WO2016021545A1 - 塗布フィルム - Google Patents
塗布フィルム Download PDFInfo
- Publication number
- WO2016021545A1 WO2016021545A1 PCT/JP2015/071943 JP2015071943W WO2016021545A1 WO 2016021545 A1 WO2016021545 A1 WO 2016021545A1 JP 2015071943 W JP2015071943 W JP 2015071943W WO 2016021545 A1 WO2016021545 A1 WO 2016021545A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- film
- coating
- polyester
- Prior art date
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
-
- 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
- C08J7/046—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
- C09D133/14—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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8093—Compounds containing active methylene 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
- 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
- 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
-
- 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
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
-
- 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
- C08J2433/14—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 halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08K3/34—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
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- 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
-
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- 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
-
- 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
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
Definitions
- the present invention relates to a coated film, and particularly relates to a coated film that is suitably used as an ITO film substrate of a touch panel and has good surface hardness, wear resistance, and adhesion between a coated layer and a polyester film. .
- Polyester film exhibits excellent properties such as mechanical properties, dimensional stability, heat resistance, transparency, electrical insulation, chemical resistance, etc., so film base materials in fields such as building materials, optical applications, and packaging applications As widely used.
- polyester film has low surface hardness and low wear resistance. Therefore, there is a problem that it is easily damaged during various processing steps and during use.
- a method of providing a hard coat layer on the surface of a polyester film is known in order to improve surface hardness and wear resistance (Cited document 1).
- a hard-coat layer has low adhesiveness with a polyester film, and may peel off during various processes or during use.
- JP-A-11-34243 Japanese Patent Laid-Open No. 10-166531 JP 2006-205545 A
- the present invention has been made in view of the above-mentioned circumstances, and the problem to be solved is to provide a coated film having excellent surface hardness and wear resistance, and having good adhesion between the polyester film and the hard coat layer. There is to do.
- the gist of the present invention is to have a coating layer formed from a coating solution containing a (meth) acrylate compound, a reactive silica having a (meth) acryloyl group and an isocyanate compound on at least one surface of a polyester film. It exists in the characteristic coating film.
- a coated film having high surface hardness and good adhesion to a polyester film can be provided, and its industrial value is high.
- the polyester film constituting the coated film of the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as the gist of the present invention is not exceeded other than the two-layer or three-layer structure. It may be a multilayer and is not particularly limited.
- the polyester used in the present invention may be a homopolyester or a copolyester.
- a homopolyester those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred.
- the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid
- examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol.
- Typical polyester includes polyethylene terephthalate and the like.
- examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (for example, p-oxybenzoic acid).
- examples of the glycol component include one or more types such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like.
- the polymerization catalyst for polyester is not particularly limited, and conventionally known compounds can be used, and examples thereof include titanium compounds, germanium compounds, antimony compounds, manganese compounds, aluminum compounds, magnesium compounds, and calcium compounds.
- titanium compounds and germanium compounds are preferable because they have high catalytic activity, can be polymerized in a small amount, and the amount of metal remaining in the film is small, so that the brightness of the film is increased.
- a germanium compound is expensive, it is more preferable to use a titanium compound.
- the titanium element content is preferably 50 ppm or less, more preferably 1 to 20 ppm, still more preferably 2 to 10 ppm. If the content of the titanium compound is too high, the polyester may be deteriorated in the process of melt-extruding the polyester, resulting in a strong yellowish film. If the content is too low, the polymerization efficiency is poor and the cost is low. In some cases, a film having a sufficient strength or a sufficient strength cannot be obtained. Moreover, when using the polyester by a titanium compound, it is preferable to use a phosphorus compound in order to reduce the activity of a titanium compound for the purpose of suppressing deterioration in the step of melt extrusion.
- the phosphorus element content is preferably in the range of 1 to 300 ppm, more preferably 3 to 200 ppm, still more preferably 5 to 100 ppm, based on the amount of polyester to be melt-extruded. If the content of the phosphorus compound is too large, it may cause gelation or foreign matter. If the content is too small, the activity of the titanium compound cannot be lowered sufficiently, and the yellowish It may be a film.
- an ultraviolet absorber can be contained in order to improve the weather resistance of the film and prevent deterioration of the liquid crystal.
- the ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays and can withstand the heat applied in the production process of the polyester film.
- an organic ultraviolet absorber there are an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
- an organic type ultraviolet absorber For example, a cyclic imino ester type, a benzotriazole type, a benzophenone type etc. are mentioned. From the viewpoint of durability, a cyclic imino ester type and a benzotriazole type are more preferable. It is also possible to use two or more ultraviolet absorbers in combination.
- particles can be blended mainly for the purpose of imparting slipperiness and preventing the occurrence of scratches in each step.
- the kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness.
- Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid.
- examples include inorganic particles such as magnesium, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin.
- precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.
- the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction
- the average particle diameter of the particles is preferably 5 ⁇ m or less, more preferably in the range of 0.01 to 3 ⁇ m. By using in the above range, a film having good transparency and slipperiness can be obtained.
- the particle content in the polyester film is preferably 5% by weight or less, more preferably in the range of 0.0003 to 3% by weight.
- the particle content in the polyester film is preferably 5% by weight or less, more preferably in the range of 0.0003 to 3% by weight.
- the method for adding particles to the polyester film is not particularly limited, and a conventionally known method can be adopted.
- it can be added at any stage for producing the polyester constituting each layer, but it is preferably added after completion of esterification or transesterification.
- antioxidants In addition to the above-described particles and ultraviolet absorber, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like can be added to the polyester film as necessary. .
- the thickness of the polyester film is not particularly limited as long as it can be formed as a film, but is preferably 10 to 350 ⁇ m, more preferably 15 to 300 ⁇ m.
- a production example of the polyester film will be specifically described, but is not limited to the following production example. That is, there is a method in which pellets obtained by drying the polyester raw material described above are extruded from a die using a single screw extruder, and a molten sheet is cooled and solidified with a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in the biaxial direction.
- the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine.
- the stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times.
- the film is stretched in the direction perpendicular to the first stretching direction.
- the stretching temperature is usually 70 to 170 ° C.
- the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there.
- heat treatment is performed at a temperature of 180 to 270 ° C. under tension or relaxation within 30% to obtain a biaxially oriented film.
- a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.
- the simultaneous biaxial stretching method is a method in which the above-mentioned unstretched sheet is stretched and oriented simultaneously in the machine direction and the width direction in a state where the temperature is usually controlled at 70 to 120 ° C., preferably 80 to 110 ° C. Is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times in terms of area magnification. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film.
- a conventionally known stretching method such as a screw method, a pantograph method, or a linear driving method can be employed.
- the coating layer constituting the coating film of the present invention
- it may be provided by in-line coating which treats the film surface during the process of forming a polyester film, or offline coating which is applied outside the system on a once produced film may be adopted.
- in-line coating which treats the film surface during the process of forming a polyester film
- offline coating which is applied outside the system on a once produced film
- In-line coating is a method of coating in the process of manufacturing a polyester film, and specifically, a method of coating at an arbitrary stage from melt-extrusion of polyester to heat-fixing and winding after stretching. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding.
- an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding.
- a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and coating layer formation can be performed at the same time.
- the coating layer can be stretched together with the base film, whereby the coating layer can be firmly adhered to the base film. Furthermore, in the production of a biaxially stretched polyester film, the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties. Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film forming property, surface hardness, and abrasion resistance of the coating layer are improved. It can make it adhere more firmly.
- the present invention it is essential to have a coating layer formed from a coating solution containing a (meth) acrylate compound, a reactive silica having a (meth) acryloyl group and an isocyanate compound on at least one surface of the polyester film.
- the coating liquid according to a preferred embodiment of the present invention further contains an acrylic resin.
- the (meth) acrylate compound conventionally known compounds can be used, and are not particularly limited, but monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or higher polyfunctional (meth) acrylate may be used. Can be mentioned. Among them, a trifunctional or higher polyfunctional (meth) acrylate is preferable in order to achieve high hardness.
- the monofunctional (meth) acrylate is not particularly limited. For example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, alkyl (meth) acrylate such as isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate such as hydroxyalkyl (meth) acrylate, Alkoxyalkyl (meth) such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, etc.
- Aromatic (meth) acrylates such as acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, amino group-containing (meth) acrylates such as diaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxyethylene glycol ( (Meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, ethylene oxide modified (meth) acrylate such as phenylphenol ethylene oxide modified (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic An acid etc. are mentioned.
- the bifunctional (meth) acrylate is not particularly limited.
- the trifunctional or higher polyfunctional (meth) acrylate is not particularly limited.
- dipentaerythritol hexa (meth) acrylate dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrile Methylolpropane tetra (meth) acrylate
- pentaerythritol tri (meth) acrylate trimethylolpropane tri (meth) acrylate, tetramethylol methane ethylene oxide modified tetra (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ⁇ - Isocyanuric acid-modified tri (meth) acrylate such as caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate hex Diisocyanate ure
- the reactive silica having the (meth) acryloyl group is used for the purpose of improving the hardness of the coating layer.
- the reactive silica having a (meth) acryloyl group represents a silica particle having a compound having a (meth) acryloyl group on at least a part of the surface.
- a method for introducing a compound having a (meth) acryloyl group into silica particles can be a conventionally known method, and is not particularly limited.
- the compound has a (meth) acryloyl group-containing silane coupling agent and the silica particle surface. Examples include a method of reacting a silanol group.
- Examples of the compound having a (meth) acryloyl group include the same compounds as the (meth) acrylate compound used for forming the coating layer described above.
- silica particles conventionally known ones can be used, and are not particularly limited, but are not limited to ordinary colloidal silica, and may be hollow silica, porous silica, or the like.
- the average particle size is preferably 300 nm or less, more preferably 10 to 200 nm, and still more preferably 15 to 100 nm. By using it in the above range, a coating layer excellent in transparency, surface hardness, and abrasion resistance can be obtained.
- the aforementioned isocyanate compound is used for the purpose of improving the adhesion between the coating layer and the polyester film. Furthermore, since the isocyanate compound has an isocyanurate structure, the adhesion with the coating layer can be improved without greatly reducing the surface hardness and wear resistance of the coating layer.
- the isocyanurate structure is a structure having an isocyanurate group in the molecule, and conventionally known ones can be used, and examples thereof include a trimer of an isocyanate compound.
- the isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate.
- isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate.
- Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate
- Alicyclic isocyanates such as bets are exemplified. Reaction products of these isocyanates with various polymers and compounds may be used. These may be used alone or in combination. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.
- examples of the blocking agent include active methylene compounds, phenol compounds, mercaptan compounds, lactam compounds, amine compounds, amide compounds, and oxime compounds. These may be used alone or in combination of two or more. Among these, an active methylene compound is preferable from the viewpoint of improving adhesion with a polyester film.
- Examples of the active methylene blocking agent include isobutanoyl acetate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, n-hexanoyl acetate, 2-ethylheptanoyl acetate, malonate, Examples thereof include acetoacetic acid esters and acetylacetone.
- isobutanoyl acetate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, n-hexanoyl acetate, 2- Ethylheptanoyl acetate is preferable, more preferably isobutanoyl acetate, n-propanoyl acetate, and n-pentanoyl acetate, and still more preferably isobutanoyl acetate.
- examples of isobutanoyl acetate include, for example, methyl isobutanoyl acetate, ethyl isobutanoyl acetate, n-propyl isobutanoyl acetate, isopropyl isobutanoyl acetate, n-butyl isobutanoyl acetate, isobutyl isobutanoyl acetate, t-butyl isobutanoyl acetate, isobutanoyl acetate
- Examples thereof include n-pentyl, n-hexyl isobutanoyl acetate, 2-ethylhexyl isobutanoyl acetate, phenyl isobutanoyl acetate, benzyl isobutanoyl acetate and the like.
- methyl isobutanoyl acetate and ethyl isobutanoyl acetate are preferred.
- n-propanoyl acetate include n-propanoyl acetate methyl, n-propanoyl acetate, n-propanoyl acetate, n-propanoyl acetate, n-propanoyl acetate, and t-butyl n-propanoyl acetate. Of these, methyl n-propanoyl acetate and ethyl n-propanoyl acetate are preferred.
- n-pentanoyl acetate examples include n-pentanoyl methyl acetate, n-pentanoyl ethyl acetate, n-pentanoyl acetate isopropyl, n-pentanoyl acetate n-butyl, and n-pentanoyl acetate t-butyl. Of these, methyl n-pentanoyl acetate and ethyl n-pentanoyl acetate are preferred.
- the isocyanate compound may be used alone, or may be used as a mixture or combination with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate-based compound, it is also possible to use a mixture or bonded product with a polyester resin or a polyurethane resin.
- the acrylic resin is used for improving the transparency and appearance of the coating layer.
- the isocyanate compound used for forming the coating layer is used for the purpose of improving the adhesion between the coating layer and the polyester film, but it has been found that the transparency and appearance deteriorate accordingly. As a result of intensive studies, it was found that transparency and appearance can be improved by using an acrylic resin together.
- Acrylic resin is a polymer composed of polymerizable monomers including acrylic and methacrylic monomers. These may be either homopolymers or copolymers, and copolymers with polymerizable monomers other than acrylic and methacrylic monomers. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included.
- a polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or a polyurethane dispersion (sometimes a mixture of polymers) is also included.
- a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in another polymer solution or dispersion is also included.
- the polymerizable monomer is not particularly limited, but particularly representative compounds include, for example, various carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid.
- Monomers, and their salts such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydroxyfumarate, monobutylhydroxyitaconate
- Various hydroxyl group-containing monomers various (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate;
- (Meth) acrylamide Various nitrogen-containing compounds such as diacetone acrylamide, N-methylol acrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, ⁇ -methylstyrene, divinylbenzene, vinyltoluene, various types such as vinyl propionate Vinyl esters; various silicon-containing polymerizable monomers
- the ratio of the nitrogen-containing compound contained in the acrylic resin is preferably 1 to 50 mol%, more preferably 1 to 20 mol%, still more preferably 1 to 10 mol%.
- various polymers other than acrylic resins can be used in combination for improving the coating appearance, transparency and adhesion. However, if the amount of the polymer is too large, the surface hardness and wear resistance of the coating layer may be lowered.
- polystyrene resin examples include polyurethane resin, polyester resin, polyvinyl (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches and the like.
- the polyurethane resin is a polymer compound having a urethane bond in the molecule, and is usually produced by a reaction between a polyol and an isocyanate.
- the polyol include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.
- Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides.
- polycarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.
- polyhydric alcohol ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 2-methyl-2-propyl- , 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexane Diol, 1,9-nonanediol
- Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction.
- Polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Examples thereof include diol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane.
- Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate.
- Examples of the polycarbonate-based polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.
- polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
- Examples of the isocyanate used for obtaining the polyurethane resin include the same isocyanate compounds as described above.
- a chain extender may be used when synthesizing the polyurethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.
- chain extender having two hydroxyl groups examples include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. And glycols such as glycols.
- chain extender having two amino groups examples include aromatic diamines such as tolylenediamine, xylylenediamine, diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1, 9-nonanediamine, 1, 10- Aliphatic diamines such as decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1, 3-Bisaminomethylcyclohexa And alicyclic diamines such as
- a crosslinking agent other than the isocyanate compound can be used in combination for improving the coating appearance, transparency, strength of the coating layer, and the like.
- crosslinking agent examples include melamine compounds, oxazoline compounds, carbodiimide compounds, epoxy compounds, silane coupling compounds, and the like.
- the melamine compound is a compound having a melamine skeleton in the compound.
- an alkylolized melamine derivative, a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and these Mixtures can be used.
- alcohol used for etherification methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used.
- a melamine compound either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used.
- a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.
- the oxazoline compound is a compound having an oxazoline group in the molecule, and is particularly preferably a polymer containing an oxazoline group, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer.
- Addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
- the other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer.
- alkyl (meth) acrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene
- Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alky
- a carbodiimide-based compound is a compound having a carbodiimide structure, and is a compound having one or more carbodiimide structures in the molecule, but for better adhesion, etc., the polycarbodiimide having two or more in the molecule More preferred are system compounds.
- the carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used.
- the diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used.
- tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.
- adding a surfactant, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, A hydroxyalkyl sulfonate may be added and used.
- the content of the carbodiimide group contained in the carbodiimide-based compound is a carbodiimide equivalent (weight of the carbodiimide compound to give 1 mol of carbodiimide group [g]), and is usually 100 to 1000, preferably 250 to 800, more preferably 300. It is in the range of -700, more preferably in the range of 350-650.
- Examples of the epoxy compound include a compound containing an epoxy group in the molecule, a prepolymer and a cured product thereof.
- Examples include condensates of epichlorohydrin with hydroxyl groups and amino groups such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A, and polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. is there.
- polyepoxy compound examples include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane.
- polyglycidyl ether and diepoxy compound examples include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether.
- Polypropylene glycol diglycidyl ether polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′,-tetraglycidyl-m-. Examples include xylylenediamine and 1,3-bis (N, N-diglycidylamino) cyclohexane.
- cross-linking agents are used in a design that improves the performance of the coating layer by reacting in the drying process or film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or mixtures thereof exist in the finished coating layer.
- particles other than reactive silica having a (meth) acryloyl group can be used in combination for forming the coating layer.
- the average particle diameter of the particles is preferably in the range of 1.0 ⁇ m or less, more preferably in the range of 0.5 ⁇ m or less, and still more preferably in the range of 0.2 ⁇ m or less from the viewpoint of the transparency of the film.
- the particles to be used include inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles.
- an antifoaming agent a coating property improver, a thickener, an organic lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant are formed as necessary for forming the coating layer.
- Foaming agents, dyes, pigments and the like may be used in combination.
- the ratio of the (meth) acrylate compound in the coating solution is preferably 10 to 95% by weight, more preferably 30 to 90% by weight, and further preferably 40 to 80% by weight. By using it in the above range, it is possible to obtain a coating layer excellent in surface hardness and wear resistance.
- the ratio of the reactive silica having (meth) acryloyl groups in the coating solution is preferably in the range of 1 to 60% by weight, more preferably 5 to 45%, still more preferably 10 to 40%. More preferably. By using it in the above range, a coating layer excellent in surface hardness, abrasion resistance, transparency, and coating appearance can be obtained.
- the ratio of the isocyanate compound in the coating liquid is preferably 1 to 60% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 25% by weight. By using it in the above range, a coating layer having excellent surface hardness, abrasion resistance, and adhesion to a polyester film can be obtained.
- the ratio is preferably in the range of 0.2 to 12% by weight, more preferably 0.3 to 8% by weight, and still more preferably 0.5 to 5% by weight. .
- a coating layer having excellent surface hardness, abrasion resistance, and adhesion to a polyester film can be obtained.
- the ratio of the acrylic resin in the coating liquid is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight, and further preferably 1 to 10% by weight. By using it in the above range, a coating layer excellent in surface hardness, abrasion resistance, transparency, and coating appearance can be obtained.
- a coating layer on the surface opposite to the surface on which the coating layer is provided.
- examples thereof include polymers such as polyester resins, acrylic resins, polyurethane resins, cross-linking agents such as oxazoline compounds, epoxy compounds, melamine compounds, isocyanate compounds, carbodiimide compounds, etc., and these materials may be used alone. A plurality of types may be used in combination.
- a coating layer formed from a coating liquid containing a (meth) acrylate compound, a reactive silica having a (meth) acryloyl group as described above, and an isocyanate compound (a coating layer having the same surface on both sides of a polyester film). It may be.
- the analysis of the components in the coating layer can be performed, for example, by analysis of TOF-SIMS, ESCA, fluorescent X-rays and the like.
- an organic solvent may be contained in the coating solution for the purpose of improving the dispersibility in water, improving the film forming property, and the like within the range not impairing the gist of the present invention. Only one type of organic solvent may be used, or two or more types may be used as appropriate.
- the film thickness of the coating layer is preferably in the range of 0.1 to 10 ⁇ m, more preferably 0.6 to 3.0 ⁇ m, and still more preferably 0.8 to 2.0 ⁇ m. By using it in the above range, a coating layer excellent in surface hardness, abrasion resistance, adhesion to a polyester film and transparency can be obtained.
- the haze of the coated film of the present invention is preferably 5.0% or less, more preferably 2.0% or less, and still more preferably 1.0% or less. By using in the said range, it can use suitably for various uses.
- the haze (haze difference) of the coating layer is preferably 1.0% or less, more preferably 0.5% or less, and still more preferably 0.2% or less. By using in the said range, it can use suitably for various uses.
- Examples of the method for forming the coating layer include gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, Conventionally known coating methods such as spray coating, calendar coating and extrusion coating can be used.
- the drying and curing conditions for forming the coating layer on the polyester film are not particularly limited.
- the coating layer is usually 80 to 200 ° C. for 3 to 40 seconds, preferably Heat treatment is preferably performed at 100 to 180 ° C. for 3 to 40 seconds as a guide.
- the method of stretching in the transverse direction after coating on a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is excellent.
- it is preferably preheated and dried at 60 to 150 ° C., more preferably 70 to 130 ° C., more preferably 75 to 120 ° C., preferably 70 to 170 ° C., more preferably 80 to 160 ° C.
- heat treatment is preferably performed at 180 to 270 ° C., more preferably 190 to 260 ° C., and still more preferably 200 to 250 ° C.
- a polyester film having excellent mechanical properties can be obtained, and at the same time, a coating layer having excellent surface hardness, abrasion resistance, and adhesion to the polyester film can be obtained. it can.
- polyester film constituting the coated film of the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.
- Coating layer thickness measurement method The coated film was embedded in an epoxy resin and cut in the thickness direction of the coated layer by an ultrathin section method. The cross section of the coating layer was measured using a SEM (S-4300N, manufactured by Hitachi High-Technologies Corporation, acceleration voltage 15 kV), and the average value at 10 locations was taken as the film thickness of the coating layer.
- Adhesion measurement method The coated layer of the coated film was scratched at 5 mm intervals with a cutter knife, a 24 mm wide tape (Cello Tape (registered trademark) CT-24 manufactured by Nichiban Co., Ltd.) was applied, and it was peeled off rapidly at a peeling angle of 180 degrees ( Adhesion 1). The coated film treated for 48 hours under the conditions of 80 ° C. ⁇ 90% RH was similarly evaluated (adhesion 2). The peeled surface was observed. If the peeled surface area was 5% or less, A was 5% and 10% or less, B was 10% and 25% or less, C, and 25% or more D.
- Pencil hardness measurement method The measurement was performed according to JIS K5600-5-4 except that the load was 500 g. A pencil hardness F or higher is a practically preferable range.
- Abrasion resistance Using a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), the film surface is rubbed (10 reciprocations) with a test load of 200 g and steel wool # 0000. If it is 5, it is B, if it is 6 or more, it is C, and if it is A or more, it is a practically preferable range.
- Haze difference (Haze of polyester film provided with coating layer) ⁇ (Haze of polyester film without coating layer)
- polyester (A) The polyester used in the examples and comparative examples was prepared as follows. ⁇ Method for producing polyester (A)> 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 30 ppm of ethyl acid phosphate with respect to the resulting polyester, and 100 ppm of magnesium acetate tetrahydrate with respect to the resulting polyester as the catalyst at 260 ° C. in a nitrogen atmosphere at 260 ° C. The reaction was allowed to proceed. Subsequently, 50 ppm of tetrabutyl titanate was added to the resulting polyester, the temperature was raised to 280 ° C. over 2 hours and 30 minutes, the pressure was reduced to 0.3 kPa in absolute pressure, and melt polycondensation was further carried out for 80 minutes. 0.63 polyester (A) was obtained.
- polyester (C) is obtained using the same method as the production method of polyester (A), except that 0.3 part by weight of silica particles having an average particle diameter of 2 ⁇ m is added before melt polymerization. It was.
- Examples of compounds constituting the coating layer are as follows.
- (Example compounds) ⁇ (Meth) acrylate compounds: (I) After mixing and stirring 100 parts of a mixture of 30% by weight of dipentaerythritol pentaacrylate and 70% by weight of dipentaerythritol hexaacrylate, 5 parts of a polyalkylene oxide surfactant, 230 parts of ion-exchanged water, An aqueous dispersion treated with a high-pressure homogenizer.
- ⁇ Reactive silica particles having a (meth) acryloyl group (II) Colloidal silica whose surface is modified with 3-methacryloxypropyltrimethoxysilane and having an average particle size of 30 nm
- Block polyisocyanate obtained by adding 58.9 parts by weight of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 parts by weight of 2-ethylhexyl acid phosphate.
- Isocyanate structure content 6.2% by weight
- Block polyisocyanate obtained by adding 58.9 parts by weight of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 parts by weight of 2-ethylhexyl acid phosphate.
- Isocyanate structure content 6.9 wt%
- Block polyisocyanate obtained by adding 58.9 parts by weight of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 parts by weight of 2-ethylhexyl acid phosphate.
- Isocyanate structure content 4.7% by weight
- Example 1 In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film.
- the finished polyester film was as shown in Table 2 and had good adhesion, pencil hardness, abrasion resistance, haze and haze difference.
- Example 1 In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. When the finished coated film was evaluated, it was as shown in Table 2, and any of the adhesion to the polyester film, pencil hardness, abrasion resistance, haze, and haze difference was inferior.
- the film of the present invention can be suitably used for applications that require surface hardness, wear resistance, and adhesion between the coating layer and the polyester film, such as an ITO film substrate for touch panels.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacturing & Machinery (AREA)
Abstract
Description
ポリエステルに非相溶な他のポリマー成分および顔料を除去したポリエステル1gを精秤し、フェノール/テトラクロロエタン=50/50(重量比)の混合溶媒100mlを加えて溶解させ、30℃で測定した。
TEM(株式会社日立ハイテクノロジーズ製 H-7650、加速電圧100kV)を使用して塗布層を観察し、粒子10個の粒径の平均値を平均粒径とした。
塗布フィルムをエポキシ樹脂中に包埋し、超薄切片法により塗布層の厚さ方向に切断した。塗布層断面をSEM(株式会社日立ハイテクノロジーズ製 S-4300N、加速電圧15kV)を用いて測定し、10箇所の平均値を塗布層の膜厚とした。
塗布フィルムの塗布層にカッターナイフで5mm間隔にキズをつけ、24mm幅のテープ(ニチバン株式会社製セロテープ(登録商標)CT-24)を貼り付け、180度の剥離角度で急激にはがした(密着性1)。80℃×90%RH条件下で48時間処理した塗布フィルムを同様に評価した(密着性2)。剥離面を観察し、剥離面積が5%以下ならばA、5%を超え10%以下ならばB、10%を超え25%以下ならC、25%を超えるならばDとした。
荷重を500gにする以外はJIS K5600-5-4に準拠して測定した。
鉛筆硬度F以上が実用上好ましい範囲である。
学振型摩擦堅牢度試験機(AB-301、テスター産業株式会社製)を用いて試験荷重200g、スチールウール#0000でフィルム表面を摩擦し(10往復)、傷が無ければA、1本~5本ならばB、6本以上ならばCとし、A以上であれば実用上好ましい範囲である。
ヘーズメーター(HM-150、株式会社村上色彩技術研究所製)を使用して、JIS K 7136に準拠してフィルム単枚のヘーズを測定した。
(8)ヘーズ差:
ヘーズと同様に測定し、下記の通り求めた。
ヘーズ差=(塗布層を設けたポリエステルフィルムのヘーズ)-(塗布層を設けていないポリエステルフィルムのヘーズ)
塗布フィルムをハロゲンライト(NIGHT BLASTER QH-2000)を使用して塗布層側から観察し、塗布ムラが無ければA、軽微で見にくい場合はB、ハロゲンライトで明瞭に確認でき、蛍光灯では軽微に確認できる場合はC、ハロゲンライトでも蛍光灯でも明瞭に確認できる場合はDとした。
<ポリエステル(A)の製造方法>
テレフタル酸ジメチル100重量部、エチレングリコール60重量部、エチルアシッドフォスフェートを生成ポリエステルに対して30ppm、触媒として酢酸マグネシウム・四水和物を生成ポリエステルに対して100ppmを窒素雰囲気下、260℃でエステル化反応をさせた。引き続いて、テトラブチルチタネートを生成ポリエステルに対して50ppm添加し、2時間30分かけて280℃まで昇温すると共に、絶対圧力0.3kPaまで減圧し、さらに80分、溶融重縮合させ、極限粘度0.63のポリエステル(A)を得た。
テレフタル酸ジメチル100重量部、エチレングリコール60重量部、触媒として酢酸マグネシウム・四水和物を生成ポリエステルに対して900ppmを窒素雰囲気下、225℃でエステル化反応をさせた。引き続いて、正リン酸を生成ポリエステルに対して3500ppm、二酸化ゲルマニウムを生成ポリエステルに対して70ppm添加し、2時間30分かけて280℃まで昇温すると共に、絶対圧力0.4kPaまで減圧し、さらに85分、溶融重縮合させ、極限粘度0.64のポリエステル(B)を得た。
ポリエステル(A)の製造方法において、溶融重合前に平均粒径2μmのシリカ粒子を0.3重量部添加する以外はポリエステル(A)の製造方法と同様の方法を用いてポリエステル(C)を得た。
(化合物例)
・(メタ)アクリレート化合物:(I)
ジペンタエリスリトールペンタアクリレート30重量%およびジペンタエリスリトールヘキサアクリレート70重量%の混合物100部、ポリアルキレンオキサイド系界面活性剤5部、イオン交換水230部を混合して撹拌した後、超音波分散機と高圧ホモジナイザーで処理をした水分散体。
・(メタ)アクリロイル基を有する反応性シリカ粒子:(II)
表面を3-メタクリロキシプロピルトリメトキシシランで変性した平均粒径30nmのコロイダルシリカ
(I)下記方法で合成したブロックポリイソシアネート
ヘキサメチレンジイソシアネート1000重量部を60℃で攪拌し、触媒としてテトラメチルアンモニウム・カプリエート0.1重量部を加えた。4時間後、リン酸0.2重量部を添加して反応を停止させ、イソシアヌレート型ポリイソシアネート組成物を得た。得られたイソシアヌレート型ポリイソシアネート組成物100重量部、数平均分子量400メトキシポリエチレングリコール42.3重量部、プロピレングリコールモノメチルエーテルアセテート29.5重量部を仕込み、80℃で7時間保持した。その後反応液温度を60℃に保持し、イソブタノイル酢酸メチル35.8重量部、マロン酸ジエチル32.2重量部、ナトリウムメトキシドの28%メタノール溶液0.88重量部を添加し、4時間保持した。n-ブタノール58.9重量部を添加し、反応液温度80℃で2時間保持し、その後、2-エチルヘキシルアシッドホスフェート0.86重量部を添加して得られたブロックポリイソシアネート。イソシアネート構造含有量=6.2重量%
(I)下記方法で合成したブロックポリイソシアネート
ヘキサメチレンジイソシアネート1000重量部を60℃で攪拌し、触媒としてテトラメチルアンモニウム・カプリエート0.1重量部を加えた。4時間後、リン酸0.2重量部を添加して反応を停止させ、イソシアヌレート型ポリイソシアネート組成物を得た。得られたイソシアヌレート型ポリイソシアネート組成物100重量部、数平均分子量200のメトキシポリエチレングリコール42.3重量部、プロピレングリコールモノメチルエーテルアセテート29.5重量部を仕込み、80℃で7時間保持した。その後反応液温度を60℃に保持し、イソブタノイル酢酸メチル35.8重量部、マロン酸ジエチル32.2重量部、ナトリウムメトキシドの28%メタノール溶液0.88重量部を添加し、4時間保持した。n-ブタノール58.9重量部を添加し、反応液温度80℃で2時間保持し、その後、2-エチルヘキシルアシッドホスフェート0.86重量部を添加して得られたブロックポリイソシアネート。イソシアネート構造含有量=6.9重量%
(I)下記方法で合成したブロックポリイソシアネート
ヘキサメチレンジイソシアネート1000重量部を60℃で攪拌し、触媒としてテトラメチルアンモニウム・カプリエート0.1重量部を加えた。4時間後、リン酸0.2重量部を添加して反応を停止させ、イソシアヌレート型ポリイソシアネート組成物を得た。得られたイソシアヌレート型ポリイソシアネート組成物100重量部、数平均分子量1000のメトキシポリエチレングリコール42.3重量部、プロピレングリコールモノメチルエーテルアセテート29.5重量部を仕込み、80℃で7時間保持した。その後反応液温度を60℃に保持し、イソブタノイル酢酸メチル35.8重量部、マロン酸ジエチル32.2重量部、ナトリウムメトキシドの28%メタノール溶液0.88重量部を添加し、4時間保持した。n-ブタノール58.9重量部を添加し、反応液温度80℃で2時間保持し、その後、2-エチルヘキシルアシッドホスフェート0.86重量部を添加して得られたブロックポリイソシアネート。イソシアネート構造含有量=4.7重量%
メチルメタクリレート:エチルメタクリレート:エチルアクリレート:アクリロニトリル:N-メチロールアクリルアミド:アクリル酸=40:22:21:10:3:4(mol%)から形成されるアクリル樹脂の水分散体(乳化剤:アニオン系界面活性剤)
エチルアクリレート:n-ブチルアクリレート:メチルメタクリレート:N-メチロールアクリルアミド:アクリル酸=67:17:10:2:4(mol%)から形成されるアクリル樹脂の水分散体(乳化剤:アニオン系界面活性剤)
メチルメタクリレート:エチルメタクリレート:エチルアクリレート:アクリロニトリル:アクリル酸=43:22:21:10:4(mol%)から形成されるアクリル樹脂の水分散体(乳化剤:アニオン系界面活性剤)
平均粒径30nmのコロイダルシリカ
ヘキサメトキシメチロールメラミン
オキサゾリン基及びポリアルキレンオキシド鎖を有するアクリルポリマー。オキサゾリン基量=4.5mmol/g
ポリグリセロールポリグリシジルエーテル。
トリレンジイソシアネート:テレフタル酸:イソフタル酸:エチレングリコール:ネオペンチルグリコール:ジメチロールプロパン酸=14:17:17:23:24:5(mol%)から形成されるポリエステル系ポリウレタン樹脂の水分散体。
モノマー組成 (酸成分)テレフタル酸:イソフタル酸:5-ソジウムスルホイソフタル酸://(ジオール成分)エチレングリコール:1,4-ブタンジオール:ジエチレングリコール=56:40:4//70:20:10(mol%)から形成されるポリエステル樹脂の水分散体。
ポリエステル(A)、(B)、(C)をそれぞれ89%、5%、6%の割合で混合した混合原料を最外層(表層)の原料とし、ポリエステル(A)、(B)をそれぞれ95%、5%の割合で混合した混合原料を中間層の原料として、2台の押出機に各々を供給し、各々285℃で溶融した後、40℃に設定した冷却ロール上に、2種3層(表層/中間層/表層=1:18:1の吐出量)の層構成で共押出し冷却固化させて未延伸シートを得た。
次いで、ロール周速差を利用してフィルム温度85℃で縦方向に3.4倍延伸した後、この縦延伸フィルムの両面に、下記表1に示す塗布液1を塗布し、テンターに導き、横方向に120℃で4.0倍延伸し、225℃で熱処理を行った後、横方向に2%弛緩し、塗布層の膜厚(乾燥後)が0.7μmの塗布層を有する厚さ125μmのポリエステルフィルムを得た。得られたポリエステルフィルムを評価したところ、フィルム基材との密着性、鉛筆硬度、耐摩耗性、ヘーズ、ヘーズ差は良好であった。このフィルムの特性を下記表2に示す。
実施例1において、塗布剤組成を表1に示す塗布剤組成に変更する以外は実施例1と同様にして製造し、ポリエステルフィルムを得た。でき上がったポリエステルフィルムは表2に示すとおりであり密着性、鉛筆硬度、耐摩耗性、ヘーズ、ヘーズ差が良好であった。
実施例1において、塗布剤組成を表1に示す塗布剤組成に変更する以外は実施例1と同様にして製造し、ポリエステルフィルムを得た。でき上がった塗布フィルムを評価したところ、表2に示すとおりであり、ポリエステルフィルムとの密着性、鉛筆硬度、耐摩耗性、ヘーズ、ヘーズ差のいずれかが劣るものであった。
Claims (5)
- ポリエステルフィルムの少なくとも片面に、(メタ)アクリレート化合物、(メタ)アクリロイル基を有する反応性シリカおよびイソシアネート系化合物を含有する塗布液から形成された塗布層を有することを特徴とする塗布フィルム。
- 塗布液中の全不揮発成分に対する(メタ)アクリレート化合物の割合が10~95重量%、(メタ)アクリロイル基を有する反応性シリカの割合が1~60重量%、イソシアネート系化合物の割合が1~60重量%である請求項1に記載の塗布フィルム。
- イソシアネート系化合物がイソシアヌレート構造を有する請求項1又は2に記載の塗布フィルム。
- 塗布液が更にアクリル樹脂を含有する請求項1~3の何れかに記載の塗布フィルム。
- 塗布液中の全不揮発成分に対するアクリル樹脂の割合が0.01~30重量%である請求項4に記載の塗布フィルム。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/910,094 US10174220B2 (en) | 2014-08-06 | 2015-08-03 | Coated film |
KR1020167003462A KR101855877B1 (ko) | 2014-08-06 | 2015-08-03 | 도포 필름 |
CN201580001542.3A CN105492511B (zh) | 2014-08-06 | 2015-08-03 | 涂布膜 |
EP15823486.4A EP3015496B1 (en) | 2014-08-06 | 2015-08-03 | Coating film |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-159954 | 2014-08-06 | ||
JP2014159954 | 2014-08-06 | ||
JP2014-202724 | 2014-10-01 | ||
JP2014202724A JP6390319B2 (ja) | 2014-10-01 | 2014-10-01 | 積層ポリエステルフィルム |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016021545A1 true WO2016021545A1 (ja) | 2016-02-11 |
Family
ID=55263810
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/071943 WO2016021545A1 (ja) | 2014-08-06 | 2015-08-03 | 塗布フィルム |
Country Status (5)
Country | Link |
---|---|
US (1) | US10174220B2 (ja) |
EP (1) | EP3015496B1 (ja) |
KR (1) | KR101855877B1 (ja) |
CN (1) | CN105492511B (ja) |
WO (1) | WO2016021545A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016037046A (ja) * | 2014-08-06 | 2016-03-22 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
CN109868024A (zh) * | 2018-07-14 | 2019-06-11 | 宁波高新区诠宝绶新材料科技有限公司 | 一种原位法制备含铕皮革外层涂饰剂的方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111629901B (zh) * | 2018-01-19 | 2022-05-06 | 东洋纺株式会社 | 易粘接性聚酯薄膜 |
CN112430424B (zh) * | 2020-11-24 | 2021-11-16 | 厦门双瑞船舶涂料有限公司 | 一种防滑耐磨聚氨酯甲板漆及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10166531A (ja) | 1996-12-06 | 1998-06-23 | Toray Ind Inc | ハードコートフィルム |
JPH1134243A (ja) | 1997-07-23 | 1999-02-09 | Oike Ind Co Ltd | 防眩性ハードコートフィルム |
JP2006205545A (ja) | 2005-01-28 | 2006-08-10 | Toray Ind Inc | ハードコートフィルム |
JP2013035275A (ja) * | 2011-07-13 | 2013-02-21 | Kansai Paint Co Ltd | 積層体及び積層体の製造方法 |
JP2013141771A (ja) * | 2012-01-10 | 2013-07-22 | Dainippon Printing Co Ltd | 光学積層体、及びその製造方法 |
JP2013537857A (ja) * | 2010-09-07 | 2013-10-07 | スリーエム イノベイティブ プロパティズ カンパニー | 硬化性樹脂組成物及びそれを使用して製造される多層積層体 |
JP2014133401A (ja) * | 2012-12-10 | 2014-07-24 | Mitsubishi Plastics Inc | 積層ポリエステルフィルム |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5863760A (ja) * | 1981-10-09 | 1983-04-15 | Nippon Paint Co Ltd | 光硬化性被覆組成物 |
US5800861A (en) * | 1985-08-15 | 1998-09-01 | The Sherwin-Williams Company | High solid infrared absorbing compositions |
JPH02129235A (ja) * | 1988-11-08 | 1990-05-17 | Mitsubishi Rayon Co Ltd | 被覆材組成物及び耐摩耗性合成樹脂成形品の製造法 |
WO1996034063A1 (fr) * | 1995-04-28 | 1996-10-31 | Nof Corporation | Composition de revetement, procede d'elaboration de cette composition et procede d'elaboration d'une dispersion de sol d'oxyde inorganique |
WO2000006654A1 (fr) * | 1998-07-31 | 2000-02-10 | Mitsubishi Rayon Co., Ltd. | Materiau de revetement et moulage de resine enduit |
DE19933098A1 (de) * | 1999-07-15 | 2001-01-18 | Herberts Gmbh & Co Kg | Mit Nanopartikeln modifizierte Bindemittel für Überzugsmittel und deren Verwendung |
US6703138B1 (en) * | 1999-10-19 | 2004-03-09 | Toyo Boseki Kabushiki Kaisha | Laminated polyester film |
KR20030025914A (ko) * | 2000-04-10 | 2003-03-29 | 세끼쑤이 케미컬 가부시기가이샤 | 대전방지 하드코트용 조성물, 대전방지 하드코트, 그제조방법 및 대전방지 하드코트를 갖는 적층체 필름 |
JP4084985B2 (ja) | 2002-10-29 | 2008-04-30 | リンテック株式会社 | ハードコートフィルム |
DK1479734T3 (da) * | 2003-05-20 | 2009-05-11 | Dsm Ip Assets Bv | Nanostruktureret overflade-coatingsproces, nanostrukturerede coatinger og artikler omfattende coatingen |
CN1835994B (zh) * | 2003-08-19 | 2010-08-25 | 东洋纺织株式会社 | 聚酯薄膜 |
TW200624510A (en) * | 2004-11-08 | 2006-07-16 | Mitsubishi Chem Corp | Radiative curable composition and cured product thereof, and laminate of the cured product |
US8871335B2 (en) * | 2005-08-31 | 2014-10-28 | Kuraray America Inc. | Solar control laminate |
US20070112164A1 (en) * | 2005-11-17 | 2007-05-17 | Bayer Materialscience Llc | Low surface energy, ethylenically unsaturated polyisocyanate addition compounds and their use in coating compositions |
US20070112161A1 (en) * | 2005-11-17 | 2007-05-17 | Bayer Materialscience Llc | Low surface energy, ethylenically unsaturated polyisocyanate addition compounds and their use in coating compositions |
US7759447B2 (en) * | 2005-11-17 | 2010-07-20 | Bayer Materialscience Llc | Low surface energy, ethylenically unsaturated polyisocyanate addition compounds and their use in coating compositions |
JP5333443B2 (ja) * | 2008-03-27 | 2013-11-06 | 藤倉化成株式会社 | プラスチック基材用塗料組成物、それより形成された塗膜、および形成体 |
EP2295481A4 (en) * | 2008-05-23 | 2011-12-28 | Showa Denko Kk | CURABLE COMPOSITION COMPRISING A REACTIVE (METH) ACRYLATE POLYMER, AND HARDENED PRODUCT THEREOF |
JP5610191B2 (ja) * | 2010-03-24 | 2014-10-22 | Dic株式会社 | 無機粒子分散体、エネルギー線硬化性樹脂組成物、及びフィルム |
JP5470166B2 (ja) * | 2010-06-11 | 2014-04-16 | 東亞合成株式会社 | 硬化型コーティング剤組成物 |
JP5896917B2 (ja) * | 2010-11-22 | 2016-03-30 | 昭和電工株式会社 | 硬化性樹脂組成物 |
US20140011036A1 (en) * | 2011-02-22 | 2014-01-09 | Mitsubishi Plastics, Inc. | Laminated polyester film |
JP5946356B2 (ja) * | 2011-08-05 | 2016-07-06 | 関西ペイント株式会社 | 塗料組成物及び塗膜形成方法 |
JP2013064093A (ja) * | 2011-09-20 | 2013-04-11 | Nagase Chemtex Corp | 赤外線吸収コーティング剤組成物 |
EP2818498B1 (en) * | 2012-02-25 | 2019-03-06 | Mitsubishi Chemical Corporation | Coated film |
CN104245766A (zh) * | 2012-04-13 | 2014-12-24 | 横滨橡胶株式会社 | 光硬化性树脂组合物 |
-
2015
- 2015-08-03 EP EP15823486.4A patent/EP3015496B1/en active Active
- 2015-08-03 KR KR1020167003462A patent/KR101855877B1/ko active IP Right Grant
- 2015-08-03 CN CN201580001542.3A patent/CN105492511B/zh active Active
- 2015-08-03 US US14/910,094 patent/US10174220B2/en active Active
- 2015-08-03 WO PCT/JP2015/071943 patent/WO2016021545A1/ja active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10166531A (ja) | 1996-12-06 | 1998-06-23 | Toray Ind Inc | ハードコートフィルム |
JPH1134243A (ja) | 1997-07-23 | 1999-02-09 | Oike Ind Co Ltd | 防眩性ハードコートフィルム |
JP2006205545A (ja) | 2005-01-28 | 2006-08-10 | Toray Ind Inc | ハードコートフィルム |
JP2013537857A (ja) * | 2010-09-07 | 2013-10-07 | スリーエム イノベイティブ プロパティズ カンパニー | 硬化性樹脂組成物及びそれを使用して製造される多層積層体 |
JP2013035275A (ja) * | 2011-07-13 | 2013-02-21 | Kansai Paint Co Ltd | 積層体及び積層体の製造方法 |
JP2013141771A (ja) * | 2012-01-10 | 2013-07-22 | Dainippon Printing Co Ltd | 光学積層体、及びその製造方法 |
JP2014133401A (ja) * | 2012-12-10 | 2014-07-24 | Mitsubishi Plastics Inc | 積層ポリエステルフィルム |
Non-Patent Citations (1)
Title |
---|
See also references of EP3015496A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016037046A (ja) * | 2014-08-06 | 2016-03-22 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
CN109868024A (zh) * | 2018-07-14 | 2019-06-11 | 宁波高新区诠宝绶新材料科技有限公司 | 一种原位法制备含铕皮革外层涂饰剂的方法 |
Also Published As
Publication number | Publication date |
---|---|
EP3015496B1 (en) | 2018-12-12 |
US10174220B2 (en) | 2019-01-08 |
CN105492511B (zh) | 2022-05-24 |
EP3015496A1 (en) | 2016-05-04 |
EP3015496A4 (en) | 2017-05-03 |
KR101855877B1 (ko) | 2018-05-09 |
US20160257840A1 (en) | 2016-09-08 |
CN105492511A (zh) | 2016-04-13 |
KR20160040578A (ko) | 2016-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5882440B2 (ja) | 積層ポリエステルフィルム | |
WO2016021545A1 (ja) | 塗布フィルム | |
WO2013125288A1 (ja) | 塗布フィルム | |
JP5608198B2 (ja) | 積層ポリエステルフィルム | |
JP6260727B2 (ja) | 積層ポリエステルフィルム | |
WO2015015900A1 (ja) | 塗布フィルム | |
JP6390319B2 (ja) | 積層ポリエステルフィルム | |
JP5726925B2 (ja) | 積層ポリエステルフィルム | |
JP5809016B2 (ja) | ポリエステルフィルム | |
WO2014097715A1 (ja) | 塗布フィルム | |
JP5943849B2 (ja) | 積層ポリエステルフィルム | |
JP5714034B2 (ja) | 積層ポリエステルフィルム | |
JP5342632B2 (ja) | 積層ポリエステルフィルム | |
JP5342631B2 (ja) | 積層ポリエステルフィルム | |
JP2017170721A (ja) | 積層ポリエステルフィルム | |
JP5907642B2 (ja) | ポリエステルフィルムの製造方法 | |
JP6061997B2 (ja) | 積層ポリエステルフィルムの製造方法 | |
JP6052845B2 (ja) | 積層ポリエステルフィルム | |
JP5822993B2 (ja) | 積層ポリエステルフィルム | |
JP5778835B2 (ja) | 積層ポリエステルフィルム | |
JP5764276B2 (ja) | 積層ポリエステルフィルム | |
JP5830210B2 (ja) | 積層ポリエステルフィルム | |
JP5830207B2 (ja) | 積層ポリエステルフィルム | |
JP2015024596A (ja) | 積層ポリエステルフィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201580001542.3 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015823486 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14910094 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20167003462 Country of ref document: KR Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15823486 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |