WO2021057804A1 - 用于塑料基材的阳离子固化组合物、涂料、塑料制品及应用 - Google Patents

用于塑料基材的阳离子固化组合物、涂料、塑料制品及应用 Download PDF

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WO2021057804A1
WO2021057804A1 PCT/CN2020/117189 CN2020117189W WO2021057804A1 WO 2021057804 A1 WO2021057804 A1 WO 2021057804A1 CN 2020117189 W CN2020117189 W CN 2020117189W WO 2021057804 A1 WO2021057804 A1 WO 2021057804A1
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curing composition
cationic curing
weight
group
plastic substrates
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PCT/CN2020/117189
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English (en)
French (fr)
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钱彬
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常州格林感光新材料有限公司
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Priority to JP2022519714A priority Critical patent/JP7350162B2/ja
Priority to US17/764,558 priority patent/US20220396677A1/en
Priority to EP20866978.8A priority patent/EP4036124A4/en
Publication of WO2021057804A1 publication Critical patent/WO2021057804A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters

Definitions

  • the present invention relates to the field of light curing, in particular to a cationic curing composition, coating, plastic product and application for plastic substrate.
  • plastics there are many types of plastics on the market. According to their uses, they can be divided into general plastics and engineering plastics; according to their chemical composition, they can be divided into polystyrene (PS), polymethylmethacrylate (PMMA), polypropylene (PP), polycarbonate (PC), polyethylene (PE), and polyethylene terephthalate (PET), etc.
  • PS polystyrene
  • PMMA polymethylmethacrylate
  • PP polypropylene
  • PC polycarbonate
  • PE polyethylene
  • PET polyethylene terephthalate
  • plastic substrates Due to its low price, plastic substrates can be widely used in vehicles, home appliances, construction, and industry. However, because plastic substrates will produce various surface defects after processing and molding and the surface is easily damaged in the downstream application process, a layer of thermosetting or photocurable coating is usually applied to the surface of the plastic substrate to harden the surface of the substrate. deal with.
  • the existing literature provides a coating composition, which can be applied to a plastic substrate to solve the problem of the substrate's scratch resistance and poor hardness.
  • Another existing document provides a coating composition for plastic substrates, which solves the problems of poor adhesion, abrasion resistance and weather resistance of coatings applied to plastic substrates.
  • the above two coating compositions have poor flexibility, especially when applied in the blister packaging industry, the coatings need to have higher flexibility.
  • the main purpose of the present invention is to provide a cationic curing composition for plastic substrates, coatings, plastic products and applications, so as to solve the problems of poor flexibility and adhesion of existing coatings when applied to plastic substrates.
  • a cationic curing composition for plastic substrates includes: polyhydroxy resin (A), epoxy compound ( B), oxetanyl group-containing compound (C) and cationic initiator (D), wherein the polyhydroxy resin (A) is polyester resin (A1), acrylic resin (A2) and/or phenol resin (A3) ), the molar ratio of the hydroxyl group, the three-membered epoxy group and the four-membered epoxy group in the cationic curing composition is 1:(3-20):(1-25).
  • the molar ratio of the hydroxyl group, the three-membered epoxy group and the four-membered epoxy group is 1:(3-10):(5-15).
  • the cationic curing composition for plastic substrates includes: (5-40) parts by weight of polyhydroxy resin (A), (10-65) parts by weight of epoxy compound (B), (10 parts by weight) ⁇ 70) parts by weight of the oxetanyl group-containing compound (C) and (0.5-10) parts by weight of the cationic initiator (D).
  • the cationic curing composition for plastic substrates includes: (5-30) parts by weight of polyhydroxy resin (A), (15-50) parts by weight of epoxy compound (B), (20) ⁇ 60) parts by weight of the oxetanyl group-containing compound (C) and (2-5) parts by weight of the cationic initiator (D).
  • the hydroxyl value of the polyester resin (A1) is 50 to 500 mgKOH/g, and the number average molecular weight is 200 to 12000; preferably, the hydroxyl value of the polyester resin (A1) is 80 to 350 mgKOH/g, and the number average molecular weight is 300 ⁇ 5000.
  • the acrylic resin (A2) has a hydroxyl value of 15 to 200 mgKOH/g, a glass transition temperature of 10 to 150°C, and a number average molecular weight of 500 to 20000; preferably, the acrylic resin (A2) has a hydroxyl value of 50 to 150mgKOH/g, glass transition temperature is 20-100 °C, number average molecular weight is 1000-8000.
  • the phenolic resin (A3) has a hydroxyl value of 50 to 300 mgKOH/g, and a number average molecular weight of 300 to 15000; preferably, the phenolic resin (A3) has a hydroxyl value of 100 to 250 mgKOH/g and a number average molecular weight of 500 to 8000.
  • the epoxy compound (B) is selected from alicyclic epoxy compounds and/or aliphatic epoxy compounds; preferably, the epoxy equivalent of the alicyclic epoxy compound is 80-500; preferably, the alicyclic epoxy compound The epoxy equivalent of the oxygen compound is 80-500.
  • the cationic curing composition for the plastic substrate further includes (0-40) parts by weight of the auxiliary agent (E); preferably, the cationic curing composition for the plastic substrate includes (1 to 10) Parts by weight of auxiliary agent (E); preferably, auxiliary agent (E) is selected from sensitizers, color materials, flame retardants, leveling agents, curing accelerators, light/heat acid generators, and adhesion promoters , UV absorbers, anti-agglomeration agents, thickeners, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, One or more of the group consisting of light stabilizer, compatibilizer, coloring agent, stabilizer, release agent, antistatic agent, defoamer and fire-resistant agent.
  • Another aspect of the present application also provides a coating, which includes the above-mentioned cationic curing composition for plastic substrates.
  • Another aspect of the present application also provides a plastic product, including a plastic substrate and a coating.
  • the coating is coated on at least a part of the plastic substrate.
  • the coating is composed of the above-mentioned cation curing composition for the plastic substrate. Cured to form.
  • Another aspect of the present application also provides an application of the above-mentioned cationic curing composition for plastic substrates in the field of energy curing.
  • the polyhydroxy resin (A), the epoxy compound (B) and the oxetanyl group-containing compound (C) can undergo a curing reaction to form a coating Floor.
  • the addition of epoxy compound (B) and oxetanyl group-containing compound (C) is beneficial to increase the curing speed of the coating, and the addition of polyhydroxy resin (A) increases the crosslinking density, which is beneficial to improve the coating.
  • the adhesion on the metal substrate and the addition of the oxetanyl group-containing compound (C) are beneficial to improve the compatibility of the components.
  • Limiting the molar ratio of the hydroxyl group, the three-membered epoxy group and the four-membered epoxy group in the above-mentioned cationic curing composition within the above range can greatly improve the adhesion, flexibility, and film formation of the coating on the plastic substrate. Properties and curing speed.
  • the cationic curing composition for plastic substrates includes: polyhydroxy resin (A), epoxy compound (B), and Oxetanyl compound (C) and cationic initiator (D), wherein the polyhydroxy resin (A) is polyester resin (A1), acrylic resin (A2) and/or phenol resin (A3), cation curing
  • the molar ratio of the hydroxyl group, the three-membered epoxy group and the four-membered epoxy group in the composition is 1:(3-20):(1-25).
  • the polyhydroxy resin (A), the epoxy compound (B) and the oxetanyl group-containing compound (C) can undergo a curing reaction to form a coating.
  • the addition of epoxy compound (B) and oxetanyl group-containing compound (C) is beneficial to increase the curing speed of the coating, and the addition of polyhydroxy resin (A) increases the crosslinking density, which is beneficial to improve the coating.
  • the adhesion on the metal substrate and the addition of the oxetanyl group-containing compound (C) are beneficial to improve the compatibility of the components.
  • Limiting the molar ratio of the hydroxyl group, the three-membered epoxy group and the four-membered epoxy group in the above-mentioned cationic curing composition within the above range can greatly improve the adhesion, flexibility, and film formation of the coating on the plastic substrate. Properties and curing speed.
  • the hydroxyl group, the three-membered epoxy group and the four-membered epoxy in the cationic curing composition used for the plastic substrate, the hydroxyl group, the three-membered epoxy group and the four-membered epoxy
  • the molar ratio of the groups is 1:(3 ⁇ 10):(5 ⁇ 15).
  • the cationic curing composition for the plastic substrate comprises: (5-40) parts by weight of polyhydroxy resin (A), (10-65) parts by weight of epoxy compound (B), (10 to 70) parts by weight of the oxetanyl group-containing compound (C), and (0.5 to 10) parts by weight of the cationic initiator (D).
  • the amount of each component in the above-mentioned cationic curing composition includes but is not limited to the above-mentioned range, and limiting it to the above-mentioned range can further exert the coordination and synergistic effect of each component, thereby further improving the adhesion of the coating formed by it. , Flexibility, etc.
  • the cationic curing composition used for the plastic substrate comprises: (5-30) parts by weight of polyhydroxy resin (A), (15-50) parts by weight of epoxy compound (B), ( 20-60) parts by weight of the oxetanyl group-containing compound (C) and (2-5) parts by weight of the cationic initiator (D).
  • the polyhydroxy resin (A) is at least one selected from the group consisting of polyester resin (A1), acrylic resin (A2), and phenol resin (A3), and may also be a mixture of two or more.
  • the polyester resin (A1) of the present application is prepared by polycondensation of polybasic acid and polyhydric alcohol.
  • the polycondensation reaction is carried out in an inert atmosphere at a temperature of 100 to 260°C, preferably 130 to 220°C.
  • Polyacids refer to compounds containing multiple carboxyl groups directly connected to hydrocarbon groups in the molecule, and can be divided into aliphatic acids, alicyclic acids, and aromatic acids.
  • the polybasic acid includes, but is not limited to, adipic acid, 1,4-cyclohexanedicarboxylic acid, fumaric acid, sebacic acid, maleic anhydride, phthalic acid, and terephthalic acid.
  • Dicarboxylic acid isophthalic acid, trimellitic anhydride, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, dichlorophthalic acid and tetrachlorophthalic acid and One or more of the group consisting of phthalic anhydride.
  • the above-mentioned polybasic acid includes, but is not limited to, adipic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. One or more.
  • Polyols refer to compounds containing multiple hydroxyl groups directly connected to aliphatic carbon chains in the molecule.
  • the above-mentioned polyols include but are not limited to ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butane Glycol, 2,3-butanediol, di- ⁇ -hydroxyethylbutanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, decanediol, Dodecanediol, neopentyl glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, methyl propylene glycol, neopentyl glycol hydroxy-tert-valerate, ethyl butyl prop
  • the hydroxyl value of the polyester resin (A1) is 50-500 mgKOH/g. Compared with other hydroxyl values, limiting the hydroxyl value of the polyester resin (A1) to the above range is beneficial to improve the adhesion, processability and crosslinking density of the coating to the plastic substrate, thereby helping to suppress attribution Embrittlement of the enthalpy-relaxed paint film during curing. More preferably, the hydroxyl value of the polyester resin (A1) is 80 to 350 mgKOH/g.
  • the number average molecular weight of the polyester resin (A1) is 200 to 12,000. Compared with other ranges, limiting the molecular weight of the polyester resin (A1) to the above range is beneficial to increase the strength of the coating and facilitate the coating operation. More preferably, the number average molecular weight of the above-mentioned polyester resin is 300-5000.
  • the acrylic resin (A2) described in the present application refers to a polymer formed by copolymerization of acrylates or methacrylates and other olefinic monomers.
  • at least one of the (meth)acrylates or other ethylenic monomers is a functional monomer containing a hydroxyl group, and the functional monomer containing a hydroxyl group preferably has the following structure:
  • R 0 is H, or CH 3 ;
  • R is a C 2 -C 10 linear or branched alkyl alcohol.
  • the above-mentioned functional monomer containing hydroxyl group is selected from the group consisting of hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, methyl
  • the functional monomer without hydroxyl is selected from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, and propyl methacrylate.
  • the hydroxyl value of the acrylic resin (A2) is 15-200 mgKOH/g.
  • the hydroxyl value of the acrylic resin (A2) of the present application within the above range is beneficial to further improve the adhesion, processability and crosslinking density of the coating formed by it to the plastic substrate, and thus is beneficial to inhibit the return.
  • the acrylic resin (A2) has a hydroxyl value of 50 to 150 mgKOH/g.
  • the glass transition temperature (Tg) of the acrylic resin (A2) is 10-150°C. Compared with other ranges, limiting the glass transition temperature of the acrylic resin (A2) to the above range is beneficial to improve its compatibility with other components in the composition, thereby increasing the composition of the above-mentioned cationic curable composition. Membranous. More preferably, the glass transition temperature (Tg) of the acrylic resin (A2) is 20 to 100°C.
  • the number average molecular weight of the above-mentioned acrylic resin (A2) is 500 to 20,000. Compared with other ranges, the molecular weight of acrylic resin in the above range is beneficial to increase the strength of the coating. More preferably, the number average molecular weight of the above-mentioned acrylic resin (A2) is 1,000 to 8,000.
  • the phenolic resin (A3) used in this application may be a phenolic resin obtained by a condensation reaction of a phenolic compound and an aliphatic aldehyde compound under acidic or alkaline conditions.
  • the phenolic compound is phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol , P-butylphenol, p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol, bisphenol A, p-phenylphenol, 2,3-xylenol, 2,4-xylenol, 2,5 -Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol
  • the phenolic compound is phenol, hydroquinone, p-tert-octylphenol, p-nonylphenol, bisphenol A, p-phenylphenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol and One or more of ⁇ -naphthol.
  • the aliphatic aldehyde compound is an aldehyde containing C1 to C8, which may include: formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, acrolein, butyraldehyde, 2-butenal, valeraldehyde, trimethyl acetaldehyde aldehyde.
  • the phenolic resin (A3) used in this application can also be an epoxy-modified phenolic resin, and there is no limitation on the modification method.
  • the phenolic resin (A3) has a hydroxyl value of 50 to 300 mgKOH/g, more preferably 100 to 250 mgKOH/g.
  • the number average molecular weight of the phenol resin used in the present application is 300 to 15,000, and more preferably 500 to 8,000.
  • the epoxy compound of the present invention is preferably an alicyclic epoxy compound and an aliphatic epoxy compound.
  • the alicyclic epoxy compound can be obtained by epoxidizing a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent, or a polyglycidyl etherate of a polyhydric alcohol having at least one alicyclic ring.
  • the compound containing epoxycyclohexane or epoxycyclopentane can be obtained by epoxidizing a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent, or a polyglycidyl etherate of a polyhydric alcohol having at least one alicyclic ring.
  • the alicyclic epoxy compound is preferably a compound having an epoxy equivalent of 80 to 500.
  • alicyclic epoxy compound commercially available products such as CELLOXIDE2021P, CELLOXIDE 2081, CELLOXIDE 2000, and CELLOXIDE 3000 (manufactured by Daicel Corporation) can be used.
  • the aforementioned aliphatic epoxy compound refers to an epoxy compound that is not classified as an aromatic epoxy compound or an alicyclic epoxy compound.
  • examples include glycidyl etherate of aliphatic alcohol, glycidyl ester of alkyl carboxylic acid, etc.
  • Multifunctional epoxy compounds such as monofunctional epoxy compounds, polyglycidyl ether products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyl esters of aliphatic long-chain polybasic acids.
  • Representative compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol diglycidyl ether.
  • Ether 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, poly Glycidyl ether of polyhydric alcohols such as diglycidyl ether of ethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin by adding one or more types Polyglycidyl etherate of polyether polyol and diglycidyl ester of aliphatic long-chain dibasic acid obtained from alkylene oxide.
  • the monoglycidyl ether of aliphatic higher alcohols or the glycidyl esters of higher fatty acids epoxidized soybean oil, epoxy octyl stearate, epoxy butyl stearate, epoxidized soybean oil, cyclic Oxidized polybutadiene and so on.
  • the aliphatic epoxy compound is preferably a compound having an epoxy equivalent of 80 to 500.
  • the above-mentioned aliphatic epoxy compounds can be commercially available products, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX- 314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX- 810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX- 941, Denacol EX-920, Denacol EX-9
  • the curing speed of the composition can be accelerated when the oxetanyl group and the epoxy group are contained at the same time.
  • the presence of the oxetanyl group also improves the flexibility of the paint film made of the composition, so that the plastic products are not prone to cracking and damage during the subsequent processing.
  • the oxetanyl group-containing compound (C) can be polymerized or crosslinked by light irradiation.
  • the oxetanyl group-containing compound may contain one or more oxetanyl groups.
  • the oxetanyl group-containing compound (C) contains an oxetanyl group, and the structural formula is as shown in formula (1):
  • R 1 is selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (such as methyl, ethyl, propyl or butyl) or an aryl group having 6 to 18 carbon atoms (such as phenyl and naphthyl, Furyl or thienyl);
  • R 2 is selected from a hydrogen atom, an epoxy group, an alkyl group having 1 to 6 carbon atoms (such as methyl, ethyl, propyl and butyl), having 6 to 18 carbon atoms
  • Aryl groups such as phenyl, naphthyl and anthracenyl
  • substituted or unsubstituted aralkyl groups with 7 to 18 carbon atoms such as benzyl, fluorobenzyl, methoxybenzyl, benzene Ethyl, styryl, cinnamyl, or ethoxybenzyl
  • groups with other aromatic rings such as aryloxyalky
  • the compound (C) containing only one oxetanyl group in the molecule is selected from 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3 -Ethyloxetane, (3-ethyl-3-oxetanylmethoxy) toluene, (3-ethyl-3-oxetanylmethoxy)benzene, 4-methoxy-( 1-(3-Ethyl-3-oxetanylmethoxy)methyl)benzene, (1-(3-ethyl3-oxetanylmethoxy)ethyl)phenyl ether, isobutoxymethyl (3-Ethyl-3-oxetanyl methyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanyl methyl) ether, ethyl diethylene glycol (3-ethyl- 3-oxetanyl methyl)
  • the oxetanyl group-containing compound (C) contains two oxetanyl ring groups, and the structural formula is as shown in formula (2):
  • R 1 is the same as defined in the above formula (1);
  • R 3 is selected from linear or branched alkylene having 1-20 carbon atoms (such as ethylene, propylene or butylene), linear or branched polyalkylene having 1-20 carbon atoms (Alkyleneoxy) (such as poly(ethyleneoxy) or poly(propyleneoxy)), linear or branched unsaturated hydrocarbon groups (such as 1,3-propylene, methyl 1,3- Propylene or butylene).
  • alkylene having 1-20 carbon atoms such as ethylene, propylene or butylene
  • Alkyleneoxy such as poly(ethyleneoxy) or poly(propyleneoxy)
  • linear or branched unsaturated hydrocarbon groups such as 1,3-propylene, methyl 1,3- Propylene or butylene.
  • R 3 is selected from the multivalent groups represented by the following formulas (3) and (4):
  • R 4 is selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (such as a chlorine atom or a bromine atom), a nitro group, a cyano group, a mercapto group, a carboxyl group or an amino group Formyl, where x is any integer from 0 to 4.
  • R 5 represents an oxygen atom, a sulfur atom, a methylene group, -NH-, -SO-, -SO 2 -, -C(CF 3 ) 2 -or -C(CH 3 ) 2 -.
  • the oxetanyl group-containing compound (C) contains two oxetanyl groups, and the structural formula is as shown in (5):
  • R 1 has the same expression as the above formula (1).
  • R 1 has the same definition as in the above molecular formula (1);
  • R 6 is selected from an organic group with a valence of 3-10.
  • the compound containing two or more oxetanyl groups in the molecule is selected from 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-( 1,3-(2-methylene(methylenyl))propanediylbis(oxymethylene)bis-(3-ethyloxetane), 1,4-bis[(3-ethyl- 3-oxetanylmethoxy)methyl]benzene, 1,2-bis((3-ethyl-3-oxetanylmethoxy)methyl)ethane, 1,3-bis(3-ethane -Oxetanyl methoxy) methyl) propane, ethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyl bis(3-ethyl-3-oxa) Cyclobutyl methyl) ether, triethylene glycol bis(3-ethyl-3-oxa)
  • the oxetane is selected from the components defined by formula (1), wherein R 1 is a hydrogen atom, a C 1 -C 4 alkyl group; Z is an oxygen atom; R 2 is a hydrogen atom, an epoxy group , C 1 ⁇ C 4 alkyl group, or phenyl group.
  • the prepared paint film is flexible and has good adhesion to plastic substrates.
  • the cationic initiator is a compound capable of generating cations or Lewis acid under irradiation of active energy rays such as ultraviolet rays and electron rays, and capable of initiating polymerization of cationic curable components such as epoxy compounds and oxetanyl-containing compounds.
  • the cationic initiator (D) can be of the type commonly used in the art.
  • it is one or two of iodonium salt, sulfonium salt, or aryl ferrocene salt.
  • iodonium salt and/or sulfonium salt photoinitiators are more preferred, and compounds having the structure represented by the following general formula are particularly preferred :
  • R 7 and R 8 are each independently selected from hydrogen, C 1 ⁇ C 20 linear or branched alkyl, C 4 ⁇ C 20 cycloalkylalkyl or alkylcycloalkyl, C 6 to C 20 substituted or unsubstituted aryl groups, and the acyclic -CH 2 -in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;
  • R 9 is selected from C 6 ⁇ C 20 substituted or unsubstituted aryl groups, C 6 ⁇ C 20 substituted or unsubstituted alkyl aryl groups, C 1 ⁇ C 20 linear or branched alkyl groups, C 4 ⁇ C 20 cycloalkyl alkyl or alkyl cycloalkyl, substituted or unsubstituted phenylthio phenyl, and the non-cyclic -CH 2 -in these groups may optionally be carbonyl, -O-, -S- or 1,4-phenylene substituted;
  • R 10 and R 11 are each independently selected from alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, Aryl, heterocyclic hydrocarbon, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, hydroxy(poly)alkyleneoxy, substitutable amino, cyano , Nitro group or halogen atom, m 1 and m 2 are each independently selected from an integer of 0-4;
  • a - is independently selected from X -, ClO 4 -, CN -, HSO 4 -, NO 3 -, CF 3 COO -, (BX 4) -, (SbX 6) -, (AsX 6) -, (PX 6) -, Al [OC ( CF 3) 3] 4 -, sulfonate ion, B (C 6 X 5) 4 - , or [(Rf) b PF 6- b] -, wherein, X is halogen, R f It represents an alkyl group in which ⁇ 80% of hydrogen atoms are replaced by fluorine atoms, b represents an integer of 1 to 5, and b R f groups are the same or different from each other.
  • R 7 and R 8 are each independently selected from hydrogen, C 1 ⁇ C 12 linear or branched alkyl, C 4 ⁇ C 10 cycloalkylalkyl or alkylcycloalkyl, C 6 ⁇ C 12 Substituted or unsubstituted aryl groups, and the acyclic -CH 2 -in these groups can be optionally substituted by -O-, -S- or 1,4-phenylene;
  • R 9 is selected from C 6 -C 10 substituted or unsubstituted aryl groups, C 6 -C 10 substituted or unsubstituted alkylaryl groups, substituted or unsubstituted phenylthiophenyl groups, and among these groups
  • R 10 and R 11 are each independently selected from C 1 to C 10 linear or branched alkyl, C 1 to C 10 linear or branched alkoxy, C 1 to C 10 alkylcarbonyl or halogen .
  • the cationic part of the cationic initiator (D) is selected from one or more of the following structures:
  • the cationic initiator (D) is an anionic moiety is selected from Cl -, Br -, PF 6 -, SbF 6 -, AsF 6 -, BF 4 -, C 4 F 9 SO 3 - , B (C 6 H 5) 4 -, C 8 F 17 SO 3 -, CF 3 SO 3 -, Al [OC (CF 3) 3] 4 -, (CF 3 CF 2) 2 PF 4 -, (CF 3 CF 2) 3 PF 3 - , [(CF 3) 2 CF 2] 2 PF 4 -, [(CF 3) 2 CF 2] 3 PF 3 -, [(CF 3) 2 CFCF 2] 2 PF 4 - or (CF 3) 2 CFCF 2] 3 PF 3 -.
  • cationic initiators with similar structures can also be used in the photoinitiator (D) of the present invention, such as those in Changzhou Qiangli Electronic New Materials Co., Ltd. produced PAG20001, PAG20002, PAG30201, PAG30101, and Irgacure250 produced by BASF. One or more.
  • the above-mentioned compounds may be used alone, or a combination of two or more may be used.
  • the above cationic curing composition also includes auxiliary (E), which includes but is not limited to sensitizers, color materials, flame retardants, leveling agents, curing agents Accelerators, light/thermal acid generators, adhesion promoters, UV absorbers, anti-agglomeration agents, thickeners, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, One or more of the group consisting of antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, stabilizers, release agents, antistatic agents, defoamers and refractory agents. More preferably, the cationic curing composition includes (0-40) parts by weight of the auxiliary agent (E) in parts by weight, and further preferably (1-10) parts by weight of the auxiliary agent (E).
  • a sensitizer can be optionally added to the above-mentioned cationic curable composition.
  • the addition of the sensitizer is beneficial to further improve the sensitivity of the composition, or to meet the light curing requirements of long-wavelength light sources, especially UV-LEDs.
  • the aforementioned sensitizer includes, but is not limited to, one or more of the group consisting of thioxanthone compounds, xanthone compounds, acridine compounds, anthracene compounds and coumarin compounds, It is more preferably an anthracene compound and/or a thioxanthone compound.
  • JRCure-1105 IX
  • JRCure-1106 DETX
  • PSS303, PSS510, PSS513, PSS515, PSS519, etc. produced by Changzhou Qiangli Electronic New Materials.
  • the sensitizer can also be selected from compounds containing the following structures:
  • the added amount of the sensitizer is 0 to 0.1 times the total weight of component A, component B, component C and component D, preferably 0.005 to 0.06 times.
  • the cationic curable composition of the present invention can optionally add color materials, wherein the color materials include one or more of the group consisting of pigments, colorants, dyes and natural pigments.
  • the blue pigment or the cyan pigment is preferably pigment blue (Pigment Blue) 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60; as green pigments, Pigment Green 7, 26, 36, and 50 can be cited.
  • the red pigment or magenta pigment is preferably Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 19, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, iron oxide, etc.; as purple pigments, pigment violet (Pigment Violet) 3, 19, 23, 29, 30, 37, 50, 88 can be cited; as orange pigments, pigment orange (Pigment Orange) 13, 16 , 20, 36.
  • the yellow pigment is preferably pigment yellow (Pigment Yellow) 1, 2, 3, 4, 5, 6, 7, 10, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193.
  • Pigment Yellow pigment yellow
  • the yellow pigment is preferably pigment yellow (Pigment Yellow) 1, 2, 3, 4, 5, 6, 7, 10, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193.
  • Black pigments are preferably pigment black (Pigment Black) 7, 28, 26, furnace carbon black, lamp black, acetylene black, channel carbon black; No. 2300, No. 900, MCF88, NO. 33, NO. .40, NO.45, NO.52, MA7, MA8, MA100; Cabot Japan Regal 400R, Regal 300R, Regal 660R, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. Carbon black.
  • the white pigment is preferably Pigment White (Pigment White) 6, 18, 21, titanium oxide, and the like.
  • the added amount of the color material is 0-40%, preferably 1-10% of the total weight of component A, component B, component C and component D.
  • the average particle diameter of the color material is not particularly limited, and can be appropriately selected according to the intended application.
  • the above-mentioned cationic curable composition further includes a dispersing monomer and/or a dispersing aid.
  • the content of the dispersing aid is 30 to 80 parts by weight, and the sum of the weight fraction of the dispersing monomer and the weight fraction of the color material is 100%.
  • a polymer dispersing agent is preferred, and more preferably, the above-mentioned polymer dispersing agent is selected from: DISPERBYK-101/102/103/106/111/161/162/163/ manufactured by BYK Chemie 164/166/167/168/170/171/174/182; EFKA additive system EFKA4010/4046/4080/5010/5207/5244/6745/6750/7414/7462/7500/7570/7575/7580; San Nopco Limited Made by DISPERSE AID 6/8/15/9100; Made by Avecia SOLSPERSE dispersant: SOLSPERSE3000/5000/9000/12000/13240/13940/17000/22000/24000/26000/28000/32000/36000/39000/41000/71000; ADEKA PLURONIC manufactured by Adeka Corporation L31/F38/L42/L44/L61/L64/F68/L72/P95/F77/
  • Another aspect of the present application also provides a coating, which includes the above-mentioned cationic curing composition.
  • the polyhydroxy resin (A), the epoxy compound (B) and the oxetanyl group-containing compound (C) can undergo a curing reaction to form a coating.
  • the addition of epoxy compound (B) and oxetanyl group-containing compound (C) is beneficial to increase the curing speed of the coating, and the addition of polyhydroxy resin (A) increases the crosslinking density, which is beneficial to improve the coating.
  • the adhesion on the metal substrate and the addition of the oxetanyl group-containing compound (C) are beneficial to improve the compatibility of the components.
  • the coating formed by the coating containing the cationic curing composition has the advantages of strong adsorption, good flexibility and film-forming properties, and fast curing speed.
  • the cationic curing composition After the cationic curing composition is coated on the plastic substrate, it is cured with actinic radiation to form a film.
  • Actinic radiation is light having electromagnetic radiation wavelengths ranging from the ultraviolet range to the visible range to the infrared range.
  • the actinic radiation that can be used to cure the cationic curing composition of the present invention usually has a radiation wavelength in the range of 150 to 2000 nm, preferably a radiation wavelength in the range of 200 to 600 nm, depending on the type of cationic polymerization initiator in the composition. And so on, appropriately choose the radiation source with high sensitivity wavelength to use.
  • Suitable ultraviolet light sources may include mercury arcs, carbon arcs, low, medium or high pressure mercury lamps, vortex plasma arcs and ultraviolet light emitting diodes.
  • the preferred ultraviolet light sources are medium pressure mercury lamps.
  • the radiation dose of the paint film is 10 to 1000 mJ/cm 2 , preferably 50 to 500 mJ/cm 2 .
  • the paint film can be heated as needed to reduce unreacted substances in the paint film and alleviate the strain of the paint film caused by actinic radiation and molding processing.
  • the heating process can sometimes improve the hardness and adhesion of the paint film.
  • the temperature of the heating process is 150-250°C, and the heating time is 1-30 min.
  • the cationic curing composition provided in the present application can be applied in the field of energy curing, and is particularly suitable for application on plastic substrates.
  • the cationic curing composition provided in this application is suitable for coating on plastic substrates.
  • the plastic substrate used in the present invention may be a conventional plastic substrate in the field, and there is no particular limitation.
  • the plastic substrate of the present invention may include polystyrene (PS), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polyurethane (PUR), Glass fiber reinforced unsaturated polyester, polymethyl methacrylate (PMMA), polyphenylene sulfide (PPS), polyoxymethylene (POM), polyphenylene oxide (PPO), polyurea, polybutylene terephthalate Alcohol ester (PBT), polyethylene terephthalate (PET), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), nylon, ethylene-propylene-diene Copolymer (EPDM) modified polypropylene, etc., can also be the plastic substrate of the above-mentioned plastic mixture. If
  • Another aspect of the present application also provides a plastic product, comprising a plastic substrate and a coating layer coated on at least a part of the above-mentioned plastic substrate, and the coating layer is formed by curing the above-mentioned cation curing composition for the plastic substrate .
  • the cationic curing composition can be coated on the plastic substrate by conventional methods, which include, but are not limited to, brushing, roller coating, dipping, pouring, spraying, and the like. It is possible to coat the entire surface of the plastic substrate, or only a part of it.
  • the thickness of the coating film can be appropriately selected according to the application. Generally, the thickness of the dry coating film is about 2 to 20 microns, more preferably 2 to 8 microns.
  • Polyester resin (A1-1) PCL210, hydroxyl value: 109 ⁇ 119mgKOH/g (Japan Daicel Co., Ltd.);
  • Phenolic resin (A3-1) F51, epoxy value: 0.51 (hydroxyl value: about 150mgKOH/g) (Changzhou Xiangyang New Materials Co., Ltd.); phenolic resin (A3-2): E44, epoxy value: 0.44 (hydroxyl Value: about 210mgKOH/g) (Miki 6101).
  • D2 Diphenyliodonium hexafluoroantimonate (Changzhou Qiangli PAG30202);
  • E2 Leveling agent BYK307 (BYK, Germany);
  • the components are pre-mixed uniformly according to the formulas shown in Tables 1 and 2, and then dispersed at a high speed for 30 minutes at a speed of 1500-2000 rpm using a mixer to make them evenly mixed. After filtering through a filter, the mixture is prepared. Color cationic curing composition.
  • Tables 1 and 2 are parts by weight of each component, and the unit is g.
  • the number in parentheses indicates the amount of the substance containing functional groups in the corresponding substance, and the unit is mol.
  • Example 1 0.25:1:2.5 1:4:10
  • Example 2 0.25:1:2.5 1:4:10
  • Example 3 0.25:2:2 1:8:8
  • Example 4 0.25:2:2 1:8:8
  • Example 5 0.25:1:2 1:4:8
  • Example 6 0.25:1:2 1:4:8
  • Example 7 0.25:2:3 1:8:12
  • Example 8 0.25:2.5:3.75 1:10:15
  • Example 9 0.25:0.75:1.25 1:3:5
  • Example 10 0.25:2:2 1:8:8
  • Example 11 0.25:0.75:0.25 1:3:1
  • Example 12 0.025:0.5:0.625 1:20:25 Comparative example 1 0.25:0.25:0.25 1:1:1
  • the pigment black is Mitsubishi MA7; the pigment white is Ishihara titanium dioxide R706; the pigment blue is BASF Phthalocyanine Blue 15:3; and the pigment red is Clariant 122.
  • the components are pre-mixed uniformly according to the formula shown in Table 5, and then dispersed at a high speed for 30 minutes at a speed of 1500-2000 rpm using a blender to make it evenly mixed. After filtering through a filter, a colored cation curing combination is prepared. Things.
  • the formula shown in Table 5 is the weight part of each component, and the unit is g.
  • the number in parentheses indicates the amount of the substance containing functional groups in the corresponding substance, and the unit is mol.
  • Example 13 0.25:2:2 1:8:8
  • Example 14 0.25:1:2.5 1:4:10
  • Example 15 0.25:1:2 1:4:8
  • Example 16 0.25:2:3 1:8:12
  • Example 17 0.25:2:3 1:8:12
  • Example 18 0.25:2:2 1:8:8 Comparative example 8 0.25:0.25:0.25 1:1:1
  • the cationic curing compositions shown in Tables 1 to 2 and Table 5 were formed into films and then subjected to performance evaluation tests.
  • Hardness test According to the national standard GB/T6739-86, prepare a set of drawing pencils with a hardness of 6B ⁇ 6H, and measure the pencil hardness of the coating film by manual method. Place the coating film board horizontally on the table, hold the pencil at an angle of 45°, and push on the coating film surface for about 1 cm at a uniform speed, leaving scratches on the coating film. Repeat 5 scratches on the pencil with the same hardness mark. If 2 or more marks are not scratched on the bottom plate of the sample, use a pencil with a hardness mark of one higher than the hardness mark until you find that the coating film is scratched by 2 or more marks. One mark less than the pencil hardness is the pencil hardness of the coating film.
  • Adhesion test Refer to the national standard GB/T9286-1998 to test the adhesion of paint film on PET film or PP film. Use a scribe knife to cut 6 parallel cuts on the coating film, cutting through the entire depth of the coating film; then cut the same 6 times, perpendicular to the former to form many small squares, and then press with a translucent 25mm wide Stick the sensitive tape on the entire cut mark, pull the tape violently, and compare with the standard to determine the grade of adhesion of the coating film.
  • Curing time test referring to the national standard GB/T1728-79, spray the composition on the PET film, and measure the curing time of the composition respectively.
  • VOC test Weigh 0.2g sample and coat it on the weighed PET film, and weigh; solidify the coated sample, cool it at room temperature for 15 minutes, and weigh it; place the coating at 110°C Dry in a ventilated oven for 1 hour, place the coating film in a desiccator to cool to room temperature, and weigh.
  • Total volatile matter% Processing volatile matter%+Potential volatile matter%
  • A is the weight of the PET film, g;
  • B is the weight of the coating film and the PET film, g;
  • Comparing Examples 1 to 12 and Comparative Examples 3-5 it can be seen that the use of the cationic curing composition provided by the present application is beneficial to greatly improving the overall performance of the coating formed by the composition. Comparing Examples 1 to 12 and Comparative Examples 1 to 2, it can be seen that limiting the molar ratio of the hydroxyl group, the three-membered epoxy group and the four-membered epoxy group within the preferred range of this application is beneficial to improve the coating performance. Comprehensive performance: Comparing Examples 13 to 18 and Comparative Examples 6 to 8, it can be seen that the use of the cationic curing composition provided in the present application is beneficial to greatly improve the comprehensive performance of the coating formed.
  • the cationic curing composition of the present invention exhibits excellent flexibility in both colorless and colored systems, has good adhesion to plastic substrates, moderate curing speed, low VOC emissions, and can be widely used In plastic products.

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Abstract

一种用于塑料基材的阳离子固化组合物、包括该组合物的涂料以及该组合物在能量固化领域的应用。阳离子固化组合物包括多羟基树脂、环氧化合物、含氧杂环丁烷基的化合物和阳离子引发剂，多羟基树脂为聚酯树脂、丙烯酸树脂和/或酚醛树脂，阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3~20):(1~25)。一种塑料制品，包括塑料基材和涂层，涂层由阳离子固化组合物固化形成。

Description

用于塑料基材的阳离子固化组合物、涂料、塑料制品及应用 技术领域
本发明涉及光固化领域，具体而言，涉及一种用于塑料基材的阳离子固化组合物、涂料、塑料制品及应用。
背景技术
目前市面上塑料种类繁多，按其用途划分，可分为通用塑料和工程塑料；按其化学组成划分，可分为聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯(PP)、聚碳酸酯(PC)、聚乙烯(PE)、和聚对苯二甲酸乙二醇酯(PET)等。塑料基材由于价格便宜，可被广泛应用于车辆、家电、建筑、及工业等领域中。但塑料基材由于在加工成型后会产生各种表面缺陷且在下游应用过程中表面易损伤，因此通常会在塑料基材表面涂布一层热固性或光固性涂料，对基材表面进行硬化处理。
现有文献提供了一种涂料组合物，其应用在塑料基材上可以解决基材不耐擦伤及硬度差的问题。另一篇现有文献提供了一种塑料基材用涂料组合物，其解决了涂料应用在塑料基材上附着力、耐磨损性和耐候性差的问题。但是上述两种涂料组合物其柔韧性不佳，尤其应用在吸塑包装行业时，需要涂料具有更高的柔韧性。
因此，需要开发出一种柔韧性优异、在塑料基材上附着力佳的涂料组合物，以满足涂料行业发展的需求。
发明内容
本发明的主要目的在于提供一种用于塑料基材的阳离子固化组合物、涂料、塑料制品及应用，以解决现有涂料应用至塑料基材上时存在柔韧性和附着力较差的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种用于塑料基材的阳离子固化组合物，用于塑料基材的阳离子固化组合物包括：多羟基树脂(A)、环氧化合物(B)、含氧杂环丁烷基的化合物(C)和阳离子引发剂(D)，其中多羟基树脂(A)为聚酯树脂(A1)、丙烯酸树脂(A2)和/或酚醛树脂(A3)，阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3～20):(1～25)。
进一步地，用于塑料基材的阳离子固化组合物中，羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3～10):(5～15)。
进一步地，按重量份计，用于塑料基材的阳离子固化组合物包括：(5～40)重量份多羟基树脂(A)、(10～65)重量份环氧化合物(B)、(10～70)重量份含氧杂环丁烷基的化合物(C)和(0.5～10)重量份阳离子引发剂(D)。
进一步地，按重量份计，用于塑料基材的阳离子固化组合物包括：(5～30)重量份多羟基树脂(A)、(15～50)重量份环氧化合物(B)、(20～60)重量份含氧杂环丁烷基的化合物(C)和(2～5)重量份阳离子引发剂(D)。
进一步地，聚酯树脂(A1)的羟值为50～500mgKOH/g，数均分子量为200～12000；优选地，聚酯树脂(A1)的羟值为80～350mgKOH/g，数均分子量为300～5000。
进一步地，丙烯酸树脂(A2)的羟值为15～200mgKOH/g，玻璃化转变温度为10～150℃，数均分子量为500～20000；优选地，丙烯酸树脂(A2)的羟值为50～150mgKOH/g，玻璃化转变温度为20～100℃，数均分子量为1000～8000。
进一步地，酚醛树脂(A3)的羟值为50～300mgKOH/g，数均分子量为300～15000；优选地，酚醛树脂(A3)的羟值为100～250mgKOH/g，数均分子量为500～8000。
进一步地，环氧化合物(B)选自脂环式环氧化合物和/或脂肪族环氧化合物；优选地，脂环式环氧化合物的环氧当量为80～500；优选地，脂肪族环氧化合物的环氧当量为80～500。
进一步地，按重量份计，用于塑料基材的阳离子固化组合物还包括(0～40)重量份助剂(E)；优选地，用于塑料基材的阳离子固化组合物包括(1～10)重量份助剂(E)；优选地，助剂(E)选自增感剂、色材、阻燃剂、流平剂、固化促进剂、光/热产酸剂、粘结促进剂、紫外吸收剂、抗凝聚剂、增稠剂、成核剂、偶联剂、填料、增塑剂、抗冲改性剂、润滑剂、抗菌剂、脱模剂、热稳定剂、抗氧化剂、光稳定剂、增容剂、着色剂、稳定剂、隔离剂、抗静电剂、消泡剂和耐火剂组成的组中的一种或多种。
本申请的另一方面还提供了一种涂料，涂料包括上述用于塑料基材的阳离子固化组合物。
本申请的又一方面还提供了一种塑料制品，包括塑料基材和涂层，涂层涂覆在塑料基材的至少部分区域上，涂层由上述用于塑料基材的阳离子固化组合物固化形成。
本申请的又一方面还提供了一种上述用于塑料基材的阳离子固化组合物在能量固化领域的应用。
应用本发明的技术方案，在引发剂(D)的引发下，多羟基树脂(A)、环氧化合物(B)和含氧杂环丁烷基的化合物(C)能够发生固化反应，形成涂层。环氧化合物(B)和含氧杂环丁烷基的化合物(C)的加入有利于提高涂层的固化速度，多羟基树脂(A)的加入提高了交联密度，有利于提高涂层在金属基材上的附着力，同时含氧杂环丁烷基的化合物(C)的加入有利于提高各组分的相容性。将对上述阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比限定在上述范围内能够大大提高涂层在塑料基材上的附着力、柔韧性、成膜性及固化速度。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术所描述的，现有的塑料包装涂料存在柔韧性和附着力较差的问题。为了解决上述技术问题，本申请提供了一种用于塑料基材的阳离子固化组合物，用于塑料基材的阳离子固化组合物包括：多羟基树脂(A)、环氧化合物(B)、含氧杂环丁烷基的化合物(C)和阳离子引发剂(D)，其中多羟基树脂(A)为聚酯树脂(A1)、丙烯酸树脂(A2)和/或酚醛树脂(A3)，阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3～20):(1～25)。
在引发剂(D)的引发下，多羟基树脂(A)、环氧化合物(B)和含氧杂环丁烷基的化合物(C)能够发生固化反应，形成涂层。环氧化合物(B)和含氧杂环丁烷基的化合物(C)的加入有利于提高涂层的固化速度，多羟基树脂(A)的加入提高了交联密度，有利于提高涂层在金属基材上的附着力，同时含氧杂环丁烷基的化合物(C)的加入有利于提高各组分的相容性。将对上述阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比限定在上述范围内能够大大提高涂层在塑料基材上的附着力、柔韧性、成膜性及固化速度。
为了进一步提高上述阳离子固化组合物形成的涂层的综合性能，在一种优选的实施例中，用于塑料基材的阳离子固化组合物中，羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3～10):(5～15)。
在一种优选的实施例中，按重量份计，用于塑料基材的阳离子固化组合物包括：(5～40)重量份多羟基树脂(A)、(10～65)重量份环氧化合物(B)、(10～70)重量份含氧杂环丁烷基的化合物(C)和(0.5～10)重量份阳离子引发剂(D)。上述阳离子固化组合物中各组分的用量包括但不限于上述范围，而将其限定在上述范围能够进一步发挥各组分的协调增效作用，进而起到进一步提高其形成的涂层的附着力、柔韧性等。更优选地，按重量份计，用于塑料基材的阳离子固化组合物包括：(5～30)重量份多羟基树脂(A)、(15～50)重量份环氧化合物(B)、(20～60)重量份含氧杂环丁烷基的化合物(C)和(2～5)重量份阳离子引发剂(D)。
<多羟基树脂(A)>
多羟基树脂(A)选自聚酯树脂(A1)、丙烯酸树脂(A2)、和酚醛树脂(A3)中的至少一种，也可以是两种及以上的混合物。
本申请的聚酯树脂(A1)是通过多元酸与多元醇缩聚来制备。缩聚反应在惰性气氛中进行，温度为100～260℃，优选130～220℃。
多元酸是指分子中含有多个与烃基直接相连羧基的化合物，可分为脂肪族酸、脂环族酸、和芳香族酸。在一种优选的实施例中，多元酸包括但不限于己二酸、1,4-环己烷二甲酸、富马 酸、葵二酸、顺丁烯二酸酐、邻苯二甲酸、对苯二甲酸、间苯二甲酸、偏苯三酸酐、均苯四酸、四氢邻苯二甲酸、六氢邻苯二甲酸、六氢对苯二甲酸、二氯邻苯二甲酸和四氯邻苯二甲酸和邻苯二甲酸酐组成的组中的一种或多种。更优选地，上述多元酸包括但不限于己二酸、1,4-环己烷二甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸和邻苯二甲酸酐组成的组中的一种或多种。
多元醇是指分子中含有多个与脂肪族碳链直接相连羟基的化合物。在一种优选的实施例中，上述多元醇包括但不限于乙二醇、二乙二醇、1，2-丙二醇、1，3-丙二醇、1，4-丁二醇、1,3-丁二醇、2，3-丁二醇、二-β-羟乙基丁二醇、1，5-戊二醇、1，6-己二醇、1，8-辛二醇、癸二醇、十二烷二醇、新戊二醇、环己烷二醇、1，4-环己烷二甲醇、甲基丙二醇、羟基叔戊酸新戊二醇酯、乙基丁基丙二醇、2,2,4-三甲基-1,3-戊二醇、2，2-双-(4-羟基环己基)丙烷、2-甲基-丙烷-1，3-二醇、2-甲基-戊烷-1，5-二醇、2，2，4(2，4，4)-三甲基己烷-1，6-二醇、甘油、三羟甲基丙烷、三羟甲基乙烷、己烷-1，2，6-三醇、丁烷-1，2，4-三醇、季戊四醇、甘露醇和山梨醇，还有二甘醇、三甘醇、四甘醇、一缩二丙二醇、聚丙二醇、聚丁二醇、亚二甲苯基二甲醇和羟基新戊酸新戊二醇酯组成的组中的一种或多种；更优选地，上述多元醇包括但不限于乙二醇、新戊二醇、季戊四醇、1,6-乙二醇、甲基丙二醇、羟基叔戊酸新戊二醇酯、乙基丁基丙二醇、2,2,4-三甲基-1,3-戊二醇、1，4-环己烷二甲醇、环己烷二甲醇、三羟甲基丙烷和甘油组成的组中的一种或多种。
在一种优选的实施例中，上述聚酯树脂(A1)的羟值为50～500mgKOH/g。相比于其它羟值，将聚酯树脂(A1)的羟值限定在上述范围内，有利于提高涂层与塑料基材的附着力、可加工性和交联密度，进而有利于抑制归因于焓松弛的漆膜固化时的脆化。更优选地，聚酯树脂(A1)的羟值为80～350mgKOH/g。
在一种优选的实施例中，上述聚酯树脂(A1)的数均分子量为200～12000。相比于其它范围，将聚酯树脂(A1)的分子量限定在上述范围内有利于提高涂层的强度，且便于涂装作业。更优选地，上述聚酯树脂的数均分子量为300～5000。
本申请所述的丙烯酸树脂(A2)是指由丙烯酸酯类或甲基丙烯酸酯类及其它烯属单体共聚而成的聚合物。其中，(甲基)丙烯酸酯类或其它烯属单体中至少有一个为含羟基的功能性单体，含羟基的功能性单体优选如下的结构：
Figure PCTCN2020117189-appb-000001
其中，R 0为H，或CH 3；R为C 2-C 10的直链或支链烷基醇。
在一种优选的实施例中，上述含羟基的功能性单体选自丙烯酸羟乙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丁酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、4-羟基丁基丙烯酸酯、丙烯醇、肉桂醇、香茅醇和2-己烯-1-醇组成的组中的一种或多种。
在另一种优选的实施例中，上述不含羟基的功能性单体选自丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酰胺、丙烯酸缩水甘油酯、丙烯酸二甲氨基丙酯、丙烯酸四氢呋喃甲酯、丙烯酸氟烷基酯、丙烯氰或苯乙烯组成的组中的一种或多种。
在一种优选的实施例中，上述丙烯酸树脂(A2)的羟值为15～200mgKOH/g。相比于其它范围，本申请丙烯酸树脂(A2)的羟值在上述范围内有利于进一步提高其形成的涂层与塑料基材的附着力、可加工性和交联密度，进而有利于抑制归因于焓松弛的漆膜固化时的脆化。更优选地，丙烯酸树脂(A2)的羟值为50～150mgKOH/g。
在一种优选的实施例中，上述丙烯酸树脂(A2)的玻璃化转变温度(Tg)为10～150℃。相比于其它范围，将丙烯酸树脂(A2)的玻璃化转变温度限定在上述范围内，有利于提高其与组合物中其他组分的相容性较好，进而提高上述阳离子固化组合物的成膜性。更优选地，上述丙烯酸树脂(A2)的玻璃化转变温度(Tg)为20～100℃。
在一种优选的实施例中，上述丙烯酸树脂(A2)的数均分子量为500～20000。相比于其它范围，丙烯酸树脂的分子量在上述范围有利于提高涂层的强度。更优选地，上述丙烯酸树脂(A2)的数均分子量为1000～8000。
本申请采用的酚醛树脂(A3)可以是由酚类化合物和脂肪族醛类化合物在酸性或碱性条件下，通过缩合反应得到的酚醛树脂。优选地，酚类化合物为苯酚、邻甲酚、间甲酚、对甲酚、邻-乙基酚、间-乙基酚、对-乙基酚、邻-丁基酚、间-丁基酚、对-丁基酚、对叔丁酚、对叔辛酚、对壬基酚、双酚A、对苯基酚、2，3-二甲酚、2，4-二甲酚、2，5-二甲酚、2，6-二甲酚、3，4-二甲酚、3，5-二甲酚、2，3，5-三甲酚、3，4，5-三甲酚、对苯二酚、间苯二酚、α-萘酚和β-萘酚。优选地，酚类化合物为苯酚、对苯二酚、对叔辛酚、对壬基酚、双酚A、对苯基酚、邻甲酚、间甲酚、对甲酚、对叔丁酚和α-萘酚中的一种或多种。所述脂肪族醛类化合物为含C1～C8的醛，可以列举出：甲醛、对-甲醛、乙醛、丙醛、丙烯醛、丁醛、2-丁烯醛、戊醛、三甲基乙醛。
本申请采用的酚醛树脂(A3)也可以是环氧改性的酚醛树脂，对改性方法没有限制。
优选地，酚醛树脂(A3)羟值为50～300mgKOH/g，更优选为100～250mgKOH/g。用于本申请的酚醛树脂的数均分子量为300～15000，更优选为500～8000。
<环氧化合物(B)>
本发明的环氧化合物优选脂环式环氧化合物和脂肪族环氧化合物。
上述脂环式环氧化合物可列举出具有至少1个脂环式环的多元醇的多缩水甘油醚化物、或者通过将含环己烯或环戊烯环的化合物用氧化剂进行环氧化而得到的含环氧环己烷或环氧环戊烷的化合物。例如，氢化双酚A二缩水甘油醚、3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯、3,4-环氧基-1-甲基环己基-3,4-环氧基-1-甲基己烷羧酸酯、6-甲基-3,4-环氧基环己基甲基-6-甲基-3,4-环氧基环己烷羧酸酯、3,4-环氧基-3-甲基环己基甲基-3,4-环氧基-3-甲基环己烷羧酸酯、3,4-环氧基-5-甲基环己基甲基-3,4-环氧基-5-甲基环己烷羧酸酯、双(3,4-环氧基环己基甲基)己二酸酯、3,4-环氧基-6-甲基环己烷羧酸酯、亚甲基双(3,4-环氧基环己烷)、丙烷-2,2-二基-双(3,4-环氧基环己烷)、2,2-双(3,4-环氧基环己基)丙烷、二环戊二烯二环氧化物、亚乙基双(3,4-环氧基环己烷羧酸酯)、环氧基六氢邻苯二甲酸二辛酯、环氧基六氢邻苯二甲酸二-2-乙基己酯、1-环氧基乙基-3,4-环氧基环己烷、1,2-环氧基-2-环氧基乙基环己烷、氧化α-蒎烯、二氧化苧烯等。
上述脂环式环氧化合物，优选环氧当量为80～500的化合物。
上述脂环式环氧化合物，可以使用市售品，例如CELLOXIDE2021P、CELLOXIDE 2081、CELLOXIDE 2000、CELLOXIDE3000(Daicel Corporation制)等。
上述脂肪族环氧化合物是指不被分类到芳香族环氧化合物或脂环式环氧化合物的环氧化合物，可列举出脂肪族醇的缩水甘油醚化物、烷基羧酸的缩水甘油酯等单官能环氧化合物或脂肪族多元醇或其环氧烷烃加成物的多缩水甘油醚化物、脂肪族长链多元酸的多缩水甘油酯等多官能环氧化合物。作为代表性化合物，可列举出烯丙基缩水甘油醚、丁基缩水甘油醚、2-乙基己基缩水甘油醚、C12～13混合烷基缩水甘油醚、1,4-丁二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、甘油的三缩水甘油醚、三羟甲基丙烷的三缩水甘油醚、山梨糖醇的四缩水甘油醚、二季戊四醇的六缩水甘油醚、聚乙二醇的二缩水甘油醚、聚丙二醇的二缩水甘油醚等多元醇的缩水甘油醚、以及通过在丙二醇、三羟甲基丙烷、甘油等脂肪族多元醇上加成1种或2种以上的环氧烷烃而得到的聚醚多元醇的多缩水甘油醚化物、脂肪族长链二元酸的二缩水甘油酯。进而，可列举出脂肪族高级醇的单缩水甘油醚或高级脂肪酸的缩水甘油酯、环氧化大豆油、环氧硬脂酸辛酯、环氧硬脂酸丁酯、环氧化大豆油、环氧化聚丁二烯等。
上述脂肪族环氧化合物，优选环氧当量为80～500的化合物。
上述脂肪族环氧化合物，可以使用市售品，可列举出例如Denacol EX-121、Denacol EX-171、Denacol EX-192、Denacol EX-211、Denacol EX-212、Denacol EX-313、Denacol EX-314、Denacol EX-321、Denacol EX-411、Denacol EX-421、Denacol EX-512、Denacol EX-521、Denacol EX-611、Denacol EX-612、Denacol EX-614、Denacol EX-622、Denacol EX-810、Denacol EX-811、Denacol EX-850、Denacol EX-851、Denacol EX-821、Denacol EX-830、Denacol EX-832、Denacol EX-841、Denacol EX-861、Denacol EX-911、Denacol EX-941、Denacol EX-920、Denacol EX-931(Nagase ChemteX Corporation制)；Epolight M-1230、Epolight 40E、Epolight 100E、Epolight 200E、Epolight 400E、Epolight 70P、Epolight 200P、Epolight 400P、Epolight 1500NP、 Epolight 1600、Epolight80MF、Epolight 100MF(共荣社化学公司制)、Adeka Glycirol ED-503、AdekaGlycirol ED-503G、Adeka Glycirol ED-506、Adeka Glycirol ED-523T(ADEKA公司制)等。
<含氧杂环丁烷基的化合物(C)>
与只含有环氧基团而不含有氧杂环丁烷基团的组合物相比，同时含有氧杂环丁烷基团和环氧基团时能够加快组合物的固化速度。同时氧杂环丁烷基团的存在也改善了由该组合物制成的漆膜的柔韧性，使塑料制品在后续的加工过程中不易出现开裂和破损的情况。
在阳离子引发剂的存在下，可用光辐照使含氧杂环丁烷基的化合物(C)进行聚合或交联。含氧杂环丁烷基的化合物可含有一个或多个氧杂环丁烷基。
出于制备成本和反应活性的考虑，选择如下几种结构作为本申请中的含氧杂环丁烷基的化合物(C)：
在一种优选的实施例中，含氧杂环丁烷基的化合物(C)中含有一个氧杂环丁烷基，结构式如式(1)所示：
Figure PCTCN2020117189-appb-000002
其中Z为氧原子；
R 1选自氢原子，具有1～6个碳原子的烷基(如甲基、乙基、丙基或丁基)或具有6～18个碳原子的芳基(如苯基和萘基，呋喃基或噻吩基)；R 2选自氢原子，环氧基，具有1～6个碳原子的烷基(如甲基、乙基、丙基和丁基)，具有6～18个碳原子的芳基(如苯基、萘基和蒽基),具有7～18个碳原子的取代或非取代的芳烷基(如苯甲基、氟苯甲基、甲氧基苯甲基、苯乙基、苯乙烯基、肉桂基或乙氧基苯甲基)或具有其它芳环的基团(如芳氧基烷基，例如苯氧甲基或苯氧乙基)。
优选地，分子中只含有一个氧杂环丁烷基的化合物(C)选自3-乙基-3-羟甲基氧杂环丁烷、3-(甲)烯丙基氧甲基-3-乙基氧杂环丁烷、(3-乙基-3-氧杂环丁基甲氧基)甲苯、(3-乙基-3-氧杂环丁基甲氧基)苯、4-甲氧基-(1-(3-乙基-3-氧杂环丁基甲氧基)甲基)苯、(1-(3-乙基3-氧杂环丁基甲氧基)乙基)苯醚、异丁氧甲基(3-乙基-3-氧杂环丁基甲基)醚、2-乙己基(3-乙基-3-氧杂环丁基甲基)醚、乙基二亚乙基甘醇(3-乙基-3-氧杂环丁基甲基)醚、二环戊二烯(3-乙基-3-氧杂环丁基甲基)醚、二环戊氧基乙基(3-乙基-3-氧杂环丁基甲基)醚、二环戊基(3-乙基-3-氧杂环丁基甲基)醚、四溴苯基(3-乙基-3-氧杂环丁基甲基)醚、2-四溴苯氧基乙基(3-乙基-3-氧杂环丁基甲基)醚、三溴苯基(3-乙基-3-氧杂环丁基甲基)醚、2-三溴苯氧基乙基(3-乙基-3-氧杂环丁基甲基)醚、2-羟乙基(3-乙基-3-氧杂环丁基甲基)醚、2-羟丙基(3-乙基-3-氧杂环丁基甲基)醚、丁氧 基乙基(3-乙基-3-氧杂环丁基甲基)醚、五氯苯基(3-乙基-3-氧杂环丁基甲基)醚、五溴苯基(3-乙基-3-氧杂环丁基甲基)醚组成的组中的一种或多种。
在另一种优选的实施例中，含氧杂环丁烷基的化合物(C)中含有两个氧杂环丁烷环基，结构式如式(2)所示：
Figure PCTCN2020117189-appb-000003
其中R 1与上述分子式(1)中定义相同；
R 3选自具有1～20个碳原子的直链或支链的亚烷基(如亚乙基、亚丙基或亚丁基)，具有1～120个碳原子的直链或支链的聚(亚烷氧基)(如聚(亚乙氧基)或聚(亚丙氧基))，直链或支链的不饱和烃基(如1，3-亚丙基、甲基1，3-亚丙基或亚丁基)。
优选地，R 3选自以下式(3)和(4)所示的多价基团：
Figure PCTCN2020117189-appb-000004
其中R 4选自具有1～4个碳原子的烷基，具有1～4个碳原子的烷氧基，卤素原子(如氯原子或溴原子)，硝基，氰基，巯基，羧基或氨基甲酰基，其中x为0～4中的任意整数。
Figure PCTCN2020117189-appb-000005
其中R 5代表氧原子、硫原子、亚甲基、-NH-、-SO-、-SO 2-、-C(CF 3) 2-或-C(CH 3) 2-。
在又一种优选的实施例中，含氧杂环丁烷基的化合物(C)中含有两个氧杂环丁烷基，结构式如(5)所示：
Figure PCTCN2020117189-appb-000006
在式(5)中，R 1与上述式(1)表述相同。
在分子中含有三个或多个氧杂环丁烷基的化合物举例如以下分子式(6)所示：
Figure PCTCN2020117189-appb-000007
其中，R 1与上述分子式(1)中定义相同；R 6选自化合价为3～10的有机基团。
优选地，分子中含有两个或多个氧杂环丁烷基的化合物选自3，7-二(3-氧杂环丁基)-5-氧杂-壬烷、3，3’-(1，3-(2-亚甲基(methylenyl))丙二基二(氧亚甲基)二-(3-乙基氧杂环丁烷)、1，4-二[(3-乙基-3-氧杂环丁基甲氧基)甲基]苯、1，2-二((3-乙基-3-氧杂环丁基甲氧基)甲基)乙烷、1，3-二(3-乙基-氧杂环丁基甲氧基)甲基)丙烷、乙二醇二(3-乙基-3-氧杂环丁基甲基)醚、二环戊烯基二(3-乙基-3-氧杂环丁基甲基)醚、三甘醇二(3-乙基-3-氧杂环丁基甲基)醚、四甘醇二(3-乙基-3-氧杂环丁基甲基)醚、三环癸二基二亚甲基(3-乙基-3-氧杂环丁基甲基)醚、三羟甲基丙烷三(3-乙基-3-氧杂环丁基甲基)醚、1，4-二(3-乙基-3-氧杂环丁基甲氧基)丁烷、1，6-二(3-乙基-3-氧杂环丁基甲氧基)己烷、季戊四醇三(3-乙基-3-氧杂环丁基甲基)醚、季戊四醇四(3-乙基-3-氧杂环丁基甲基)醚、聚乙二醇二(3-乙基-3-氧杂环丁基甲基)醚、二季戊四醇六(3-乙基-3-氧杂环丁基甲基)醚、二季戊四醇五(3-乙基-3-氧杂环丁基甲基)醚、二季戊四醇四(3-乙基-3-氧杂环丁基甲基)醚、二三羟甲基丙烷四(3-乙基-3-氧杂环丁基甲基)醚组成的组中的一种或多种。
优选地，氧杂环丁烷选自式(1)所定义的组分，其中R 1为氢原子、C 1～C 4的烷基；Z为氧原子；R 2为氢原子、环氧基、C 1～C 4的烷基、或苯基。更优选地，3-乙基-3-羟甲基氧杂环丁烷、(3-乙基-3-氧杂环丁基甲氧基)甲苯、3-苄氧甲基-3-乙基氧杂环丁烷、(3-乙基-3-氧杂环丁基甲氧基)苯、3,3'-[氧基双亚甲基]双[3-乙基]氧杂环丁烷、3-乙基-3-[(氧化乙烯-2-甲氧基)甲基]氧杂环丁烷、2-乙己基(3-乙基-3-氧杂环丁基甲基)醚、1，4-二((3-乙基-3-氧杂环丁基甲氧基)甲基)苯、1，2-二((3-乙基-3-氧杂环丁基甲氧基)甲基)乙烷、1，3-二((3-乙基-3-氧杂环丁基甲氧基)甲基)丙烷、和二(3-乙基-3-氧杂环丁基甲基)。
从反应活性的角度选择，氧杂环丁烷基团与环氧基团的摩尔比为(5～15):(3～10)时，有利于提高阳离子固化组合物对光辐射的活性。从组合物应用性能的角度选择，羟基、三元环氧基团及四元环氧基团的摩尔比值为1:(3～10):(5～15)时，有利于提高阳离子固化组合物制得的漆膜柔韧性，且对塑料基材的附着力好。
<阳离子引发剂(D)>
阳离子引发剂是在紫外线、电子射线等活性能量射线的照射下能够产生阳离子或路易斯酸，并能够引发环氧化合物、含氧杂环丁烷基的化合物等阳离子固化性成分聚合的化合物。
本申请提供的阳离子固化组合物中，阳离子引发剂(D)可以采用本领域常用的种类。优选为碘鎓盐、硫鎓盐或芳基茂铁盐中的一种或两种。基于成本、配合使用的效果(如光引发 效率、固化速度)等综合因素的考虑，更优选碘鎓盐和/或硫鎓盐类光引发剂，特别优选为具有如下通式所示结构的化合物：
Figure PCTCN2020117189-appb-000008
上述通式中，R 7和R 8各自独立地选自氢、C 1～C 20的直链或支链烷基、C 4～C 20的环烷基烷基或烷基环烷基、C 6～C 20的取代或未取代的芳基，且这些基团中的非环-CH 2-可任选地被-O-、-S-或1,4-亚苯基所取代；
R 9选自C 6～C 20的取代或未取代芳基、C 6～C 20的取代或未取代的烷基芳基、C 1～C 20的直链或支链烷基、C 4～C 20的环烷基烷基或烷基环烷基、取代或未被取代的苯硫基苯基，且这些基团中的非环-CH 2-可任选地被羰基、-O-、-S-或1,4-亚苯基所取代；
R 10和R 11各自独立地选自烷基、羟基、烷氧基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、芳硫基羰基、酰氧基、芳硫基、芳基、杂环烃基、芳氧基、烷基亚磺酰基、芳基亚磺酰基、烷基磺酰基、芳基磺酰基、羟基(聚)亚烷基氧基、可取代的氨基、氰基、硝基或卤原子，m 1、m 2各自独立地选自0～4的整数；
A -各自独立地选自X -、ClO 4 -、CN -、HSO 4 -、NO 3 -、CF 3COO -、(BX 4) -、(SbX 6) -、(AsX 6) -、(PX 6) -、Al[OC(CF 3) 3] 4 -、磺酸根离子、B(C 6X 5) 4 -或[(Rf) bPF 6-b] -，其中，X为卤素，R f表示≥80％的氢原子被氟原子取代的烷基，b表示1～5的整数，且b个R f基团相同或互不相同。
R 7和R 8各自独立地选自氢、C 1～C 12的直链或支链烷基、C 4～C 10的环烷基烷基或烷基环烷基、C 6～C 12的取代或未取代芳基，且这些基团中的非环-CH 2-可任选地被-O-、-S-或1,4-亚苯基所取代；
R 9选自C 6～C 10的取代或未取代芳基、C 6～C 10的取代或未取代的烷基芳基、取代或未被取代的苯硫基苯基，且这些基团中的非环-CH 2-可任选地被羰基、-O-、-S-或1,4-亚苯基所取代；
R 10和R 11各自独立地选自C 1～C 10的直链或支链烷基、C 1～C 10的直链或支链烷氧基、C 1～C 10的烷基羰基或卤素。
在一种优选的实施例中，阳离子引发剂(D)中的阳离子部分选自以下结构的中一种或多种：
Figure PCTCN2020117189-appb-000009
Figure PCTCN2020117189-appb-000010
Figure PCTCN2020117189-appb-000011
Figure PCTCN2020117189-appb-000012
Figure PCTCN2020117189-appb-000013
Figure PCTCN2020117189-appb-000014
在一种优选的实施例中，阳离子引发剂(D)中的阴离子部分选自Cl -、Br -、PF 6 -、SbF 6 -、AsF 6 -、BF 4 -、C 4F 9SO 3 -、B(C 6H 5) 4 -、C 8F 17SO 3 -、CF 3SO 3 -、Al[OC(CF 3) 3] 4 -、(CF 3CF 2) 2PF 4 -、(CF 3CF 2) 3PF 3 -、[(CF 3) 2CF 2] 2PF 4 -、[(CF 3) 2CF 2] 3PF 3 -、[(CF 3) 2CFCF 2] 2PF 4 -或(CF 3) 2CFCF 2] 3PF 3 -。
此外，具有同类结构的市售阳离子引发剂也可用于本发明的光引发剂(D)，如常州强力电子新材料股份有限公司生产PAG20001、PAG20002、PAG30201、PAG30101，及BASF公司生产的Irgacure250中的一种或多种。
本发明的阳离子引发剂(D)组分，可以单独使用上述的化合物，也可以使用两种及以上组合物。
<助剂(E)>
为了进一步提高阳离子固化组合物的综合性能，上述阳离子固化组合物中还包括助剂(E)，助剂(E)包括但不限于增感剂、色材、阻燃剂、流平剂、固化促进剂、光/热产酸剂、粘结促进剂、紫外吸收剂、抗凝聚剂、增稠剂、成核剂、偶联剂、填料、增塑剂、抗冲改性剂、润滑剂、抗菌剂、脱模剂、热稳定剂、抗氧化剂、光稳定剂、增容剂、稳定剂、隔离剂、抗静电剂、消泡剂和耐火剂组成的组中的一种或多种。更优选地，按重量份计，上述阳离子固化组合物包括(0～40)重量份助剂(E)，进一步优选为(1～10)重量份所述助剂(E)。
在一种优选的实施例中，上述阳离子固化组合物可选择性地添加增感剂。增感剂的添加有利于进一步提高组合物的感光度，或者满足长波长光源特别是UV-LED下的光固化需求。更优选地，上述增感剂包括但不限于硫杂蒽酮类化合物、氧杂蒽酮类化合物、吖啶类化合物、蒽类化合物和香豆素类化合物组成的组中的一种或多种，进一步优选为蒽类化合物和/或硫杂蒽酮类化合物。如天津久日新材料生产的JRCure-1105(ITX)、JRCure-1106(DETX)；常州强力电子新材料生产的PSS303、PSS510、PSS513、PSS515、PSS519等。
此外，增感剂还可选自含有如下结构的化合物：
Figure PCTCN2020117189-appb-000015
Figure PCTCN2020117189-appb-000016
Figure PCTCN2020117189-appb-000017
在一种优选的实施例中，增感剂的添加量为组分A、组分B、组分C和组分D总重量的0～0.1倍，优选为0.005～0.06倍。
在另一种优选的实施例中，本发明的阳离子固化组合物可选择性地添加色材，其中作为色材包括颜料、着色剂、染料和天然色素组成的组中的一种或多种。
蓝色颜料或青色颜料优选为颜料蓝(Pigment Blue)1、2、3、15、15:1、15:2、15:3、15:4、15:6、16、17-1、22、27、28、29、36、60；作为绿色颜料，可举出颜料绿(Pigment Green)7、26、36、50。
红色颜料或品红色颜料优选为颜料红(Pigment Red)1、2、3、4、5、6、7、8、9、10、19、22、31、38、42、43、48:1、48:2、48:3、48:4、48:5、49:1、53:1、57:1、57:2、58:4、63:1、81、81:1、81:2、81:3、81:4、88、104、108、112、122、123、144、146、149、166、168、169、170、177、178、179、184、185、208、216、226、257、氧化铁等；作为紫色颜料，可列举出颜料紫(Pigment Violet)3、19、23、29、30、37、50、88；作为橙色颜料，可列举颜料橙(Pigment Orange)13、16、20、36。
黄色颜料优选为颜料黄(Pigment Yellow)1、2、3、4、5、6、7、10、12、13、14、17、34、35、37、55、74、81、83、93、94、95、97、108、109、110、120、137、138、139、153、154、155、157、166、167、168、180、185、193。
黑色颜料优选为颜料黑(Pigment Black)7、28、26、炉法炭黑、灯黑、乙炔黑、槽法炭黑；三菱化学制NO.2300、NO.900、MCF88、NO.33、NO.40、NO.45、NO.52、MA7、MA8、MA100；Cabot Japan制Regal 400R、Regal 300R、Regal 660R、Monarch 800、Monarch 880、Monarch 900、Monarch 1000、Monarch 1100、Monarch 1300、Monarch 1400等炭黑。
白色颜料优选为颜料白(Pigment White)6、18、21、氧化钛等。
本发明阳离子固化组合物中，色材的添加量为组分A、组分B、组分C和组分D总重量的0～40％，优选1～10％。色材的平均粒径没有特别限制，可以根据目的应用适当选择。
在本发明中，为稳定地将色材分散在本发明的阳离子固化组合物中，优选地，上述阳离子固化组合物还包括分散单体和/或分散助剂。相对于100重量份色材，分散助剂的含量为30～80重量份，分散单体重量分数和色材重量分数之和为100％。
作为可用于本发明的分散助剂，优选为聚合物分散剂，更优选地，上述聚合物分散剂选自：BYK Chemie制DISPERBYK-101/102/103/106/111/161/162/163/164/166/167/168/170/171/174/182；EFKA添加剂制EFKA4010/4046/4080/5010/5207/5244/6745/6750/7414/7462/7500/7570/7575/7580；San Nopco Limited制DISPERSE AID 6/8/15/9100；由Avecia制SOLSPERSE分散剂：SOLSPERSE3000/5000/9000/12000/13240/13940/17000/22000/24000/26000/28000/32000/36000/39000/41000/71000；Adeka Corporation制ADEKA PLURONIC L31/F38/L42/L44/L61/L64/F68/L72/P95/F77/P84/F87/P94/L101/P103/F108/L121。作为可用于本发明的分散单体，没有特别限制。例如，可以使用具有低分子量的可聚合化合物，优选低粘度的可聚合化合物。
本申请的另一方面还提供了一种涂料，涂料包括上述阳离子固化组合物。
在引发剂(D)的引发下，多羟基树脂(A)、环氧化合物(B)和含氧杂环丁烷基的化合物(C)能够发生固化反应，形成涂层。环氧化合物(B)和含氧杂环丁烷基的化合物(C)的加入有利于提高涂层的固化速度，多羟基树脂(A)的加入提高了交联密度，有利于提高涂层在金属基材上的附着力，同时含氧杂环丁烷基的化合物(C)的加入有利于提高各组分的相容性。将对上述阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比限定在上述范围内能够大大提高涂层在基材上的附着力、柔韧性、成膜性及固化速度。在此基础上，含有上述阳离子固化组合物的涂料形成的涂层具有吸附力强、柔韧性和成膜性好及固化速度快等优点。
<固化光源>
将阳离子固化组合物涂覆于塑料基材之后，进行光化辐射固化成膜。
“光化辐射”为具有范围在紫外光范围至可见光范围、至红外光范围的电磁辐射波长的光。可用于固化本发明所述的阳离子固化组合物的光化辐射通常具有范围在150～2000nm的辐射波长，优选为具有范围在200～600nm的辐射波长，可根据组合物中阳离子聚合引发剂的种类等，适当选择具有高敏感度波长的照射源使用。合适的紫外光源可列举出：汞弧、碳弧、低、中或高压汞灯，涡流等离子弧和紫外光发光二极管，优选的紫外光源为中压汞灯。漆膜的照射剂量为10～1000mJ/cm 2，优选为50～500mJ/cm 2。
此外，在光化辐射后，可以根据需要对漆膜进行加热，以通过加热减少漆膜中的未反应物，并缓和由光化辐射和成型加工产生的漆膜应变。加热过程有时能提高漆膜的硬度和附着力。优选地，上述加热过程的温度为150～250℃，加热时间为1～30min。
本申请提供的阳离子固化组合物可以应用在能量固化领域，尤其适合应用于塑料基材上。
<塑料基材>
本申请提供的阳离子固化组合物适用于涂覆在塑料基材上。用在本发明中的塑料基材可以为本领域常规的塑料基材，没有特别的限制。在一种优选的实施例中，本发明所述的塑料基材可包括聚苯乙烯(PS)、聚丙烯(PP)、聚乙烯(PE)、聚氯乙烯(PVC)、聚氨酯(PUR)、玻璃纤维增强的不饱和聚酯、聚甲基丙烯酸甲酯(PMMA)、聚苯硫醚(PPS)、聚甲醛(POM)、聚苯醚(PPO)、聚脲、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、尼龙、用乙烯-丙烯-二烯共聚物(EPDM)改性的聚丙烯等，也可以是上述塑料混合物的塑料基材。如有必要，上述塑料基材可通过已知方法进行预处理，如脱脂、水洗等。
<含有塑料基材的涂装制品>
本申请的又一方面还提供了一种塑料制品，包括塑料基材和涂覆在上述塑料基材的至少部分区域的涂层，涂层由上述用于塑料基材的阳离子固化组合物固化形成。阳离子固化组合物可通过常规的方式涂覆于塑料基材上，其中常规的方式包括但不限于刷涂、辊涂、浸渍、浇涂、喷涂等。可以涂覆整个塑料基材表面，或仅仅涂覆一部分。涂布的膜厚可根据用途适当选择，通常，干燥涂膜厚度约为2～20微米，更优选为2～8微米。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例及比较例中采用的原料如下：
<多羟基树脂(A)>
聚酯树脂(A1-1)：PCL210，羟值：109～119mgKOH/g(日本大赛璐有限公司)；
聚酯树脂(A1-2)：Capa TM，羟值：294～328mgKOH/g(柏斯托)；
聚酯丙烯酸树脂(A2-1)：RA35.2，羟值：95～105mgKOH/g(唯盛化工)；
丙烯酸树脂(A2-2)：
Figure PCTCN2020117189-appb-000018
6522，羟值：79mgKOH/g(湛新树脂)；
酚醛树脂(A3-1)：F51，环氧值：0.51(羟值：约150mgKOH/g)(常州向阳新材有限公司)；酚醛树脂(A3-2)：E44，环氧值：0.44(羟值：约210mgKOH/g)(三木6101)。
<环氧化合物(B)>
B1：
Figure PCTCN2020117189-appb-000019
(泰特尔TTA21)；
B2：
Figure PCTCN2020117189-appb-000020
B3：
Figure PCTCN2020117189-appb-000021
(常州强力TCM234)；
B4：
Figure PCTCN2020117189-appb-000022
B5：
Figure PCTCN2020117189-appb-000023
B6：
Figure PCTCN2020117189-appb-000024
<含氧杂环丁烷基的化合物(C)>
C1：
Figure PCTCN2020117189-appb-000025
(常州强力TCM101)；
C2：
Figure PCTCN2020117189-appb-000026
(常州强力TCM104)；
C3：
Figure PCTCN2020117189-appb-000027
(常州强力TCM201)；
C4：
Figure PCTCN2020117189-appb-000028
(常州强力TCM207)；
C5：
Figure PCTCN2020117189-appb-000029
(常州强力TCM207)；C6：
Figure PCTCN2020117189-appb-000030
(常州强力TCM210)；
<阳离子引发剂(D)>
D1：三苯基硫鎓六氟磷酸盐(常州强力PAG20002s)；
D2：二苯基碘鎓六氟锑酸盐(常州强力PAG30202)；
<助剂(E)>
E1：增感剂PSS306(常州强力)；
E2：流平剂BYK307(德国毕克)；
E3：消泡剂BYK055(德国毕克)；
<无色阳离子固化组合物>
在室温、黄光灯下，根据表1和2所示配方将各组分预先混合均匀后，使用搅拌机在1500～2000rpm转速条件下高速分散30min，使其混合均匀，经过滤网过滤后，制得无色阳离子固化组合物。
表1和2所示配方为各组分的重量份，单位为g。括号内数字表示相应物质含有官能团的物质的量，单位为mol。
表1
Figure PCTCN2020117189-appb-000031
表2
Figure PCTCN2020117189-appb-000032
实施例1至12及比较例1至2的阳离子固化组合物中，羟基、三元环氧基团与四元环氧基团的摩尔数之比见表3。
表3
  羟基、三元环氧基团与四元环氧基团的摩尔比 换算后
实施例1 0.25:1:2.5 1:4:10
实施例2 0.25:1:2.5 1:4:10
实施例3 0.25:2:2 1:8:8
实施例4 0.25:2:2 1:8:8
实施例5 0.25:1:2 1:4:8
实施例6 0.25:1:2 1:4:8
实施例7 0.25:2:3 1:8:12
实施例8 0.25:2.5:3.75 1:10:15
实施例9 0.25:0.75:1.25 1:3:5
实施例10 0.25:2:2 1:8:8
实施例11 0.25:0.75:0.25 1:3:1
实施例12 0.025:0.5:0.625 1:20:25
比较例1 0.25:0.25:0.25 1:1:1
比较例2 0.25:0.25:3 1:1:12
<有色阳离子固化组合物>
颜料分散体制备：
在室温下，根据表4所示配方将各组分预先混合均匀后，使用搅拌机在800-1000rpm转速条件下搅拌1h，再以2000-3000rpm转速搅拌至颜料分散体的D90(使用欧美克TopSizer激光粒度分析仪进行测试)到1.50μm以下时，停止搅拌制得颜料分散体-1、分散体-2、分散体-3和分散体-4。
表4所示配方为各组分的重量份，单位为g。
表4
Figure PCTCN2020117189-appb-000033
上述配方中，颜料黑为三菱MA7；颜料白为石原钛白R706；颜料蓝为巴斯夫酞青蓝15:3；颜料红为科莱恩122。
有色阳离子固化组合物制备：
在室温、黄光灯下，根据表5所示配方将各组分预先混合均匀后，使用搅拌机在1500-2000rpm转速条件下高速分散30min，使其混合均匀，经过滤网过滤后制得有色阳离子固化组合物。
表5所示配方为各组分的重量份，单位为g。括号内数字表示相应物质含有官能团的物质的量，单位为mol。
表5
Figure PCTCN2020117189-appb-000034
实施例13至18及比较例8的阳离子固化组合物中，羟基、三元环氧基团与四元环氧基团的摩尔比见表6。
表6
  羟基、三元环氧基团与四元环氧基团的摩尔比 换算后
实施例13 0.25:2:2 1:8:8
实施例14 0.25:1:2.5 1:4:10
实施例15 0.25:1:2 1:4:8
实施例16 0.25:2:3 1:8:12
实施例17 0.25:2:3 1:8:12
实施例18 0.25:2:2 1:8:8
比较例8 0.25:0.25:0.25 1:1:1
性能测试
将表1至2和表5中所示的阳离子固化组合物成膜后进行性能评价测试。
操作如下：
使用PET和PP作为基材，用丙酮擦拭后进行涂布，涂层厚度在25±5μm，固化完全后测试其性能，测试结果见表7和8。
测试方法：
(1)硬度测试：参照国家标准GB/T6739-86，准备一组硬度为6B～6H的绘图铅笔，用手动法测定涂膜的铅笔硬度。将涂膜板水平放置在台面上，手持铅笔成45°角，以均匀的速度用力在涂膜面上推压约1cm，并在涂膜上留下刮划。对同一硬度标号的铅笔重复刮划5道，如有2道或以上未刮划到样板的底板，则换用硬度大一标号的铅笔，直至找到涂膜被擦伤2道或以上。比该铅笔硬度小一标号即为涂膜的铅笔硬度。
(2)附着力测试：参照国家标准GB/T9286-1998分别测试漆膜在PET膜或PP膜上的附着。用划刀在涂膜上切6道平行切痕，应切穿涂膜的整个深度；然后再切同样的6道，与前者垂直，形成许多小方格，然后用宽为25mm的半透明压敏胶带贴在整个切痕划格上，猛拉胶带，并与标准比较，确定涂膜附着力的级数。
(3)柔韧性测试：参照国家标准GB1731，将组合物涂覆在PET膜上，固化后，将漆膜面朝上，将测试样品紧压在所需直径的轴棒上，绕棒弯曲，弯曲后两拇指应对称于轴棒的中心线。目视或4倍放大镜观察漆膜有无网纹、裂纹及剥落等破坏现象，以样板在不同直径的轴棒上弯曲而不引起漆膜破坏的最小轴棒直径表示该漆膜的柔韧性，轴棒直径越小，柔韧性越好。
(4)固化时间测试：参照国家标准GB/T1728-79，将组合物喷涂在PET膜上，分别测定组合物的固化时间。
(5)VOC测试：称取0.2g样品涂覆到称过重量的PET膜上，称重；将涂布后的样品进行固化，室温下冷却15min，称重；将涂膜放置于110℃的通风烘箱中干燥1h，将涂膜放置在干燥器中冷却至室温，称重。
加工挥发物＝100[(B-C)/(B-A)]；潜在挥发物＝100[(C-D)/(B-A)]；
总的挥发物％＝加工挥发物％+潜在挥发物％，
其中：A为PET膜的重量，g；B为涂膜和PET膜的重量，g；
C为固化后涂膜和PET膜的重量，g；D为固化并加热后涂膜和PET膜的重量，g。
表7
Figure PCTCN2020117189-appb-000035
表8
Figure PCTCN2020117189-appb-000036
由表7和表8可以看出：
比较实施例1至12及比较例3-5可知，采用本申请提供的阳离子固化组合物有利于大幅提高其形成的涂层的综合性能。比较实施例1至12及比较例1至2可知，将羟基、三元环氧基团和四元环氧基团的摩尔比限定在本申请优选的范围内有利于提高其形成的涂层的综合性能；比较实施例13至18及比较例6至8可知，采用本申请提供的阳离子固化组合物有利于大幅提高其形成的涂层的综合性能。
综上所述，本发明的阳离子固化组合物在无色体系和有色体系中均表现出优异的柔韧性，且与塑料基材的附着力好，固化速度适中，VOC排放低，可广泛应用于塑料制品中。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (12)

  1. 一种用于塑料基材的阳离子固化组合物，其特征在于，所述用于塑料基材的阳离子固化组合物包括：多羟基树脂(A)、环氧化合物(B)、含氧杂环丁烷基的化合物(C)和阳离子引发剂(D)，其中多羟基树脂(A)为聚酯树脂(A1)、丙烯酸树脂(A2)和/或酚醛树脂(A3)，所述阳离子固化组合物中羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3～20):(1～25)。
  2. 根据权利要求1所述的用于塑料基材的阳离子固化组合物，其特征在于，所述用于塑料基材的阳离子固化组合物中，羟基、三元环氧基团和四元环氧基团的摩尔比为1:(3～10):(5～15)。
  3. 根据权利要求1或2所述的用于塑料基材的阳离子固化组合物，其特征在于，按重量份计，所述用于塑料基材的阳离子固化组合物包括：(5～40)重量份所述多羟基树脂(A)、(10～65)重量份所述环氧化合物(B)、(10～70)重量份所述含氧杂环丁烷基的化合物(C)和(0.5～10)重量份所述阳离子引发剂(D)。
  4. 根据权利要求3所述的用于塑料基材的阳离子固化组合物，其特征在于，按重量份计，所述用于塑料基材的阳离子固化组合物包括：(5～30)重量份所述多羟基树脂(A)、(15～50)重量份所述环氧化合物(B)、(20～60)重量份所述含氧杂环丁烷基的化合物(C)和(2～5)重量份所述阳离子引发剂(D)。
  5. 根据权利要求1所述的用于塑料基材的阳离子固化组合物，其特征在于，所述聚酯树脂(A1)的羟值为50～500mgKOH/g，数均分子量为200～12000；
    优选地，所述聚酯树脂(A1)的羟值为80～350mgKOH/g，数均分子量为300～5000。
  6. 根据权利要求1所述的用于塑料基材的阳离子固化组合物，其特征在于，所述丙烯酸树脂(A2)的羟值为15～200mgKOH/g，玻璃化转变温度为10～150℃，数均分子量为500～20000；
    优选地，所述丙烯酸树脂(A2)的羟值为50～150mgKOH/g，玻璃化转变温度为20～100℃，数均分子量为1000～8000。
  7. 根据权利要求1所述的用于塑料基材的阳离子固化组合物，其特征在于，所述酚醛树脂(A3)的羟值为50～300mgKOH/g，数均分子量为300～15000；
    优选地，所述酚醛树脂(A3)的羟值为100～250mgKOH/g，数均分子量为500～8000。
  8. 根据权利要求1至4中任一项所述的用于塑料基材的阳离子固化组合物，其特征在于，所述环氧化合物(B)选自脂环式环氧化合物和/或脂肪族环氧化合物；
    优选地，所述脂环式环氧化合物的环氧当量为80～500；
    优选地，所述脂肪族环氧化合物的环氧当量为80～500。
  9. 根据权利要求5至8中任一项所述的用于塑料基材的阳离子固化组合物，其特征在于，按重量份计，所述用于塑料基材的阳离子固化组合物还包括(0～40)重量份助剂(E)；
    优选地，所述用于塑料基材的阳离子固化组合物包括(1～10)重量份所述助剂(E)；
    优选地，所述助剂(E)选自增感剂、色材、阻燃剂、流平剂、固化促进剂、光/热产酸剂、粘结促进剂、紫外吸收剂、抗凝聚剂、增稠剂、成核剂、偶联剂、填料、增塑剂、抗冲改性剂、润滑剂、抗菌剂、脱模剂、热稳定剂、抗氧化剂、光稳定剂、增容剂、着色剂、稳定剂、隔离剂、抗静电剂、消泡剂和耐火剂组成的组中的一种或多种。
  10. 一种涂料，其特征在于，所述涂料包括权利要求1至9中任一项所述的用于塑料基材的阳离子固化组合物。
  11. 一种塑料制品，包括塑料基材和涂层，所述涂层涂覆在所述塑料基材的至少部分区域上，其特征在于，所述涂层由权利要求1至9中任一项所述的用于塑料基材的阳离子固化组合物固化形成。
  12. 一种权利要求1至9中任一项所述的用于塑料基材的阳离子固化组合物在能量固化领域的应用。
PCT/CN2020/117189 2019-09-29 2020-09-23 用于塑料基材的阳离子固化组合物、涂料、塑料制品及应用 WO2021057804A1 (zh)

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