Classifications

• • 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
• • 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
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
  • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• • 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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
  • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
  • B05D3/065—After-treatment
  • B05D3/067—Curing or cross-linking the coating
• • 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
• • 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
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • 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
  • 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
  • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/132—Phenols containing keto groups, e.g. benzophenones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • 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
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • 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
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/48—Stabilisers against degradation by oxygen, light or heat
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/67—Particle size smaller than 100 nm
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • 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
  • B05D2201/00—Polymeric substrate or laminate
• • 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
  • B05D2518/00—Other type of polymers
  • B05D2518/10—Silicon-containing polymers
• • 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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/007—After-treatment
• • 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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
• • 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
  • B05D7/52—Two layers
  • B05D7/53—Base coat plus clear coat type
  • B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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  • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • 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
  • C08J2433/04—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 esters
  • C08J2433/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
  • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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  • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to a coated article and a method for manufacturing the same. More specifically, it includes an organic resin base material such as plastic, a primer layer provided on the base material, a hard coat layer provided on the primer layer, and a layer formed on the surface layer of the hard coat layer.
• the present invention relates to a coated article having a photomodified layer and a method for manufacturing the same.
• plastic base materials especially polycarbonate resins
• have excellent transparency, impact resistance, heat resistance, etc. so they are used as structural members in place of glass for various applications such as windows of buildings and vehicles, instrument covers, etc. It is currently used for this purpose.
• surface properties such as scratch resistance and weather resistance are inferior to glass, there is a strong desire to improve the surface properties of polycarbonate resin molded products.
• Patent Document 1 discloses that a protective film is provided using a siloxane-based hard coat paint, and the surface of the protective film is further modified using vacuum ultraviolet light. , a method of forming a photo-modified film has been proposed. On the other hand, the photo-modified film cannot follow the thermal expansion of the resin when the resin molded product is placed under high temperatures, and cracks are likely to occur, resulting in problems in heat resistance and weather resistance.
• Patent Documents 2 and 3 a mesh mask is placed over a siloxane-based hard coat layer, and light is irradiated from above the mesh mask to illuminate the hard coat layer from the openings of the mesh mask to correspond to the shape of the openings of the mesh mask.
• a method has been proposed in which a photo-modified layer and a siloxane-based hard coat layer are alternately formed on the surface of a resin substrate, thereby alleviating the stress applied to the photo-modifying layer due to expansion of the resin substrate and improving heat resistance.
• a simpler manufacturing method is desired.
• the thickness of the primer layer containing the acrylic polymer is set to 10 ⁇ m or more, or the primer layer containing 20 to 60 parts by mass of silica particles is formed with respect to 100 parts by mass of the acrylic polymer, and then It has been reported that heat resistance when heated to 80° C. is improved by forming a siloxane-based hard coat layer and a photo-modifying layer. On the other hand, if the primer layer is thickened or a large amount of silica particles are added, it is likely to cause cracks, early peeling, and whitening of the paint film during weather resistance tests, which poses problems in weather resistance. Further, polycarbonate resins are sometimes required to have heat resistance at higher temperatures exceeding 100°C.
• the present invention was made in view of the above circumstances, and an object of the present invention is to provide a coated article having scratch resistance comparable to that of glass, as well as excellent heat resistance and weather resistance.
• a predetermined primer layer containing a vinyl (co)polymer containing an alkoxysilyl group in its molecular structure on a resin base material A coated article having a predetermined siloxane-based hard coat layer provided on a primer layer and a photo-modifying layer formed on the surface layer of the hard coat layer has scratch resistance comparable to that of glass and excellent scratch resistance. They discovered that it has both heat resistance and weather resistance, and completed the present invention.
• the present invention 1.
• the primer layer is Cured film of a primer composition containing (A) 100 parts by mass of a vinyl (co)polymer, and (B) 1 to 19 parts by mass of inorganic particles with a median diameter of 1 to 100 nm as measured by dynamic light scattering.
• the hard coat layer is (a) The following formula (1): R 1 m Si (OR 2 ) 4-m (1)
• R 1 is each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and a plurality of R 1 may be bonded to each other to form a linking group
• Each R 2 is independently an alkyl group having 1 to 3 carbon atoms, and m is 0, 1 or 2.
• a silicone resin obtained by (co)hydrolyzing and condensing at least one selected from alkoxysilanes represented by and their (partial) hydrolyzed condensates; (b) colloidal silica, (c) a coated article, which is a cured coating of a silicone composition containing an ultraviolet absorber, and the hard coat layer has a thickness of 1 to
• the ultraviolet absorber (c) contains a reactive ultraviolet absorber represented by the following general formula (2) and a (partial) hydrolyzed condensate thereof, [In the formula, R 3 is each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following general formula (3), and at least one of R 3 is It is a group represented by the following general formula (3).
• R 4 and R 5 are each independently an alkyl group having 1 to 5 carbon atoms, j is an integer of 1 to 8, and k is an integer of 0 to 2.
• Asterisk * represents a bond with an adjacent atom.
• the primer composition further contains (C) one or more ultraviolet absorbers selected from triazine derivatives and benzophenone derivatives.
• the primer composition further contains (D) a hindered amine light stabilizer.
• the primer layer has a thickness of 3 to 15 ⁇ m
• the hard coat layer has a thickness of 3 to 13 ⁇ m. 10.
• a method for producing a coated article according to any one of 1 to 9 Provided is a method for producing a coated article, which includes the step of irradiating the surface of a hard coat layer with light having a wavelength of 300 nm or less to form a photo-modified layer on the surface layer of the hard coat layer.
• the present invention it is possible to provide a coated article that has scratch resistance comparable to glass and has excellent heat resistance and weather resistance. Further, according to the present invention, no special operation or equipment is required when photo-modifying the hard coat layer, and no special post-treatment is required after photo-modifying. Therefore, it is possible to more easily impart excellent scratch resistance, heat resistance, and weather resistance to resin base materials of various shapes.
• the coated article of the present invention includes a resin base material, a primer layer provided on the resin base material, a hard coat layer provided on the primer layer, and a surface layer of the hard coat layer. and a photo-modified layer
• the primer layer is a cured film of a primer composition containing a vinyl (co)polymer having an alkoxysilyl group
• the hard coat layer is a coated article in which the hard coat layer is a cured film of a silicone composition containing (a) a silicone resin, (b) colloidal silica, and (c) an ultraviolet absorber.
• the hard coat layer contains an ultraviolet absorber.
• an ultraviolet absorber in the hard coat layer prevents light from reaching the primer layer during photomodification by irradiating the hard coat layer with light, as described below, and prevents peeling of the film and improves adhesion. The deterioration of abrasion resistance caused by a decrease in is suppressed.
• the alkoxysilyl group contained in the primer layer and/or the silanol group generated by its hydrolysis It imparts reactivity with the siloxane in the siloxane-based hard coat layer, improves the adhesion between the base material and the hard coat layer via the primer layer, and also improves the adhesion between the alkoxysilyl group and/or the silanol produced by its hydrolysis.
• crosslinking the groups heat resistance is improved and excellent scratch resistance and weather resistance are exhibited.
• the resin base material in the coated article of the present invention is not particularly limited, but various organic resin base materials are preferably used, and specific examples include polycarbonate resin, polystyrene resin, acrylic resin, modified acrylic resin, Examples include urethane resins, thiourethane resins, polycondensates of halogenated bisphenol A and ethylene glycol, acrylic urethane resins, acrylic resins containing halogenated aryl groups, and sulfur-containing resins. Among these, polycarbonate resin is preferred. Furthermore, examples of these resin base materials include those whose surfaces have been treated, specifically, those which have been subjected to chemical conversion treatment, corona discharge treatment, plasma treatment, treatment with acid or alkaline liquid, etc.
• a laminate or the like in which the surface layer is formed of a different type of resin from the base material body can also be used.
• the laminate include a laminate with an acrylic resin layer or a urethane resin layer on the surface layer of a polycarbonate resin base material manufactured by a coextrusion method or a lamination method, and a laminate with an acrylic resin layer on the surface layer of a polyester resin base material. Examples include laminates and the like.
• the primer layer in the coated article of the present invention consists of a cured film of a primer composition containing the following components (A) and (B).
• (A) Vinyl (co)polymer (1) (A-1) Vinyl-based (co)polymer having an alkoxysilyl group
• the vinyl-based (co)polymer of component (A) is (A-1) a vinyl-based (co)polymer having an alkoxysilyl group. Including coalescence.
• Examples of the vinyl (co)polymer having an alkoxysilyl group as the component (A-1) include a vinyl (co)polymer in which an alkoxysilyl group is bonded to the main chain via a Si-C bond, etc. can be mentioned.
• Such (co)polymers include polymers of vinyl monomers in which alkoxysilyl groups are bonded via Si-C bonds, or vinyl monomers in which alkoxysilyl groups are bonded via Si-C bonds. Examples include copolymers of monomers and other vinyl monomers.
• the vinyl monomer in which an alkoxysilyl group is bonded via a Si-C bond contains one vinyl polymerizable functional group and one or more alkoxysilyl groups in one molecule. You can use whatever you have.
• vinyl-based polymerizable functional groups include organic groups having 2 to 12 carbon atoms, including vinyl, vinyloxy, (meth)acryloxy, ( ⁇ -methyl)styryl groups, and the like. Specific examples include vinyl, 5-hexenyl, 9-decenyl, vinyloxymethyl, 3-vinyloxypropyl, (meth)acryloxymethyl, 3-(meth)acryloxypropyl, 11-(meth)acryloxyundecyl , vinylphenyl (styryl), isopropenylphenyl ( ⁇ -methylstyryl), vinylphenylmethyl group (vinylbenzyl group), and the like. Among these, (meth)acryloxypropyl group is preferred in terms of reactivity and availability.
• (meth)acrylic means acrylic and/or methacryl.
• alkoxy group in the alkoxysilyl group examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups.
• methoxy group and ethoxy group are preferred from the viewpoint of easy control of hydrolyzability and easy availability.
• substituents bonded to silicon atoms other than the above alkoxy groups include alkyl groups such as methyl, ethyl, n-propyl, n-hexyl, and n-decyl groups, and aryl groups such as phenyl groups.
• alkyl groups such as methyl, ethyl, n-propyl, n-hexyl, and n-decyl groups
• aryl groups such as phenyl groups.
• methyl group is preferred because of its easy availability.
• vinyl monomers in which alkoxysilyl groups are bonded via Si-C bonds include: methacryloxymethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxyundecyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyltriethoxysilane, Acryloxypropyltrimethoxysilane, acryloxypropylmethyldimethoxysilane, acryloxypropyldimethylmethoxysilane, acryloxypropyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxyundecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, allyltrimethoxysilane, styryltrimethoxysilane,
• methacryloxypropyltrimethoxysilane methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylmethoxysilane, Acryloxypropyltrimethoxysilane, Acryloxypropylmethyldimethoxysilane is preferred.
• the amount of alkoxysilyl groups in component (A) is preferably 1 to 50% by mass, more preferably 2 to 30% by mass based on the entire component (A). %, more preferably 3 to 15% by mass.
• the amount is 1% by mass or more, the formation of a siloxane network through crosslinking between the above-mentioned vinyl (co)polymers and inorganic fillers will be sufficient, and the linear expansion coefficient of the film will be lowered, resulting in better heat resistance and durability. improves. Further, due to the reaction with the siloxane in the hard coat layer, the adhesion with the hard coat layer and weather resistance are further improved.
• component (A) when the amount of alkoxysilyl groups in component (A) is 50% by mass or less, the crosslinking density does not become too high, and a decrease in adhesiveness due to excessive hardness is suppressed, and unreacted alkoxysilyl groups are removed over time. It is possible to suppress the occurrence of cracks in the film due to post-crosslinking.
• vinyl monomers that can be copolymerized with the vinyl monomer to which the alkoxysilyl group is bonded via a Si-C bond are not particularly limited as long as they are copolymerizable vinyl monomers. , (meth)acrylic monomers, (meth)acrylic esters, (meth)acrylonitrile, (meth)acrylamide, alkyl vinyl ethers, alkyl vinyl esters, styrene, and derivatives thereof.
• (meth)acrylic esters and their derivatives include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate.
• n-butyl isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, (meth)acrylic acid n-hexyl, isohexyl (meth)acrylate, n-heptyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Isooctyl, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-undecyl (meth)acrylate, n-(meth)acrylate Dodecyl,
• (meth)acrylonitrile derivatives include ⁇ -chloroacrylonitrile, ⁇ -chloromethylacrylonitrile, ⁇ -trifluoromethylacrylonitrile, ⁇ -methoxyacrylonitrile, ⁇ -ethoxyacrylonitrile, vinylidene cyanide, and the like.
• (meth)acrylamide derivatives include N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N- Methoxy(meth)acrylamide, N,N-dimethoxy(meth)acrylamide, N-ethoxy(meth)acrylamide, N,N-diethoxy(meth)acrylamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide, N- (2-hydroxyethyl)(meth)acrylamide, N,N-dimethylaminomethyl(meth)acrylamide, N-(2-dimethylamino)ethyl(meth)acrylamide, N,N'-methylenebis(meth)acrylamide, N, Examples include N'-ethylenebis(meth)acrylamide and the like.
• alkyl vinyl ether examples include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and the like.
• alkyl vinyl esters include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, vinyl stearate, and the like.
• styrene and its derivatives include styrene, ⁇ -methylstyrene, vinyltoluene, and the like.
• (meth)acrylic acid esters are preferred, including methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate.
• the component (A-1) a product obtained by chemically bonding (C) an ultraviolet absorber to a vinyl copolymer, which will be described later, can be used.
• the above polymer can be obtained, for example, by copolymerizing a (meth)acrylic monomer having an ultraviolet absorbing group in the molecule.
• the (meth)acrylic monomer having an ultraviolet absorbing group include benzotriazole compounds represented by the following general formula (4).
• X is a hydrogen atom or a chlorine atom
• R 6 is a hydrogen atom, a methyl group , or a tertiary alkyl group having 4 to 8 carbon atoms
• It is a chain alkylene group having 2 to 10 carbon atoms
• R 8 represents a hydrogen atom or a methyl group.
• the tertiary alkyl group having 4 to 8 carbon atoms for R 6 is a tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, di-tert-octyl group. etc.
• the alkylene group having 2 to 10 carbon atoms for R 7 may be linear or branched, such as ethylene, trimethylene, propylene, tetramethylene, 1,1-dimethyltetramethylene, pentamethylene, hexamethylene. , heptamethylene, octamethylene, nonamethylene, decamethylene groups, and the like.
• benzotriazole compound represented by the above general formula (4) examples include 2-(2'-hydroxy-5'-(meth)acryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloxymethylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-(meth)acryloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(2-(meth)acryloxyethyl)phenyl]-5-chloro-2H-benzotriazole, Examples include 2-[2'-hydroxy-3'-methyl-5'-(8-(meth)acryloxyoctyl)phenyl]-2H-benzotriazole.
• the amount of the ultraviolet absorbing group bonded to the vinyl copolymer is preferably 1 to 20% by weight, more preferably 5 to 15% by weight in the vinyl copolymer of component (A-1). It is preferable to contain 1% by mass or more of the above-mentioned ultraviolet absorbing group, since the ultraviolet absorption properties and weather resistance will be good. When the content is 20% by mass or less, it is preferable because whitening of the coating can be prevented and crack resistance becomes good.
• Component (A-1) may be used alone or in combination of two or more.
• component (A-1) those having the following structural units (i) to (iii) are particularly preferred. Furthermore, vinyl copolymers having an alkoxysilyl group and an ultraviolet absorbing group can also be preferably used, and those containing the following structural units (i) to (iv) are more preferable. Note that the order of each structural unit contained in component (A-1) is arbitrary, and component (A-1) may be any of an alternating copolymer, a random copolymer, and a block copolymer. .
• Component (A-1) is a radical polymerization initiator selected from peroxides such as dicumyl peroxide and benzoyl peroxide, and azo compounds such as azobisisobutyronitrile, in a solution containing the above monomer. It can be obtained by adding an agent and carrying out a polymerization reaction under heating (for example, at 50 to 150°C, particularly 70 to 120°C, for 1 to 10 hours, especially 3 to 8 hours).
• the polystyrene equivalent weight average molecular weight of the vinyl (co)polymer of component (A-1) determined by gel permeation chromatography (GPC) is preferably 50,000 to 1,000,000, and preferably 60,000 to 800. ,000 is more preferable.
• the molecular weight is 1,000,000 or less, the viscosity does not become too high and the handling properties are excellent, and when it is 50,000 or more, appearance defects such as whitening of the film are suppressed, and better adhesiveness and durability are achieved. Provides durability and weather resistance.
• the primer composition of the present invention also contains (A-2) a vinyl-based copolymer not containing an alkoxysilyl group. You can stay there.
• the above-mentioned vinyl-based (co)polymer not containing an alkoxysilyl group is not particularly limited, but may include a monomer other than the vinyl-based monomer to which the above-mentioned alkoxysilyl group is bonded via a Si-C bond. Obtained by polymerization.
• Monomers other than vinyl monomers in which alkoxysilyl groups are bonded via Si-C bonds, which are raw materials for component (A-2), include component (A-1), in which alkoxysilyl groups are bonded to Si-C bonds.
• Examples of other copolymerizable monomers other than the vinyl monomer bonded via a -C bond include the same monomers as those exemplified, and specific examples thereof also include the same ones.
• the vinyl monomers that are the raw materials for component (A-2) these monomers may be used alone or in combination of two or more.
• (meth)acrylic acid esters are preferred, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
• n-hexyl (meth)acrylate 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, 4-methylcyclohexyl (meth)acrylate, More preferred are 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc., and methyl (meth)acrylate. is even more preferable.
• Polymerization conditions such as reaction temperature, time, and polymerization initiator are not particularly limited, and may be carried out under known conditions.
• peroxides such as dicumyl peroxide and benzoyl peroxide, and azobisisobutyro It can be easily obtained by using a radical polymerization initiator selected from azo compounds such as nitriles and reacting at 50 to 150°C, particularly 70 to 120°C, for 1 to 10 hours, particularly 3 to 8 hours.
• component (A-2) commercially available products may be used.
• Component (A-2) may be used alone or in combination of two or more.
• the weight average molecular weight of component (A-2) measured by GPC in terms of polystyrene is preferably 50,000 to 1,000,000, more preferably 60,000 to 800,000. If the molecular weight is too large, the viscosity may become too high, making it difficult to synthesize or handle; if the molecular weight is too small, it may cause poor appearance such as whitening of the film, or it may not be possible to obtain sufficient adhesion, durability, and weather resistance. There may be no.
• the weight average molecular weight of the entire component (A-1) and (A-2) in terms of polystyrene by GPC is 6,000 to 1,000. ,000 is preferred, and 50,000 to 800,000 is more preferred. If the molecular weight is too large, the viscosity may become too high, making it difficult to synthesize or handle; if the molecular weight is too small, it may cause poor appearance such as whitening of the film, or it may not be possible to obtain sufficient adhesion, durability, and weather resistance. There may be no.
• Component (B) is an inorganic particle with a median diameter of 1 to 100 nm as measured by dynamic light scattering.
• the inorganic particles for example, particles of known inorganic oxides such as silica, alumina, cerium oxide, zirconium oxide, zinc oxide, and titanium oxide can be used singly or in combination of two or more. Among these, particles of silica, zinc oxide, titanium oxide and cerium oxide are preferred. By using the above particles, the hardness and scratch resistance of the coating can be increased. In addition, by using particles such as cerium oxide, zirconium oxide, zinc oxide, titanium oxide, etc., the ultraviolet shielding ability can be further enhanced. Among the above-mentioned particles, silica particles and/or zinc oxide particles are particularly preferred because they provide good coating appearance and weather resistance.
• the inorganic particles have a median diameter of 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 40 nm in a volume particle size distribution measured by a dynamic light scattering method. If the median diameter exceeds 100 nm, the coating will lack transparency due to light scattering in the visible region, and if it is less than 1 nm, the coating will have poor hardness, scratch resistance, and weather resistance.
• an apparatus such as Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) can be used for measurement by dynamic light scattering.
• the amount of the inorganic particles blended is 1 to 19 parts by weight, preferably 3 to 16 parts by weight, and more preferably 5 to 15 parts by weight, per 100 parts by weight of the vinyl (co)polymer of component (A). preferable. If it is less than 1 part by mass, weather resistance will be insufficient, and if it exceeds 19 parts by mass, poor film appearance such as decreased adhesion or whitening will occur, and cracks will easily occur during weather resistance tests, resulting in poor weather resistance. Getting worse.
• the primer composition preferably contains (C) an ultraviolet absorber and (D) a hindered amine light stabilizer as an ultraviolet stabilizer for the purpose of preventing yellowing and surface deterioration of the resin base material.
• the ultraviolet absorber as component (C) may be contained in the vinyl (co)polymer as component (A-1) in the form of a chemical bond, as described above, or it may be contained as an additive. good. When introduced as an additive, benzophenone derivatives, benzotriazole derivatives, cyanoacrylate derivatives, triazine derivatives, etc. are preferred.
• the total amount thereof is preferably 2 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of component (A).
• the amount is 2 parts by mass or more, the weather resistance is further improved, and when it is 50 parts by mass or less, poor coating appearance such as decreased adhesion and whitening of the coating can be suppressed.
• a triazozine derivative When a triazozine derivative is used as an ultraviolet absorber, it is preferably used in an amount of 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of component (A). It is preferable to contain 1 part by mass or more of the triazozine derivative, since the ultraviolet absorption properties and weather resistance will be good. When it is contained in an amount of 10 parts by mass or less, whitening of the coating can be prevented and crack resistance can be improved, which is preferable. When a benzophenone derivative is used as a UV absorber, it is preferably 7 to 40 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of component (A).
• the benzophenone derivative When the benzophenone derivative is contained in an amount of 7 parts by mass or more, the ultraviolet absorption characteristics become good and the weather resistance becomes good, which is preferable. When it is contained in an amount of 40 parts by mass or less, whitening of the coating can be prevented and crack resistance can be improved, which is preferable.
• the primer composition preferably contains (D) a hindered amine light stabilizer. Particularly preferred are those having one or more cyclic hindered amine structures in the molecule, having good compatibility with the primer composition used in the present invention, and having low volatility.
• hindered amine light stabilizers include 3-dodecyl-1-(2,2',6,6'-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-methyl-3-dodecyl -1-(2,2',6,6'-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1-(2,2',6,6'- Tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, bis(2,2',6,6'-tetramethyl-4-piperidyl) sebacate, bis(1,2,2',6, 6'-pentamethyl-4-piperidyl), tetrakis (2,2',6,6'-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2' , 6,6'-penta
• a silylation-modified light stabilizer as described in Japanese Patent Publication No. 61-56187, for example, 2,2,6,6-tetramethylpiperidino-4-propyl trimethoxysilane, 2,2',6,6'-tetramethylpiperidino-4-propylmethyldimethoxysilane, 2,2',6,6'-tetramethylpiperidino-4-propyltriethoxysilane, Examples include 2,2',6,6'-tetramethylpiperidino-4-propylmethyldiethoxysilane and (partial) hydrolysates thereof.
• These light stabilizers can be used alone or in combination of two or more. Among these, a neutral hindered amine light stabilizer (TINUVIN249, manufactured by BASF Japan Ltd.) is preferred.
• the blending amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and 1 to 5 parts by weight, based on 100 parts by weight of component (A). Mass % is more preferred. A content of 0.1 parts by mass or more is preferable because weather resistance becomes good, and a content of 10 parts by mass or less is preferable because poor coating appearance such as decreased adhesion and whitening of the coating can be suppressed.
• the primer composition may contain a solvent.
• the solvent is not particularly limited as long as it dissolves or disperses the above components, but highly polar organic solvents are preferred.
• organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, t-butanol, cyclohexanol, and diacetone alcohol; methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone and diacetone alcohol; Ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; ethyl acetate, Examples include esters such as
• the solid content concentration of the primer composition is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. Outside this range, defects may occur in the film cured from the composition. That is, if the concentration is less than the above range, the coating tends to sag, curl, or become uneven, and the desired hardness and scratch resistance may not be obtained. Furthermore, if the concentration exceeds the above range, brushing, whitening, and cracking of the film may easily occur.
• a dispersing agent for the inorganic particle component (B) may be added to the primer composition as long as the effect of the present invention is not impaired.
• the dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, various silane compounds or siloxane compounds that are reactive with particle surfaces, such as silane coupling agents.
• the above primer composition may absorb water during storage or use, and the alkoxysilyl group in the vinyl (co)polymer (A) may be hydrolyzed, resulting in a decrease in storage stability.
• a dehydrating agent may be added.
• the dehydrating agent include orthocarboxylic acid esters such as methyl orthoformate, ethyl orthoformate, and ethyl orthoacetate; dialkylcarbodiimides such as dicyclohexylcarbodiimide; solid adsorbents such as silica gel and molecular sieve.
• the primer composition may optionally contain a leveling agent, a metal powder, an antioxidant, a heat ray reflection/absorption agent, a flexibility agent, an antistatic agent, as long as it does not impede the effects of the present invention.
• An antifouling agent, a water repellent agent, etc. may be added.
• the pH of the solution of the primer composition is preferably 2 to 8, more preferably 3 to 6. If the pH is outside this range, storage stability may be reduced.
• the method for adjusting the pH is not particularly limited, but it can also be adjusted to the above range by adding a pH adjuster.
• a pH adjuster When the pH of the primer composition is outside the above range, if it is on the acidic side than this range, you can adjust the pH by adding a basic compound such as ammonia or ethylenediamine, or if it is on the basic side, add hydrochloric acid.
• the pH may be adjusted using an acidic compound such as nitric acid, acetic acid, or citric acid.
• the primer composition used in the present invention can be obtained by mixing the above-mentioned components according to a conventional method. Furthermore, a primer layer can be formed by applying the obtained primer composition onto a resin base material and curing it.
• examples of the coating method of the primer composition include various coating methods such as brush coating, spraying, dipping, flow coating, roll coating, curtain coating, spin coating, and knife coating.
• the primer composition may be cured by leaving it in the air and drying it, or by heating it.
• the curing temperature and curing time are not particularly limited, but for example, it is preferable to heat at a temperature below the heat resistant temperature of the base material for 10 minutes to 2 hours, and more preferably to heat at 80 to 135°C for 30 minutes to 2 hours. preferable.
• the thickness of the primer layer needs to be 1 to 20 ⁇ m, and 3 to 15 ⁇ m in order to satisfy the requirements for film hardness, scratch resistance, long-term stable adhesion, and no cracking. is preferable, and more preferably 5 ⁇ m or more and less than 10 ⁇ m. If the film thickness is less than 1 ⁇ m, the ultraviolet shielding ability will be insufficient and peeling of the film will occur, and if the film thickness exceeds 20 ⁇ m, cracks will occur in the film.
• the coated article of the present invention has a hard coat layer formed on the primer layer.
• the hard coat layer in the coated article of the present invention is a cured film of a silicone composition containing the following components (a) to (c).
• R 1 is each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group
• R 2 is each independently an alkyl group having 1 to 3 carbon atoms
• m is , 0, 1 or 2).
• a silicone resin obtained by (co)hydrolyzing and condensing at least one selected from alkoxysilanes represented by and their (partial) hydrolyzed condensates; (b) colloidal silica, (c) Ultraviolet absorber
• Component (a) is a silicone resin obtained by (co)hydrolyzing and condensing at least one selected from alkoxysilanes represented by the following general formula (1) and (partially) hydrolyzed condensates thereof.
• each R 1 is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 1s are bonded to each other to form a linking group.
• each R 2 independently represents an alkyl group having 1 to 3 carbon atoms, and m is 0, 1 or 2.
• the monovalent hydrocarbon group R 1 may be linear, branched, or cyclic, and has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms; cycloalkyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; alkenyl having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms Groups include aryl groups having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms.
• R 1 monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; vinyl and allyl groups; Alkenyl groups such as groups; aryl groups such as phenyl groups, and the like.
• some or all of the hydrogen atoms of these groups may be substituted with other substituents, specific examples of which include chloromethyl, ⁇ -chloropropyl, 3,3,3-trifluoropropyl.
• Halogen-substituted hydrocarbon groups such as ⁇ -(meth)acryloxypropyl, ⁇ -glycidoxypropyl, 3,4-epoxycyclohexylethyl, ⁇ -mercaptopropyl, ⁇ -aminopropyl, ⁇ -isocyanatepropyl groups, etc.
• Examples include (meth)acryloxy, epoxy, mercapto, amino, and isocyanate group-substituted hydrocarbon groups.
• Another example is an isocyanurate group in which a plurality of isocyanate group-substituted hydrocarbon groups are bonded to each other.
• alkyl groups are preferred when used in applications that require scratch resistance and weather resistance, and when toughness and dyeability are required, epoxy, (meth)acryloxy, and isocyanurate-substituted carbonized Hydrogen groups are preferred.
• Examples of the alkyl group having 1 to 3 carbon atoms for R 2 include methyl, ethyl, n-propyl, and isopropyl groups. Among these, methyl group and ethyl group are preferred, considering their high reactivity in hydrolysis and condensation and the fact that the alcohol R 2 OH produced has a high vapor pressure and is easily distilled off.
• tetraalkoxysilane represented by the general formula: Si(OR 2 ) 4 and its partially hydrolyzed condensate (a-0) include tetramethoxysilane, Partially hydrolyzed condensate of tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetramethoxysilane (product name "M Silicate 51", manufactured by Tama Chemical Industry Co., Ltd., product name "MSI51”, manufactured by Colcoat Co., Ltd.) , product names "MS51", “MS56”, manufactured by Mitsubishi Chemical Corporation), partial hydrolyzed condensates of tetraethoxysilane (product names "Silicate 35", “Silicate 45", manufactured by Tama Chemical Industry Co., Ltd.), products name “ESI40", “ESI48”, manufactured by Colcoat Co., Ltd.), co-partial hydrolysis conden
• trialkoxysilane (a-1) represented by the general formula: R 1 Si (OR 2 ) 3 and its partially hydrolyzed condensate include hydrogentrified Methoxysilane, hydrogentriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimeth
• Partially hydrolyzed condensate of silylpropyl) isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, and methyltrimethoxysilane product name: KC-89S, X-40-9220, Shin-Etsu Chemical Co., Ltd.
• a partially hydrolyzed condensate of methyltrimethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane (trade name "X-41-1056", manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
• dialkoxysilane represented by the general formula: R 1 2 Si (OR 2 ) 2 and its (partial) hydrolyzed condensate (a-2) are: , methylhydrogendimethoxysilane, methylhydrogendiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxy Silane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -(3,4-epoxycyclohexyl)eth
• the silicone resin of component (a) may be prepared using the components (a-0), (a-1), and (a-2) in any ratio, but it also has storage stability, scratch resistance,
• the number of silicon atoms derived from (a-0) is 0 compared to the total number of Si atoms of (a-0), (a-1) and (a-3). ⁇ 50%, the number of silicon atoms derived from (a-1) is preferably 50 to 100%, the number of silicon atoms derived from (a-2) is preferably 0 to 50%, and the number of silicon atoms derived from (a-0) is preferably used.
• the number of silicon atoms derived from (a-1) is 70-100%, and the number of silicon atoms derived from (a-2) is 0-30%.
• the main component (a-1) is 50% or more because the curability is good and the hardness of the cured film is appropriate.
• components (a-0), (a-1), and (a-2) may be (co)hydrolyzed and condensed by a known method.
• the alkoxysilanes of components (a-0), (a-1), and (a-2), their (partial) hydrolyzed condensates, or mixtures thereof are used at a pH of 1 to 7.5, preferably 2 to 7.5.
• Silicone resin is obtained by (co)hydrolyzing and condensing with water in step 7. At this time, metal oxide fine particles such as silica sol dispersed in water may be used.
• Metal oxide fine particles may also be used as a catalyst. Further, during hydrolysis, metal oxide fine particles such as silica sol dispersed in water or an organic solvent may coexist.
• the amount of water used is preferably 20 to 3,000 parts by mass based on a total of 100 parts by mass of components (a-0), (a-1), and (a-2).
• Use of excessive water may not only reduce the efficiency of the device, but also cause a reduction in coatability and drying properties of the final composition due to the influence of the remaining water.
• the amount is preferably 50 parts by mass or more and less than 150 parts by mass.
• reaction solvent may contain an organic solvent, but preferably does not contain an organic solvent. This is because the molecular weight of the obtained silicone resin tends to decrease as the organic solvent is contained.
• the condensation step may be carried out continuously following the hydrolysis step, and is usually carried out at room temperature or under heating at a liquid temperature of 100° C. or lower. At temperatures higher than 100°C, gelation may occur. Furthermore, condensation can be promoted by distilling off the alcohol produced by hydrolysis at 80° C. or higher and under normal pressure or reduced pressure. Furthermore, for the purpose of promoting condensation, a condensation catalyst such as a basic compound, an acidic compound, or a metal chelate compound may be added. Before or during the condensation process, an organic solvent may be added for the purpose of adjusting the progress and concentration of condensation.Also, metal oxide fine particles such as silica sol dispersed in water or an organic solvent may be used. May be added.
• the organic solvent to be added should be one that dissolves the silicone resin well and has a boiling point of 80.
• a relatively highly polar organic solvent having a temperature of 0.degree. C. or higher is preferable.
• Specific examples of such organic solvents include alcohols such as isopropyl alcohol, n-butanol, isobutanol, t-butanol, cyclohexanol, and diacetone alcohol; methylpropyl ketone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone.
• ketones such as diacetone alcohol
• ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; propyl acetate, acetic acid
• esters such as butyl and cyclohexyl acetate.
• the polystyrene equivalent weight average molecular weight in GPC analysis of the obtained silicone resin is preferably 1,500 to 50,000, more preferably 2,000 to 20,000.
• the molecular weight is 1,500 or more, the film has excellent toughness and can suppress the occurrence of cracks, while when the molecular weight is 50,000 or less, the hardness may become too low or the resin in the film may undergo phase separation. It is possible to suppress the whitening of the film due to this.
• Component (b) is colloidal silica.
• the component (b), colloidal silica preferably has a form in which silica is colloidally dispersed in a medium such as water or an organic solvent, and commercially available aqueous dispersion and organic dispersion types can be used. Specific examples include Snowtex-O, OS, O40, OL, methanol silica sol, IPA-ST, IBA-ST, PMA-ST, and MEK-ST manufactured by Nissan Chemical Co., Ltd. Silica having a median diameter of 5 to 50 nm as measured by a dynamic light scattering method is preferable from the viewpoint of transparency and hardness of the resulting hard coat layer.
• the amount of colloidal silica to be blended is preferably 3 to 100 parts by weight, more preferably 6 to 50 parts by weight, and even more preferably 10 to 30 parts by weight, based on 100 parts by weight of component (a). be.
• Component (c) is an ultraviolet absorber.
• the ultraviolet absorber (c) include benzophenone derivatives, benzotriazole derivatives, cyanoacrylate derivatives, and triazine derivatives. Specific examples include 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2
• silanes in which a part of the above compound is substituted with an alkoxysilyl group Coupling agent type reactive UV absorbers can be used.
• a silane coupling agent type reactive ultraviolet absorber in which a portion of the above compound is substituted with an alkoxysilyl group is preferred.
• the reactive ultraviolet absorber is preferably a benzophenone derivative having one or more alkoxysilyl groups represented by the following general formula (2).
• R 3 is each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following general formula (3), and at least one of R 3 is the following: It is a group represented by general formula (3).
• R 4 and R 5 are each independently an alkyl group having 1 to 5 carbon atoms, j is an integer of 1 to 8, and k is an integer of 0 to 2.
• Asterisk * represents a bond with an adjacent atom.
• the alkyl group of R 3 has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and may be linear or branched. Specific examples include methyl, ethyl , n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl groups, and the like.
• at least one of R 3 is a group represented by the above general formula (3).
• the ultraviolet absorber is immobilized within the hard coat layer and bleed-out over time is suppressed, which is effective in suppressing whitening and cracking of the hard coat layer. It is true.
• at least one of R 3 is a hydroxy group because the ultraviolet absorbability becomes better, and R 3 other than the group represented by the above general formula (3) and the hydroxy group are hydrogen atoms. It is preferable that there be.
• the alkyl group having 1 to 5 carbon atoms in R 4 and R 5 preferably has 1 to 3 carbon atoms, and specific examples thereof include the same groups as those exemplified for R 3 respectively. can be mentioned.
• R 4 is preferably a methyl group or an ethyl group.
• R 5 is preferably a methyl group or an ethyl group in view of high reactivity in hydrolysis and condensation, high vapor pressure of alcohol R 5 OH produced, and ease of distillation.
• the blending amount of component (c) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (a).
• the silicone composition preferably contains a curing catalyst that promotes the condensation reaction of condensable groups such as silanol groups and alkoxy groups contained in the silicone resin (a).
• curing catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium propionate, potassium propionate, sodium acetate, potassium acetate, sodium formate, potassium formate, trimethylbenzylammonium hydroxide, Basics such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium acetate, n-hexylamine, tributylamine, diazabicycloundecene (DBU), dicyandiamide, etc.
• DBU diazabicycloundecene
• the amount of the curing catalyst is not particularly limited as long as it is an amount effective for curing the silicone resin of component (a).
• the amount is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass. If it is 0.0001% by mass or more, curing will be sufficient, and if it is 1% by mass or less, cracks in the film and a decrease in water resistance can be suppressed.
• the silicone composition contains a solvent.
• the solvent include those similar to those used in the above primer composition.
• the amount thereof is such that the solid content concentration of the silicone composition is preferably 5 to 40% by mass, more preferably 10 to 35% by mass.
• the silicone composition may contain a pH adjuster, a leveling agent, a thickener, a pigment, a dye, metal oxide particles other than silica, metal powder, and an antioxidant, as necessary, within a range that does not impair the effects of the present invention. , an ultraviolet stabilizer, a heat ray reflection/absorption agent, a flexibility agent, an antistatic agent, an antifouling agent, a water repellent agent, and the like.
• the silicone composition used in the present invention can be obtained by mixing the above-mentioned components according to a conventional method. Furthermore, a hard coat layer can be formed by applying the obtained silicone composition onto the primer layer and curing it.
• the method for applying the silicone composition includes the same methods as those exemplified for the primer composition.
• the silicone composition may be cured by leaving it in the air and drying it, or by heating it.
• the curing temperature and curing time are not particularly limited, but for example, it is preferable to heat at a temperature below the heat resistant temperature of the base material for 10 minutes to 2 hours, and more preferably to heat at 80 to 135°C for 30 minutes to 2 hours. preferable.
• the thickness of the obtained hard coat layer is not particularly limited, but it should be 1 to 15 ⁇ m in order to satisfy the requirements of hardness, scratch resistance, long-term stable adhesion, and absence of cracks. It is necessary, preferably 3 to 13 ⁇ m, more preferably 5 to 10 ⁇ m. If the thickness is less than 1 ⁇ m, the ultraviolet shielding ability will be insufficient, peeling of the coating will occur, and the hardness and scratch resistance of the coating will be insufficient. Moreover, if the film thickness exceeds 15 ⁇ m, cracks will occur in the film.
• the hard coat layer preferably has a surface hardness of 0.10 to 0.50 GPa, more preferably 0.20 to 0.40 GPa, and more preferably 0.25 to 0.35 GPa, as measured by a nanoindentation method. More preferred.
• Examples of devices for measuring the elastic modulus of such a film include a nanoindenter (Hysitron Libo Indenter, manufactured by Bruker Japan Co., Ltd.; ENT-NEXUS, manufactured by Elionix Co., Ltd.), and the like.
• the surface hardness is 0.10 GPa or more, it is preferable because the abrasion resistance when forming the photo-modified layer becomes good.
• the siloxane hard coat layer can effectively relieve the stress that the photomodified layer receives from the resin base material during heat resistance tests and weather resistance tests, so the resistance This is preferable because crack resistance is improved and the film has good heat resistance and weather resistance.
• the above hardness is determined by indenting a Berkovich type indenter onto the surface of the siloxane hard coat layer at a room temperature of 23° C. using a nanoindenter (ENT-NEXUS, manufactured by Elionix Co., Ltd.) under a load of 0. This is a value obtained by analyzing data obtained when pushing with 5 mN using dedicated software.
• the coated article of the present invention has a photo-modifying layer formed on the surface layer of the hard coat layer.
• the photo-modifying layer in the coated article of the present invention is preferably a hard thin film layer containing silicon dioxide as a main component obtained by irradiating the surface of the hard coat layer with light having a wavelength of 300 nm or less.
• the energy of short wavelength light of 300 nm or less cuts the bond chains of organic polymers and destroys the C-H, Si-C, Si- By sequentially and selectively cutting O-Si bonds and recombining the cleaved oxygen atoms and silicon atoms, a part of the hard coat layer is modified into a hard thin film layer mainly composed of silicon dioxide. It is known that it is possible.
• Examples of light sources for vacuum ultraviolet light having a short wavelength of 300 nm or less include excimer lasers, excimer lamps, and low-pressure mercury lamps.
• Examples of excimer lasers include Ar 2 laser with a wavelength of 126 nm, F 2 laser with a wavelength of 157 nm, ArF excimer laser with a wavelength of 193 nm, KrF excimer laser with a wavelength of 248 nm, XeCl excimer laser with a wavelength of 307 nm, etc. can be mentioned.
• light sources of vacuum ultraviolet light of 300 nm or less are Ar 2 laser, F 2 laser, ArF laser, and KrF excimer laser.
• excimer lamps have wavelengths of 126 nm (Ar 2 ), 146 nm (Kr 2 ), 165 nm (ArBr), 172 nm (Xe 2 ), 175 nm (ArCl), 193 nm (ArF), 207 nm (KrBr), and 222 nm (KrCl). , 253 nm (XeCl), 283 nm (XeBr), and 308 nm (XeCl).
• the ultraviolet irradiation method is not particularly limited, but examples thereof include a method in which the hard coat layer is irradiated with ultraviolet rays having a wavelength of 300 nm or less using the above light source in the atmosphere or an inert gas atmosphere such as nitrogen or argon.
• the cumulative light amount is preferably 0.1 J/cm 2 or more, more preferably 0.5 J/cm 2 or more.
• the thickness of the photo-modified layer is preferably 0.1 to 1.0 ⁇ m, more preferably 0.2 to 0.8 ⁇ m, and even more preferably 0.3 to 0.6 ⁇ m.
• the film thickness is 0.1 ⁇ m or more, it is preferable because wear resistance becomes good.
• the film thickness is 1.0 ⁇ m or less, it is preferable because heat resistance and weather resistance become good.
• the coated article of the present invention may further have an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor-deposited film layer, etc. on the photo-modifying layer.
• the visible light transmittance of the coating is the visible light transmittance of the coating.
• evaluation can be made by the haze value of the film. Since the haze increases as the film thickness increases, in the present invention, the haze at a film thickness of 20 ⁇ m or less is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less.
• the haze of the film can be measured, for example, with a turbidity meter NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
• One of the characteristics of the coated article of the present invention is good adhesion between the coating and the base material.
• it can be evaluated by a checkerboard peel test according to JIS K5400. Using a razor blade, make 25 vertical and 6 horizontal cuts in the film at 2 mm intervals to create 25 grids, and after adhering Sellotape (registered trademark, manufactured by Nichiban Co., Ltd.) well, 90° The number of squares (X) that remains without the coating peeling off when rapidly peeled off in the front direction is expressed as X/25.The closer the value of the number of squares (X) is to 25, the better the adhesion. You can say that.
• a base material having a cured film is boiled in water at 100° C. for 2 hours and a similar grid test is performed, it can be used as an index of water-resistant adhesion.
• the coated article of the present invention has excellent scratch resistance.
• the haze difference ( ⁇ Hz) before and after the Taber abrasion test can be used for evaluation. Based on ASTM1044, ⁇ Hz (% points) when wearing a wear wheel CS-10F with a Taber abrasion tester and measuring the haze after 500 rotations under a load of 500 gf (haze (%) after the test) - When evaluated by (haze (%) before test), ⁇ Hz at a film thickness of 20 ⁇ m or less is preferably 10 points or less, more preferably 5 points or less, and still more preferably 2 points or less. In this field, if the haze difference ( ⁇ Hz) is 2 points or less in the above test, it is common to judge that the material has scratch resistance equivalent to or higher than that of glass.
• One of the characteristics of the coated article of the present invention is good heat resistance.
• An example of a heat resistance test is a method in which the specimen is stored in an oven at 110° C. for 100 to 1000 hours, and the appearance of the specimen is observed every 100 hours.
• One of the characteristics of the coated article of the present invention is good weather resistance.
• it can be determined by the change in the appearance of the film in a weather resistance test.
• a weather resistance test an eye super UV tester W-151 manufactured by Iwasaki Electric Co., Ltd. was used to irradiate ultraviolet light for 4 hours (irradiation intensity 90 mW/cm 2 , black panel temperature 63°C, humidity 70%) for 4 hours.
• irradiation intensity 90 mW/cm 2 black panel temperature 63°C, humidity 70%
• evaluation can be performed visually or using a microscope.
• Microscopes that can be used for this purpose are not particularly limited, but include, for example, a laser microscope (manufactured by Keyence Corporation, device name "VK-8710").
• a laser microscope manufactured by Keyence Corporation, device name "VK-8710"
• the cumulative energy when irradiated with ultraviolet light with an intensity of 900 W/m 2 for 1 hour is 0.9 kWh/m 2 , which is equal to 3.24 MJ (megajoule) according to the rules for converting units of assembly. . Therefore, the cumulative irradiation amount after 600 hours of the above SUV test is 600 (test time) x 1/3 (light irradiation test ratio) x 3.24 (MJ/m 2 h) ⁇ 648 (MJ/m 2 ) becomes.
• test conditions and environment for the weather resistance test in the present invention can be set arbitrarily, the correlation between the test conditions and outdoor exposure can be easily estimated.
• an ultraviolet light meter I Ultraviolet Light Meter UVP365-1, manufactured by Iwasaki Electric Co., Ltd.
• UVP365-1 ultraviolet light meter
• UVP365-1 ultraviolet light meter
• the cumulative irradiation amount after 600 hours of the above SUV test corresponds to the cumulative irradiation amount received by the sample after approximately 9 years of outdoor use in Japan, based on the following formula. 648 (MJ/m 2 , cumulative irradiation amount after 600 hours test) / 72 (MJ/m 2 ⁇ year, annual light irradiation amount in Japan) ⁇ 9 (year). Since the outdoor environment changes depending on latitude and climate, the test conditions may be changed as appropriate depending on the environment in which the cured film is used.
• % represents mass %
• parts represent parts by mass
• Me represents a methyl group.
• the weight average molecular weight was measured by gel permeation chromatography (GPC) using standard polystyrene.
• a monomer mixed solution prepared in advance (90 g of ⁇ -methacryloxypropyltrimethoxysilane, 270 g of methyl methacrylate, 22.5 g of glycidyl methacrylate, RUVA-1 (2-[2'-Hydroxy-5'-(2-methacryloxyethyl)phenyl]-2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) 67.5 g, 2,2'-azobis(2- A mixture of 1 g of methylbutyronitrile) was added dropwise at 80 to 90°C over 1.5 hours, and the mixture was further stirred at 80 to 90°C for 5 hours.
• A-2-1 Polymethyl methacrylate resin (Dyanal BR-88, manufactured by Mitsubishi Rayon Co., Ltd., Mw: 576,900, Tg: 105°C)
• A-2-2 Polymethyl methacrylate resin (Dyanal BR-85, manufactured by Mitsubishi Rayon Co., Ltd., Mw: 263,800, Tg: 105°C)
• B-1 Silica propylene glycol monomethyl ether dispersion (PMA-ST, solid content concentration 30%, primary particle size 10-15 nm, manufactured by Nissan Chemical Co., Ltd.)
• B-2 Alcohol dispersion of zinc oxide (ZNTANB15WT%-E34, solid content concentration 15%, primary particle diameter 10-15 nm, manufactured by CIK Nanotech Co., Ltd.)
• C-1 2-[2-hydroxy-4-(1-octyloxycarbonylethoxy)phenyl]-4,6-bis(4-phenylphenyl)-1,3,5-triazine (TINUVIN479, BASF Japan Ltd. ) made)
• C-2 2,4-dihydroxybenzophenone (Seesorb 106, manufactured by Cipro Kasei Co., Ltd.)
• G-1 LE-604 (manufactured by Kyoeisha Chemical Co., Ltd.)
• a silicone composition (HC-1 or HC-2 prepared in Synthesis Example 4 or Comparative Synthesis Example 1) described in Table 2 and Table 3 was further applied on the primer layer.
• a silicone composition (HC-1 or HC-2 prepared in Synthesis Example 4 or Comparative Synthesis Example 1) described in Table 2 and Table 3 was further applied on the primer layer.
• a silicone composition (HC-1 or HC-2 prepared in Synthesis Example 4 or Comparative Synthesis Example 1) described in Table 2 and Table 3 was further applied on the primer layer. ) was applied as a cured film by a dip coating method to a thickness of 5 ⁇ m or more and less than 10 ⁇ m, and was cured at 120° C. for 60 minutes to form a siloxane hard coat layer.
• the surface of the siloxane hard coat layer was irradiated with light at a light dose of 2 J/cm 2 in an N 2 atmosphere to form a film with a thickness of 0.2 J/cm 2 .
• Comparative example 5 Test of Comparative Example 5 was carried out in the same manner as Examples 1 to 8 and Comparative Examples 1 to 4 above, except that the primer layer was coated with a dip coating method so that the thickness of the primer layer was 22 ⁇ m, and the thickness of the hard coat layer was 16 ⁇ m. Got a piece.
• Comparative example 6 A test piece of Comparative Example 6 was obtained in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 4, except that no photo-modified layer was formed.
• the hardness of the film in the present invention was determined by a nanoindentation method using a nanoindenter (ENT-NEXUS, manufactured by Elionix Co., Ltd.). Specifically, the resin base material having the siloxane-based hard coat layer on the outermost surface prepared in the above Examples and Comparative Examples was cut into 15 mm x 15 mm, and a special sample fixing base material (10 mm x 10 mm, thickness A measurement sample was obtained by applying an instant adhesive (Aron Alpha quick-acting multi-purpose, manufactured by Toagosei Co., Ltd.) to a 1 mm thick film and adhering the base material side of the sample to the fixing base material.
• an instant adhesive Aron Alpha quick-acting multi-purpose, manufactured by Toagosei Co., Ltd.
• the obtained measurement sample was fixed on a dedicated sample fixing table with the siloxane hard coat layer side in contact with the indenter, and a Berkovich type indenter was pressed into the coating surface at a room temperature of 23°C, and a load of 0.5 mN was applied.
• the surface hardness of the film was determined by analyzing the data obtained when the film was pushed in with special software. The surface hardness was determined by performing the same operation at three different points on each sample, and the average value was calculated.
• the coated articles of Examples 1 to 8 that meet the requirements of the present invention have good coating transparency and adhesion to the polycarbonate resin base material, and have a scratch resistance ⁇ Hz of 2 points or less. It showed excellent scratch resistance. In addition, even after the heat resistance test and the SUV weather resistance test, there was no coating cracking or peeling, making it clear that the film had both excellent heat resistance and weather resistance.

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