己内酯二元醇的重均分子量为2000～2500，聚己内酯二元醇的重均分子量为3000～3500，聚碳酸酯二元醇的重均分子量为3000～3500；
小分子二元醇包括1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A，1,4-丁二醇、1,4-环己烷二甲醇以及羟乙基化双酚A的重量比为1：0.3：0.1；
含羟基丙烯酸酯单体为羟基丙烯酸甲酯；异氰酸酯为六亚甲基二异氰酸酯；
柔性透明膜层材料为PVC膜；
所述多涂层辐射固化预涂装膜的制备方法同实施例1。
实施例4
本发明的实施例4提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，所述柔性透明膜层1与辐射固化涂层3之间没有设置一层用于对柔性透明膜层1表面进行预处理的预处理层2。
实施例5
本发明的实施例5提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，预处理层2的制备原料包括0份两官能度聚氨酯丙烯酸酯树脂、3份氯醋树脂、35份两官能度丙烯酸酯单体、40份溶剂以及0.5份引发剂。
实施例6
本发明的实施例6提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，预处理层2的制备原料包括25份两官能度聚氨酯丙烯酸酯树脂、3份氯醋树脂、35份两官能度丙烯酸酯单体、40份溶剂以及0.5份引发剂。
实施例7
本发明的实施例7提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，按重量份计，预处理层2的制备原料包括6份两官能度 聚氨酯丙烯酸酯树脂、0份氯醋树脂、35份两官能度丙烯酸酯单体、40份溶剂以及0.5份引发剂。
实施例8
本发明的实施例8提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，所述辐射固化弹性耐磨底漆层312的底层没有设置辐射固化弹性附着底漆层311。
实施例9
本发明的实施例9提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，辐射固化弹性附着底漆层311的制备原料包括0份两官能度聚氨酯丙烯酸酯树脂、30份两官能度丙烯酸酯单体、13份单官能度丙烯酸酯以及3份引发剂。
实施例10
本发明的实施例10提供一种多涂层辐射固化预涂装膜，其具体实施方式同实施例1，不同之处在于，辐射固化弹性附着底漆层311的制备原料包括15份两官能度聚氨酯丙烯酸酯树脂、30份两官能度丙烯酸酯单体、13份单官能度丙烯酸酯以及3份引发剂。
性能评估
将实施例所得预涂装膜层材料以及SPC基板加热到175℃，通过钢辊压5s，冷却成型，即得复合材料。
1.附着力测试：将实施例1～10所得预涂装膜制备的复合材料按照ASTM D3359标准测定材料的附着力，测试结果见表1；
2.PVC预涂膜加工性能测试：观察实施例1～10所得预涂装膜制备的复合材料过程中PVC预涂膜是否出现开裂的问题，每个实施例对应100个样品，计算开裂的概率，测试结果见表1。
表1 性能测试结果
  附着力 开裂(％)
实施例1 5B 0
实施例2 5B 2
实施例3 5B 1
实施例4 2B 42
实施例5 4B 36
实施例6 4B 16
实施例7 3B 9
实施例8 4B 59
实施例9 4B 39
实施例10 4B 12
由实验结果可知，本发明利用附着底层以及弹性底层以配合PVC柔性膜材料，提高PVC预涂装膜层在基板表面的附着力，同时有利于在高温条件下也可保持较好的加工型，不会造成发白、开裂、变黄等问题。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种多涂层辐射固化预涂装膜，其特征在于，由下至上依次包括柔性透明膜层(1)与辐射固化涂层(3)，所述辐射固化涂层(3)由下至上依次包括辐射固化弹性底漆层(31)和辐射固化耐磨面漆层(32)，所述辐射固化弹性底漆层(31)和辐射固化耐磨面漆层(32)均至少设置一层，所述辐射固化弹性底漆层(31)由下至上依次包括辐射固化弹性耐磨底漆层(312)和辐射固化弹性哑光/亮光底漆层(313)。
  2. 根据权利要求1所述的多涂层辐射固化预涂装膜，其特征在于，所述柔性透明膜层(1)与辐射固化涂层(3)之间设有一层用于对柔性透明膜层(1)表面进行预处理的预处理层(2)。
  3. 根据权利要求1或2所述的多涂层辐射固化预涂装膜，其特征在于，所述辐射固化弹性耐磨底漆层(312)的底层设有辐射固化弹性附着底漆层(311)。
  4. 根据权利要求2或3所述的多涂层辐射固化预涂装膜，其特征在于，按重量份计，预处理层(2)的制备原料包括2～10份两官能度聚氨酯丙烯酸酯树脂、0～5份氯醋树脂、30～40份两官能度丙烯酸酯单体、30～50份溶剂以及0-1份的引发剂。
  5. 根据权利要求3所述的多涂层辐射固化预涂装膜，其特征在于，按重量份计，辐射固化弹性附着底漆层(311)的制备原料包括30～60份两官能度聚氨酯丙烯酸酯树脂、20～40份两官能度丙烯酸酯单体、10～15份单官能度丙烯酸酯以及0～5份引发剂。
  6. 根据权利要求5所述的多涂层辐射固化预涂装膜，其特征在于，单官能度丙烯酸酯选自丙烯酸异冰片酯、丙烯酰吗啉，甲基丙烯酸羟乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸月桂酯、丙烯酸硬脂酸酯、丙烯酸异丙酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、乙氧基乙基丙烯酸酯中的任一种或多种的组合。
  7. 根据权利要求4或5所述的多涂层辐射固化预涂装膜，其特征在于，两官能度聚氨酯丙烯酸酯树脂的相对分子量大于3000；优选地，两官能度聚氨酯丙烯酸酯树脂的制备原料包括多元醇、异氰酸酯以及含羟基丙烯酸酯单体；其中，多元醇与异氰酸酯的摩尔比为1：2～5。
  8. 根据权利要求7所述的多涂层辐射固化预涂装膜，其特征在于，多元醇包括 A组分多元醇与B组分多元醇，A组分的相对分子量为500～10000；B组分的相对分子量为450～30；优选地，A组分与B组分的摩尔比为(1～3)：1。
  9. 根据权利要求7或8所述的多涂层辐射固化预涂装膜，其特征在于，A组分多元醇的分子式为OH-R 3-COO-R 1-COO-R 2-OH，且R 3、R 1、R 2选自任意基团；优选地，B组分多元醇选自1,4-丁二醇、1,4-环己烷二甲醇、羟乙基化双酚A、乙二醇、丙二醇、己二醇、对苯二醇、新戊二醇、二乙二醇中的任一种或多种的组合。
  10. 一种含有如权利要求1～9任一项所述多涂层辐射固化预涂装膜的复合材料。
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