WO2013099829A1 - 加飾成形用積層フィルム、ポリウレタン樹脂および加飾成形体の製造方法 - Google Patents
加飾成形用積層フィルム、ポリウレタン樹脂および加飾成形体の製造方法 Download PDFInfo
- Publication number
- WO2013099829A1 WO2013099829A1 PCT/JP2012/083384 JP2012083384W WO2013099829A1 WO 2013099829 A1 WO2013099829 A1 WO 2013099829A1 JP 2012083384 W JP2012083384 W JP 2012083384W WO 2013099829 A1 WO2013099829 A1 WO 2013099829A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane resin
- group
- molding
- decorative
- protective layer
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
- B32B2451/00—Decorative or ornamental articles
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
- C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/001—Presence of polyester in the barrier layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/001—Presence of polyurethane in the barrier layer
-
- 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
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- 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
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
Definitions
- the present invention relates to a laminated film for decorative molding used when film decoration is applied to a decorative object used in automobile parts, electrical appliances, etc., and to a decorative object having a complicated shape such as deep drawing.
- the present invention relates to a method for producing a decorative molded laminated film, a polyurethane resin, and a decorative molded body, which have good conformability to a mold during decorative molding and are less likely to be scratched on the surface.
- a method of decorating molded parts such as automobile parts and electrical appliances
- a plurality of layers having different functions such as an adhesive layer, a colored layer, and a protective layer are sequentially spray-coated on the surface of the part.
- a technique for imparting durability and design properties and decorating a body to be decorated is employed.
- spray coating requires a baking process, which increases the number of manufacturing processes, and requires a heat amount and time for drying, which increases the cost.
- film decoration methods such as a vacuum forming method and a pressure forming method that can be applied to a three-dimensional object to be decorated have been studied.
- the protective layer that covers the outermost surface of the molded product has durability [resistance to scratching (scratch resistance), weather resistance, chemical resistance and Water resistance etc.] and plays an important role in the decoration of the molded product.
- the size of the molded product becomes large and the shape becomes complicated, so that it is necessary to follow the mold at the time of decorative molding. That is, when the size of a molded product becomes large in the film decoration method, it is necessary to be able to decorate so as to cover all the areas from the top to the bottom of the molded product at once. Further, when the shape becomes complicated, it is necessary that the decorative molded laminated film is deformed along the concavo-convex shape and the entire surface follows the shape.
- the protective layer of decorative molded laminated films requires scratch resistance and the ability to follow the mold at the time of decorative molding as decorative molded laminated films, and the demand for these properties has increased. Yes.
- the film decoration method is applied to parts such as automobiles, it is required that the productivity is high, that is, the molding is completed with a small number of processes.
- Patent Document 3 a molding film is proposed which has a urethane resin as a main and has a protective layer that is cured only by thermal curing.
- JP 2004-299223 A Japanese Patent Laid-Open No. 2003-212938 JP 2010-260942 A
- the present invention provides a decorative molded laminated film having a protective layer with high productivity, good stretchability suitable for film decorative molding, and good scratch resistance.
- the purpose is to provide.
- the present invention employs the following configurations [1] to [19].
- the polyurethane resin (U) is a polyurethane resin (U1) having an alkoxysilyl group and / or a silanol group in the molecule.
- the organic isocyanate component (B) is an alicyclic polyisocyanate (b1) having 6 to 18 carbon atoms and / or an aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms, [1] to [4 ]
- a process comprising at least a polycarbonate skeleton having an alicyclic hydrocarbon group, an alkoxysilyl group and / or a silanol group, which is formed from at least an active hydrogen component (A) and an organic isocyanate component (B).
- a process comprising at least a polycarbonate skeleton having an alicyclic hydrocarbon group, an alkoxysilyl group and / or a silanol group, which is formed from at least an active hydrogen component (A) and an organic isocyanate component (B).
- A active hydrogen component
- B organic isocyanate component
- the ratio of the mass of Si atoms derived from the alkoxysilyl group and / or silanol group of the polyurethane resin (U1) to the total mass of the active hydrogen component (A) and the organic isocyanate component (B) is 0.05 to The polyurethane resin according to any one of [7] to [9], which is 2.0% by mass.
- the organic isocyanate component (B) is an alicyclic polyisocyanate (b1) having 6 to 18 carbon atoms and / or an aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms, [7] to [10 ]
- the polyurethane resin in any one of.
- Polyurethane resin (U2) formed of at least an active hydrogen component (A) and an organic isocyanate component (B) and having a polycarbonate skeleton having an alicyclic hydrocarbon group and an amino group or a carboxyl group and / or a salt thereof And a laminated film for decorative molding containing a compound (X) having a glycidyl ether group and an alkoxysilyl group and / or silanol group.
- the ratio of the mass of Si atoms derived from the alkoxysilyl group and / or silanol group of compound (X) to the total mass of active hydrogen component (A) and organic isocyanate component (B) is 0.05-2.
- the organic isocyanate component (B) is an alicyclic polyisocyanate (b1) having 6 to 18 carbon atoms and / or an aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms.
- the polyurethane resin composition according to any one of [16].
- the polyurethane resin (U) has an alkoxysilyl group and / or a silanol group in the molecule.
- the protective layer contains a compound (X) having a glycidyl ether group and an alkoxysilyl group and / or a silanol group, and the polyurethane resin (U) has a carboxyl group and / or a salt thereof.
- the laminated film for decorative molding of the present invention is excellent in followability to the mold during decorative molding, and further, the curing of the protective layer is sufficiently advanced and completed by the heat during molding.
- laminated film for decoration molding it is highly productive and has good decoration and followability to mold during decoration molding and durability (scratch resistance, weather resistance, chemical resistance, water resistance, etc.) A molded body can be obtained.
- a polyurethane resin (U) having a polycarbonate skeleton formed of at least an active hydrogen component (A) and an organic isocyanate component (B) and having an alicyclic hydrocarbon group.
- Polyurethane resin (U) is a polyurethane resin (U1) having an alkoxysilyl group and / or a silanol group in the molecule.
- the protective layer contains a compound (X) having a glycidyl ether group and an alkoxysilyl group and / or a silanol group
- the polyurethane resin (U) is an amino group or a carboxyl group and / or a salt thereof.
- a polyurethane resin (U2) having The laminated film for decorative molding satisfying any of the above is laminated on the surface of the object to be decorated and laminated to the object to be decorated by thermoforming and pasted on the object to be decorated Can be applied.
- the constituent order of the colored layer and the adhesive layer the following forms (i) to (iii) can be adopted.
- a to-be-decorated body is not contained in the laminated
- a composite layer from the protective layer having the following respective configurations (a) to (c) formed on the object to be decorated to the adhesive layer may be referred to as a decorative layer.
- the number can be reduced, and the production efficiency of a molded product having a decorative layer is improved. This makes it possible to reduce the cost.
- this laminated film for decorative molding has a protective layer satisfying at least one of the above conditions (1) and (2), curing of the protective layer proceeds with heat during molding, and energy rays are separately provided. Since no irradiation step is required, productivity is high, scratch resistance is good, and followability to the mold during decorative molding is good. By using such a laminated film for decorative molding, it is possible to obtain a decorative molded body having a good appearance.
- the elongation at break at 100 ° C. is 150% or more, and polyolefin, polyester, polyvinyl chloride, poly (meth) acrylate, polyamide, polyesteramide, polyether, polystyrene, polyetherester, polycarbonate Any film such as an unstretched film, a uniaxially stretched film, or a biaxially stretched film may be used as long as it is a film obtained by processing a thermoplastic resin.
- the molding film of the decorative molded laminated film does not peel from the adjacent layer during handling or decorative molding.
- the interface between the protective layer side surface of the molding film and the protective layer should not be peeled off when handling as described above or during decorative molding.
- the surface on the protective layer side of the molding film has releasability from the protective layer after the decorative molding, in addition to the adhesion with the protective layer before the decorative molding and during the decorative molding. It is preferable. Since these are contradictory characteristics, the adhesion reducing means and the increasing means shown below can be used and adjusted appropriately.
- a method of forming a composite film by coextruding or laminating a layer made of a material having a low affinity with a protective layer such as polyolefin on one surface (protective layer side) of the molding film examples thereof include a method of coating a mold agent to form a composite film.
- the means for increasing the adhesion include a method of applying a corona treatment to one side (protective layer side) of the molding film.
- the laminated film for decorative molding takes the form (ii) or (iii)
- both sides of the molding film are releasable from the adjacent layers. It is not necessary to have a high adhesiveness. Therefore, a necessary adhesion may be obtained by applying a method of coating the surface with an adhesive or the like to form a composite film, a method of modifying the surface of the molded film by corona treatment, or the like.
- the thickness of the molding film is preferably 50 to 500 ⁇ m, more preferably 75 to 200 ⁇ m, from the viewpoint of the breaking strength and shape retention of the decorative layer after molding.
- the thickness can be calculated by measuring with a micrometer in accordance with JIS C 2151: 2006 every time each layer is formed, during the manufacturing process of the decorative molded laminated film.
- molding can be measured by observing a cross section with a differential interference microscope, a laser microscope, an electron microscope, etc.
- the protective layer used in the decorative molded laminated film When the protective layer used in the decorative molded laminated film is applied to the decorative molded body, it will be positioned on the outermost layer, so the followability to the mold during decorative molding of the decorative molded laminated film It is preferable to impart design characteristics such as transparency and gloss, and coating film characteristics such as scratch resistance, impact resistance, water resistance, chemical resistance and weather resistance.
- a decorative molded body When applied to a decorative molded body, a colored layer or an adhesive layer located on the side of the body to be decorated relative to the protective layer, a molding film [only when the decorative molded laminated film is in the form of (ii) and (iii) It is used by being positioned closer to the object to be decorated than the protective layer.
- a protective layer having such characteristics a protective layer containing a polyurethane resin (U) having a polycarbonate skeleton having an alicyclic hydrocarbon group formed from at least an active hydrogen component (A) and an organic isocyanate component (B). Used. Because the polyurethane resin has a polycarbonate skeleton having an alicyclic hydrocarbon group, it has high crystallinity, is easy to obtain scratch resistance and design characteristics, and ensures followability to the mold during decorative molding. it can.
- Such a polyurethane resin (U) is preferably an active hydrogen component (A) containing a polycarbonate polyol (a1) having an alicyclic hydrocarbon group having a 4-membered ring to a 10-membered ring (particularly preferably a 6-membered ring). And a polyurethane resin formed from the organic isocyanate component (B).
- Examples of the polycarbonate polyol (a1) having an alicyclic hydrocarbon group include an alicyclic polyvalent (2 to 3 or more) alcohol having 6 to 20 carbon atoms or an acyclic polycyclic having 2 to 20 carbon atoms.
- One or a mixture of two or more valent (2 to 3 or more) alcohols preferably an alkylene diol having an alkylene group having 6 to 10 carbon atoms, more preferably 6 to 9 carbon atoms
- Condensation with a compound for example, a dialkyl carbonate having 1 to 6 carbon atoms in an alkyl group, an alkylene carbonate having 2 to 6 carbon atoms, a diaryl carbonate having 6 to 9 carbon atoms, or the like
- the polycarbonate polyol etc. which are manufactured by making it be mentioned.
- a compound name such as “polycarbonate polyol having an alicyclic hydrocarbon group (a1)” with a symbol attached may be simply represented by only a
- Examples of the alicyclic polyvalent (2 to 3 or more) alcohol having 6 to 20 carbon atoms include 1,2-cyclobutanediol, 2,2,4,4, -tetramethyl-1,3-cyclobutanediol, 1,2- or 1,3-cyclopentanediol, 3-methyl-1,2-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 4-methyl-1,2- Cyclohexanediol, 1,2-, 1,3- or 1,4-cyclohexanedimethanol, 1,1'-bicyclohexane-1,1'-diol, 1,1'-bicyclohexane-2,2'-diol 1,1'-bicyclohexane-4,4'-diol, hydrogenated bisphenol A, hydrogenated bisphenol F, 1,2- or 1,3-cycloheptanediol and 1,2-, 1, 4- or 1,5 cyclooctan
- 1,4-cyclohexanediol and cyclohexanedimethanol are preferred from the viewpoint of scratch resistance and followability to the mold of the protective layer obtained, and 1,4-cyclohexanedimethanol is more preferred. .
- Examples of the acyclic polyvalent (2 to 3 or more) alcohol having 2 to 20 carbon atoms include ethylene glycol, 1,2- or 1,3-propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1 , 2-, 1,3-, 2,3- or 1,4-butanediol, 3-methyl-1,2-butanediol, 1,2-, 1,4-, 1,5- or 2,4 -Pentanediol, 2- or 3-methyl-1,5-pentanediol, 2- or 3-methyl-4,5-pentanediol, 2,3-dimethyltrimethylene glycol, 2,2,4-trimethyl-1 , 3-pentanediol, 1,4-, 1,5-, 1,6- or 2,5-hexanediol, 1,7-heptanediol, 2- or 3-methyl-1,6-he Sundiol, 2-, 3- or 4-methyl-1,7-heptanediol, 1,8
- linear diols having 1 to 6 carbon atoms (1,3-propylene glycol, 1,4-butanediol, 1 , 5-pentanediol and 1,6-hexanediol).
- the above alicyclic polyvalent (2 to 3 or more) alcohols having 6 to 20 carbon atoms are preferable from the viewpoint of conformability to the mold.
- the range of the number average molecular weight (hereinafter abbreviated as Mn) of the polycarbonate polyol (a1) having an alicyclic hydrocarbon group is preferably 500 to 5,000, from the viewpoint of followability to the mold of the protective layer to be obtained. More preferably, it is 600 to 3,000, particularly preferably 750 to 2,000.
- Mn in this invention can be measured on condition of the following, for example using a gel permeation chromatography.
- Solution injection volume 100 ⁇ l
- Flow rate 1 ml / min
- Measurement temperature 40 ° C
- Detector Refractive index detector
- Reference material Standard polystyrene
- the content of the alicyclic hydrocarbon group derived from the polycarbonate polyol (a1) having an alicyclic hydrocarbon group in the polyurethane resin (U) is an active hydrogen component from the viewpoint of scratch resistance and design characteristics of the protective layer.
- the content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass with respect to the total mass of (A) and the organic isocyanate component (B).
- the active hydrogen component (A) other than the polycarbonate polyol (a1) having an alicyclic hydrocarbon group those conventionally used in the production of polyurethane can be used.
- a polymer polyol (a2) having a Mn of 500 or more other than (a1), a carboxyl group-containing polyol and its salt (a3), a chain extender (a4), a reaction terminator (a5), and the like can be used.
- polymer polyol (a2) having an Mn of 500 or more other than (a1) polymer polyols conventionally used in the production of polyurethane can be used, such as polyester polyol (a21) and polyether polyol (a22). Is mentioned.
- polyester polyol (a21) examples include an aliphatic polycarbonate polyol (a211) having no alicyclic hydrocarbon group, a dehydration condensation type polyester polyol (a212), and a polylactone polyol (a213).
- Examples of the aliphatic polycarbonate polyol (a211) having no alicyclic hydrocarbon group include the acyclic polyvalent (2 to 3 or more) alcohols having 2 to 20 carbon atoms or a mixture of two or more thereof.
- Low molecular carbonate compounds for example, dialkyl carbonates having 1 to 6 carbon atoms in the alkyl group, alkylene carbonates having 2 to 6 carbon atoms, diaryl carbonates having 6 to 9 carbon atoms, etc.
- dealcohol Examples include polycarbonate polyol produced by condensation while reacting.
- aliphatic polycarbonate polyol (a211) having no alicyclic hydrocarbon group examples include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly (tetramethylene / hexamethylene) carbonate diol.
- a diol obtained by condensing 1,4-butanediol and 1,6-hexanediol with a dealcoholization reaction with a dialkyl carbonate for example, a diol obtained by condensing 1,4-butanediol and 1,6-hexanediol with a dealcoholization reaction with a dialkyl carbonate.
- Examples of the dehydration-condensation polyester polyol (a212) include the alicyclic polyvalent (2 to 3 or higher) alcohol having 6 to 20 carbon atoms and / or the acyclic polyvalent (2 to 20 carbon atoms). ( ⁇ Trivalent or higher) polyester polyols formed from alcohols and C2-C10 polyvalent carboxylic acids or ester-forming derivatives thereof.
- polyhydric carboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof that can be used in the dehydration-condensed polyester polyol (a212) include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, and Maleic acid, etc.), alicyclic dicarboxylic acids (dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.) ), Their anhydrides (such as succinic anhydride, maleic anhydride, phthalic anhydride and trimellitic anhydride), their acid halides (such as adipic acid dichloride), their low molecular weight alkyl esters (dimethyl succinate and phthalate) Dimethyl acid and the like) and mixtures
- dehydration condensation type polyester polyol (a212) examples include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene.
- Adipate diol polybutylene hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate Diols, polybutylene sebacate diols and polyneopentyrene terf Rate diol.
- the polylactone polyol (a213) includes the alicyclic polyvalent (2 to 3 or more) alcohol having 6 to 20 carbon atoms and / or the acyclic polyvalent (2 to 3) having 2 to 20 carbon atoms. And the like.
- Examples of the lactone used include lactones having 4 to 12 carbon atoms (for example, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone). .
- polylactone polyol (a213) examples include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.
- polyether polyol (a22) examples include an aliphatic polyether polyol (a221) and an aromatic polyether polyol (a222).
- aliphatic polyether polyol examples include polyoxyethylene polyol [polyethylene glycol and the like], polyoxypropylene polyol [polypropylene glycol and the like], polyoxyethylene / propylene polyol and polyoxytetramethylene glycol.
- aromatic polyether polyol (a222) examples include ethylene oxide (hereinafter abbreviated as EO) adduct of bisphenol A [EO2 mol adduct of bisphenol A, EO4 mol adduct of bisphenol A, and EO6 mol adduct of bisphenol A.
- EO ethylene oxide
- PO bisphenol A propylene oxide
- Mn in (a2) is preferably 500 to 5,000, more preferably 600 to 4,000, and particularly preferably 700 to 3,000 from the viewpoint of scratch resistance of the protective layer and followability to the mold. .
- an aliphatic polycarbonate polyol (a211) having no alicyclic hydrocarbon group is preferable. More preferred are linear diols having 3 to 6 carbon atoms (1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol) or two of these. This is a polycarbonate polyol produced by condensing the above mixture with the low-molecular carbonate compound while subjecting it to a dealcoholization reaction.
- Examples of the carboxyl group-containing polyol and its salt (a3) include dialkyrol alkanoic acids having 6 to 24 carbon atoms [for example, 2,2-dimethylolpropionic acid (hereinafter abbreviated as DMPA), 2,2-dimethylolbutanoic acid. 2,2-dimethylol heptanoic acid and 2,2-dimethylol octanoic acid] and the like and salts thereof.
- DMPA 2,2-dimethylolpropionic acid
- 2,2-dimethylolbutanoic acid 2,2-dimethylol heptanoic acid and 2,2-dimethylol octanoic acid
- salts include ammonium salts, amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propylamine and octylamine) salts, secondary monoamines (such as dimethylamine, Diethylamine and dibutylmine) salts and tertiary monoamines (eg, aliphatic tertiary monoamines such as trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine) salts, etc.
- amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propylamine and octylamine) salts, secondary monoamines (such as dimethylamine, Diethylamine and dibutylmine) salts and tertiary monoamines (eg, aliphatic tertiary
- the salt is particularly preferably used when the polyurethane resin (U) is produced as an aqueous dispersion to be described later.
- the salts the water resistance and chemical resistance of the protective layer obtained and the stability of the urethane resin aqueous dispersion are improved.
- the basic compound constituting the salt has a boiling point of ⁇ 40 ° C. to 150 ° C. at normal pressure, specifically, ammonium salt, triethylamine salt and N, N-dimethylethanolamine salt. Etc.
- Examples of the chain extender (a4) include water, the above acyclic polyhydric (2 to trivalent or higher valent) alcohol having 2 to 20 carbon atoms, EO and / or PO of these acyclic polyhydric alcohols.
- Low molar adducts (chemical formula or Mn less than 500), diamines having 2 to 10 carbon atoms (eg ethylenediamine, propylenediamine, 1,2-propanediamine, butylenediamine, hexamethylenediamine, 2,2,4- or 2 , 4,4-trimethylhexamethylenediamine, isophoronediamine and other aliphatic or alicyclic diamines; o-, m- or p-phenylenediamine, toluenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane and Aromatic polyamines such as 4,4'-diamino-3,3'-diethyldiphenyl
- reaction terminator (a5) examples include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, butanol, cellosolves and carbitols) and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, Monobutylamine, dibutylamine, monooctylamine, monoethanolamine, diethanolamine, etc.).
- components (a1) to (a5) of the active hydrogen component (A) one kind may be used alone, or two or more kinds may be used in combination.
- organic isocyanate component (B) those conventionally used for the production of polyurethane can be used.
- the alicyclic polyisocyanate (b1) having 6 to 18 carbon atoms, the aliphatic polyisocyanate having 4 to 22 carbon atoms ( b2), an aromatic polyisocyanate having 8 to 26 carbon atoms (b3), an araliphatic polyisocyanate having 10 to 18 carbon atoms (b4), a modified product of these polyisocyanates (b5), and the like are used.
- the organic isocyanate component (B) one of these may be used alone, or two or more may be used in combination.
- Examples of the alicyclic polyisocyanate (b1) having 6 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, methyl Mention may be made of cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.
- IPDI isophorone diisocyanate
- MDI 4,4-dicyclohexylmethane diisocyanate
- cyclohexylene diisocyanate methyl Mention may be made of cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene
- Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.
- ethylene diisocyanate tetramethylene diisocyanate
- hexamethylene diisocyanate hereinafter abbreviated as HDI
- dodecamethylene diisocyanate 1,6,11-unde
- aromatic polyisocyanate (b3) having 8 to 26 carbon atoms examples include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), and crude TDI.
- MDI 4,4′- or 2,4′-diphenylmethane diisocyanate
- crude MDI polyarylpolyisocyanate
- 4,4′-diisocyanatobiphenyl 3,3′-dimethyl-4,4 '-Diisocyanatobiphenyl
- 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane 1,5-naphthylene diisocyanate
- Examples of the araliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate.
- the modified polyisocyanate (b5) of (b1) to (b4) is a modified polyisocyanate (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group or Oxazolidone group-containing modified products, etc .; free isocyanate group content is usually 8 to 33% by mass, preferably 10 to 30% by mass, particularly 12 to 29% by mass, specifically modified MDI (urethane modified) MDI, carbodiimide-modified MDI and trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.
- organic isocyanate components (B) from the viewpoint of the weather resistance of the protective layer obtained, preferred are alicyclic polyisocyanates (b1) having 6 to 18 carbon atoms and aliphatic polyisocyanates (b2) having 4 to 22 carbon atoms. More preferred are alicyclic diisocyanates having 6 to 18 carbon atoms and aliphatic diisocyanates having 4 to 22 carbon atoms, particularly preferred are IPDI, hydrogenated MDI, HDI and mixtures thereof, and particularly preferred is IPDI. Hydrogenated MDI and mixtures thereof, most preferred are hydrogenated MDI.
- the total value of the urethane group concentration and the urea group concentration in the polyurethane resin (U) is 1.0 to 6 on the basis of the weight of (U) from the viewpoint of scratch resistance and followability to the mold of the protective layer obtained.
- 0.0 mmol / g more preferably 1.5 to 5.0 mmol / g, particularly preferably 2.0 to 4.0 mmol / g.
- Mn of the polyurethane resin (U) is 10,000 to 1,000,000, more preferably 10,000 to 500,000, particularly preferably 10,000 from the viewpoint of water resistance, chemical resistance and mold conformability of the protective layer obtained. ⁇ 200,000, most preferably 10,000 ⁇ 100,000.
- the melting temperature of the polyurethane resin (U) is preferably 50 to 280 ° C., more preferably 60 to 200 ° C., and particularly preferably 80 to 160 ° C., from the viewpoint of followability of the protective layer to the mold.
- the melting temperature of the polyurethane resin (U) is “Melt Indexer I type” manufactured by Tester Sangyo Co., Ltd. as a melt mass flow rate measuring device in JIS K 7210: 1999 (plastic-thermoplastic melt mass flow rate test method). The temperature at which the melt mass flow becomes 10 g / 10 min at a load of 2.16 kg.
- the polyurethane resin (U) is a polyurethane resin (U1) having an alkoxysilyl group and / or a silanol group in the molecule.
- Condition (2) The protective layer contains a compound (X) having a glycidyl ether group and an alkoxysilyl group and / or a silanol group, and the polyurethane resin (U) has an amino group or a carboxyl group and / or a salt thereof. (U2).
- Examples of the method for producing a polyurethane resin (U) having an alkoxysilyl group and / or silanol group in the molecule defined in the condition (1) include a polyurethane resin having an amino group or a carboxyl group and / or a salt thereof. (U2) and a method (1-1) in which a compound (X) having a glycidyl ether group and an alkoxysilyl group and / or a silanol group in the molecule is reacted; a polyurethane resin having an isocyanate group and an amino group in the molecule; Examples thereof include a method (1-2) for reacting a compound (Y) having an alkoxysilyl group and / or a silanol group.
- Examples of the compound (X) used in the method (1-1) include glycidoxyalkyltrialkoxysilane having 7 to 20 carbon atoms, glycidoxyalkyl (alkyl) dialkoxysilane having 7 to 20 carbon atoms, and 7 carbon atoms.
- glycidoxyalkyl (dialkyl) alkoxysilanes and the like and their hydrolysates in which the alkoxy groups in the above compounds are converted into hydroxyl groups to form silanol groups
- hydrolysates specifically 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like and their hydrolysates (the alkoxy group in the above compound is Converted to a hydroxyl group to form a silanol group) It is.
- Compound (X) may be used alone or in combination of two or more.
- a chain is used in the description of the production of the polyurethane resin.
- the molar amount of the isocyanate group is excessive with respect to the active hydrogen (hydroxyl group, amino group, etc.) that reacts with the isocyanate group.
- this method after introducing an isocyanate group at the terminal, it is reacted with water to form a terminal amino group, which has a ketimine bond (—C ⁇ N—).
- Noamin after introducing a ketimine resin bound end, a method in which the terminal amino group by hydrolyzing the ketimine bond.
- the monoamine having a ketimine bond is not particularly limited as long as it has one amino group and at least one ketimine bond in one molecule.
- the boiling point of acetone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, etc. Is preferably 120 ° C. or lower.
- a urethane resin As a method for obtaining a polyurethane resin (U2) having a carboxyl group and / or a salt thereof among the polyurethane resin (U2) having an amino group or a carboxyl group and / or a salt thereof used in the method (1-1), a urethane resin is used.
- the method of using the said carboxyl group-containing polyol and its salt (a3) as an active hydrogen component (A) at the time of manufacture is mentioned.
- Conditions such as the temperature and time of the reaction between the glycidyl ether group and the amino group or carboxyl group and / or a salt thereof may be the same as those usually used for the reaction of these groups.
- the compound (Y) used in the method (1-2) includes aminoalkyltrialkoxysilane having 4 to 20 carbon atoms, aminoalkyl (alkyl) dialkoxysilane having 4 to 20 carbon atoms, and amino having 4 to 20 carbon atoms.
- Alkyl (dialkyl) alkoxysilanes and the like and hydrolysates thereof include 3-aminopropyltriethoxysilane, 3- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropylmethyldimethoxysilane etc. and their hydrolysates (in the above compounds That the alkoxy group is converted to a hydroxyl group and was the silanol group).
- a compound (Y) may be used individually by 1 type, and may use 2 or more types together.
- the polyurethane resin (U) is a polyurethane resin (U1) having an alkoxysilyl group and / or silanol group in the molecule, it has excellent followability to the mold before heating during decorative molding, A crosslinked structure is formed by crosslinking alkoxysilyl groups and / or silanol groups by heating at the time of decorative molding, and a protective layer having excellent water resistance, chemical resistance and scratch resistance is obtained.
- the compound (X) having a glycidyl ether group and an alkoxysilyl group and / or silanol group specified in the condition (2) the compound (X) used in the method (1-1) can be used.
- the polyurethane resin (U2) having an amino group or carboxyl group or a salt thereof defined in the condition (2) a polyurethane resin having an amino group, a carboxyl group or a salt thereof used in the method (1-1) ( U2) can be used as the polyurethane resin (U2) having an amino group, a carboxyl group or a salt thereof used in the method (1-1) ( U2) can be used.
- the amount of the carboxyl group and the salt in the polyurethane resin is the reactivity with the compound (X). From the viewpoint of (X), it is preferably equal to or more than the number of moles of the glycidyl ether group possessed by (X), and from the viewpoint of water resistance and chemical resistance, the carboxyl group in the polyurethane resin after the reaction with (X) and its It is preferable that the salt content is 1.3 mmol / g or less.
- the content of the carboxyl group in the polyurethane resin in the present invention is such that 3 to 10 g of the polyurethane resin (U) is heated and dried at 130 ° C. for 45 minutes, washed with water, then heated and dried again at 130 ° C. for 45 minutes, and dimethylformamide It can be calculated from the acid value measured by the method described in JIS K 0070: 1992 (potentiometric titration method).
- the amount of the amino group in the polyurethane resin is (X) from the viewpoint of reactivity with the compound (X). It is preferably equal to or more than the number of moles of glycidyl ether groups, and from the viewpoint of water resistance and chemical resistance, the amount of amino groups in the polyurethane resin (U) after reaction with (X) is 0.35 mmol / The amount is preferably g or less.
- the polyurethane resin (U2) having an amino group or a carboxyl group and / or a salt thereof and the compound (X) were mixed in advance.
- examples thereof include a method using a polyurethane resin composition, a method of mixing a polyurethane resin (U2) and a compound (X) at the time of producing a decorative molded laminated film.
- Conditions such as temperature and time for the reaction of the glycidyl ether group with the amino group or carboxyl group and / or a salt thereof may be the same as those usually used for the reaction of these groups.
- compound (X) When compound (X) is contained in the protective layer, compound (X) has a good followability to the mold before heating at the time of decorative molding and the like by heating at the time of decorative molding.
- the glycidyl ether group reacts with the amino group or carboxyl group of the polyurethane resin (U2) and / or a salt thereof, and further the alkoxysilyl group and / or silanol group introduced into the polyurethane resin by the compound (X) in the above reaction.
- the amount of (X) and / or (Y) used is based on the total mass of (A) and (B) from the viewpoint of the water resistance, chemical resistance and scratch resistance of the resulting protective layer and the ability to follow the mold. It is preferable that the total mass ratio of Si atoms derived from the alkoxysilyl group and / or silanol group of (X) and / or (Y) is 0.05 to 2.0% by mass, and further 0 The amount is preferably from 1 to 1.5% by mass, particularly from 0.2 to 1.0% by mass.
- the polyurethane resin (U) is preferably one that can be used as a solvent solution or an aqueous dispersion from the viewpoint of coatability when forming a laminated film for decorative molding.
- a method for producing a solvent solution or an aqueous dispersion of the polyurethane resin (U) a known method can be used.
- Examples of the method for preparing the solvent solution include a method of reacting each raw material in a solvent and a method of dissolving the polyurethane resin (U) reacted in the absence of a solvent in a solvent.
- the solvent examples include known organic solvents such as ketone solvents having 3 to 10 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester solvents having 2 to 10 carbon atoms (ethyl acetate, butyl acetate, ⁇ -butyrolactone, etc.) ), Ether solvents having 4 to 10 carbon atoms (such as tetrahydrofuran and diethylene glycol dimethyl ether), amide solvents having 3 to 10 carbon atoms (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone) And N-methylcaprolactam, etc.), C1-8 alcohol solvents (methanol, ethanol, isopropyl alcohol, octanol, etc.) and C4-10 hydrocarbon solvents (n-butane, cyclohexane, toluene, xylene, etc.) )
- a polar solvent having a boiling point of 100 ° C. or lower such as acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran and isopropyl alcohol should be used. Is preferred.
- the carboxyl group-containing polyol and its salt (a3) are used as the active hydrogen component (A) from the viewpoints of dispersion stability and water resistance and chemical resistance of the resin. Is preferred.
- the content of the carboxyl group and / or the salt derived from the carboxyl group-containing polyol and the salt (a3) in the polyurethane resin (U) in the case of obtaining the aqueous dispersion depends on the dispersion stability and the water resistance of the resulting protective layer.
- the total mass of the active hydrogen component (A) and the organic isocyanate component (B) is preferably 0.05 to 1.3 mmol / g, more preferably 0.1 to 1.1 mmol. / G, particularly preferably 0.15 to 0.90 mmol / g.
- the polyurethane resin (U) for obtaining the aqueous dispersion is a polyurethane resin (U1) having an alkoxysilyl group and / or silanol group in the molecule
- the active hydrogen component (A) for obtaining (U1) As described above, a carboxyl group and / or a salt thereof can be introduced into (U1) by using the carboxyl group-containing polyol and its salt (a3).
- the polyurethane resin (U) for obtaining the aqueous dispersion has a carboxyl group and / or a salt thereof in the polyurethane resin (U2) having an amino group or a carboxyl group and / or a salt thereof
- the carboxyl group and / or salt thereof introduced to impart dispersion stability of the aqueous dispersion of this polyurethane resin is used in the reaction with the compound (X) having the above-mentioned glycidyl ether group and alkoxysilyl group and / or silanol group. Also contribute.
- Examples of the method for forming the protective layer using the polyurethane resin (U) include the following methods.
- a solvent solution of the polyurethane resin (U) or an aqueous dispersion of the polyurethane resin (U) is applied onto a molding film by a known application method (for example, bar coating, roll coating, gravure coating, curtain coating, spray coating, silk screen)
- a polycarbonate-based polyurethane layer can be formed by thinly and evenly applying the film using a printing method, etc., and reacting in a hot air oven or the like.
- the protective layer formed of the polyurethane resin (U) thus formed may further contain a resin other than the polyurethane resin (U).
- a resin other than the polyurethane resin (U) for example, acrylic polyurethane, polyether polyurethane, polyester Polyurethane etc. can be contained.
- the protective layer may contain a curing accelerator, a binder, a surface conditioner, a pigment, a dye, a plasticizer, an ultraviolet absorber, a light stabilizer and the like as necessary.
- the total content of resins and additives other than the polycarbonate-based polyurethane resin in the protective layer is preferably 15% by mass or less, preferably 10% by mass or less, based on the total mass of the polyurethane resin (U). More preferred. If a resin other than the polycarbonate-based polyurethane resin is included in the above range, the original performance of the protective layer may not be obtained.
- the thickness of the protective layer is preferably 10 to 70 ⁇ m, more preferably 20 to 50 ⁇ m.
- the thickness can be calculated by measuring with a micrometer in accordance with JIS C 2151: 2006 every time each layer is formed, during the manufacturing process of the decorative molded laminated film.
- molding can be measured by observing a cross section with a differential interference microscope, a laser microscope, an electron microscope, etc.
- a colored layer used for a decorative molded laminated film it is a layer that can be given to a body to be decorated to decorate a desired color and texture, and is concealing when molded into a decorative molded body If it is a layer which has, there will be no restriction
- it may be a colored resin layer or a metal thin film layer in which a binder resin, a pigment and a dye are mixed.
- a colored resin layer in which a binder resin and a pigment are mixed is more preferable from the viewpoint of easy color adjustment and good followability to a mold during decorative molding.
- thermosetting resin examples include unsaturated polyester resin, phenol resin, epoxy resin, acrylic resin, urethane resin, melamine resin, urea resin, and polycarbonate resin.
- thermoplastic resin examples include polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin, and polystyrene resin.
- photo-curable resin examples include urethane acrylate resin, polyester acrylate resin, unsaturated polyester resin, silicone acrylate resin, and epoxy acrylate resin. If necessary, one or more selected from these may be used. A mixture of a photopolymerization initiator and the like may be used.
- these resins may be mixed with a curing agent, a curing accelerator, a binder, a surface conditioner, a plasticizer, an ultraviolet absorber, a light stabilizer and the like.
- the resin may be a copolymer or a mixture of different resins, but it is preferable to use a thermosetting resin that has good heat resistance, is easy to handle, and is inexpensive. it can.
- a mixture containing a urethane resin and an acrylic resin as a binder resin from the viewpoint of following the mold at the time of decorative molding.
- any of inorganic pigments and organic pigments such as aluminum powder, carbon black, titanium dioxide, mica, phthalocyanine green, and dioxazine violet may be used.
- this pigment may be used independently and may be used in mixture of 2 or more types.
- concentration of this pigment can be adjusted in the range which does not inhibit the effect of this invention.
- the colored layer thickness is preferably 15 to 50 ⁇ m, more preferably 20 to 40 ⁇ m.
- the thickness can be calculated by measuring with a micrometer in accordance with JIS C 2151: 2006 every time each layer is formed, during the manufacturing process of the decorative molded laminated film.
- molding can be measured by observing a cross section with a differential interference microscope, a laser microscope, an electron microscope, etc.
- the laminated film for decorative molding further includes an adhesive layer on the molded film or the colored layer.
- an adhesive layer By having an adhesive layer, the decorative molded laminated film can be stretched at the time of molding, and at the same time can be attached to the object to be decorated.
- the adhesive layer is not particularly limited as long as it has adhesiveness with the object to be decorated. For example, from an adhesive such as an acrylic adhesive, a urethane adhesive, a polyester adhesive, and an olefin adhesive.
- the thickness of the adhesive layer is preferably 5 to 50 ⁇ m, and more preferably 10 to 40 ⁇ m. When the thickness is 5 ⁇ m or more, it is easy to impart adhesion to the object to be decorated, which is preferable.
- the thickness is 50 ⁇ m or less because the thickness becomes appropriate, the surface of the adhesive layer becomes flat, and a good appearance can be obtained.
- the thickness can be usually measured with a micrometer according to JIS C 2151: 2006. Even in the state where the decorative layer is already laminated on the molding film, the thickness of the adhesive layer can be measured by observing the cross section with a differential interference microscope, a laser microscope, an electron microscope or the like.
- the method for producing the decorative molded body is not particularly limited as long as it is a known thermoforming method that can decorate a three-dimensional object to be decorated such as a vacuum forming method or a pressure forming method. Heating the laminated film for decorative molding to a temperature equal to or higher than the softening point of the layer with the highest softening point in the decorative layer under reduced pressure conditions from the standpoint of following the mold and adhesion to the object to be decorated And the method of making the contact bonding layer of this film contact the surface of a to-be-decorated body, and affixing on a to-be-decorated body by thermoforming is preferable.
- a part represents a mass part.
- Example 1 165.5 parts of polycarbonate diol of Mn 1,000 obtained by the reaction of 1,4-cyclohexanedimethanol as (a1) with ethylene carbonate in a simple pressure reactor equipped with a stirrer and a heating device, (a2 66.2 parts of a polycarbonate diol of Mn 2,000 obtained by reaction of a mixture of 1,4-butanediol and 1,6-hexanediol (molar ratio 70:30) as ethylene carbonate with ethylene carbonate, as (a3) 21.3 parts of DMPA, 0.26 part of ethylene glycol as (a4), 104.4 parts of IPDI as organic polyisocyanate component (B) and 153.3 parts of acetone as a reaction solvent were stirred at 85 ° C.
- a method for producing a decorative molded laminated film will be described.
- a molding film 1 apply a urethane adhesive (TR-7233, manufactured by Shin-Nakamura Chemical Co., Ltd.) to an unstretched polyethylene terephthalate film (Toray, FL10) with a thickness of 100 ⁇ m with a bar coater to 0.5 ⁇ m. Then, a 40 ⁇ m thick unstretched polypropylene film (manufactured by Tosero Co., Ltd., SC) and a dry laminate were used.
- TR-7233 manufactured by Shin-Nakamura Chemical Co., Ltd.
- the polyurethane resin (U1-1) aqueous dispersion was applied to the unstretched polypropylene film side of the molding film using an applicator so that the thickness after drying was 40 ⁇ m, and then dried at 80 ° C. for 10 minutes.
- a protective layer 2 was formed.
- an applicator is applied on the protective layer 2 formed on the molding film 1 so that the paint (R2325, manufactured by Nippon Bee Chemical Co., Ltd.) for forming the colored layer 3 is 40 ⁇ m after drying. After coating using, it was dried at 80 ° C. for 10 minutes to form a colored layer 3.
- the thickness after drying a coating material (M-28, manufactured by Toyobo Co., Ltd.) for forming the adhesive layer 4 on the colored layer 3 further formed on the protective layer 2 formed on the molding film becomes 20 ⁇ m.
- a coating material M-28, manufactured by Toyobo Co., Ltd.
- Example 2 A protective layer 2 was formed on the molding film 1 in the same manner as in Example 1 except that an unstretched polyethylene terephthalate film having a thickness of 100 ⁇ m (FL10, manufactured by Toray Industries, Inc.) was used as the molding film 1.
- the colored layer 3 was formed in the same manner as in Example 1 except that the colored layer 3 was formed on the surface opposite to the protective layer 2 side of the molding film 1.
- an adhesive layer 4 was formed on the colored layer 3 in the same manner as in Example 1 to obtain a decorative molded laminated film shown in FIG.
- Example 3 First, using the same molding film 1 as in Example 2, a colored layer 3 was formed on the molding film 1 under the same colored layer coating conditions as in Example 2. Next, a protective layer 2 was formed on the colored layer 3 formed on the molding film 1 under the same coating conditions as in Example 1. Next, the adhesive layer 4 is formed in the same manner as in Example 1 except that the adhesive layer 4 is formed on the surface opposite to the protective layer 2 further formed on the colored layer 3 formed on the molding film 1. Thus, a decorative molding film shown in FIG. 3 was obtained.
- Example 4 An aqueous dispersion of a polyurethane resin (U1-2) having a silanol group in the molecule was obtained in the same manner as in Example 1 except that the type and amount of raw materials used were changed to those shown in Table 1. Next, a decorative molded laminated film was obtained in the same manner as in Example 1 except that the polyurethane resin (U1-2) was used.
- Example 5 From a reaction between a mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 50:50) as (a1) and ethylene carbonate in a simple pressure reactor equipped with a stirrer and a heating device.
- aqueous dispersion containing a polyurethane resin (U2-1) having a carboxyl group and its salt in the molecule and 3-glycidoxypropylsilanetriol by adding 15.3 parts of propyltrimethoxysilane and stirring for 10 minutes 1,000 parts were obtained.
- a decorative molded laminated film was obtained in the same manner as in Example 1 except that an aqueous dispersion containing polyurethane resin (U2-1) and 3-glycidoxypropylsilanetriol was used.
- Example 6 A mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol as (a1) (molar ratio 50:50) was added to a KRC kneader (manufactured by Kurimoto Seiko Co., Ltd.), which is a twin-screw kneader in a nitrogen atmosphere.
- a1 molar ratio 50:50
- the reaction product was taken out, rolled with a pressure press machine heated to 180 ° C., and then cut with a square pelletizer [manufactured by Horai Co., Ltd.] to obtain a polyurethane resin. Subsequently, 289 parts of the polyurethane resin obtained in a pressure-controllable container with temperature control, 14 parts of 25% by weight ammonia water as a neutralizing agent and 660.5 parts of water were added, and Claremix [Mtechnic Co., Ltd.] was prepared. A polyurethane resin aqueous dispersion was obtained by carrying out dispersion treatment at 12,000 rpm for 3 minutes at 150 ° C.
- Examples 7-9 The polyurethane resins (U2-3) to (U2-5) having a carboxyl group and a salt thereof in the molecule were the same as in Example 4 except that the types and amounts used of the raw materials were changed to those shown in Table 1. An aqueous dispersion containing any one of 3-glycidoxypropylsilanetriol was obtained. Next, a decorative molding laminate was produced in the same manner as in Example 1 except that an aqueous dispersion containing polyurethane resins (U2-3) to (U2-5) and 3-glycidoxypropylsilanetriol was used. A film was obtained.
- Comparative Example 1 A polyurethane resin (U2′-1) having a carboxyl group and its salt in the molecule and 3-glycidoxy in the same manner as in Example 6 except that the type and amount used of the raw materials were changed to those shown in Table 1. An aqueous dispersion containing propylsilanetriol was obtained. Next, a decorative molded laminated film was obtained in the same manner as in Example 1 except that an aqueous dispersion containing polyurethane resin (U2′-1) and 3-glycidoxypropylsilanetriol was used.
- Comparative Example 2 The polyurethane resin having a carboxyl group and its salt in the molecule (U2′-) was changed in the same manner as in Example 6 except that the type and amount used of the raw material were changed to those shown in Table 1 and compound (X) was not added. An aqueous dispersion of 2) was obtained. Next, a decorative molded laminated film was obtained in the same manner as in Example 1 except that an aqueous dispersion of polyurethane resin (U2′-2) was used.
- Example 10 From a reaction between a mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 50:50) as (a1) and ethylene carbonate in a simple pressure reactor equipped with a stirrer and a heating device.
- Example 11 A laminated film for decorative molding was produced in the same manner as in Example 2 except that the methyl ethyl ketone solution containing the polyurethane resin (U2-6) obtained in Example 10 and 3-glycidoxypropyltrimethoxysilane was used. Obtained.
- Example 12 A laminated film for decorative molding was prepared in the same manner as in Example 3 except that the methyl ethyl ketone solution containing the polyurethane resin (U2-6) obtained in Example 10 and 3-glycidoxypropyltrimethoxysilane was used. Obtained.
- Examples 13-22 A polyurethane resin having a carboxyl group in its molecule (U2-7) to any one of (U2-16) and 3 in the same manner as in Example 8 except that the type and amount used of the raw material are changed to those shown in Table 2.
- a methyl ethyl ketone solution containing glycidoxypropyltrimethoxysilane or 3-glycidoxypropylmethyldimethoxysilane was obtained.
- Examples were used except that any of the polyurethane resins (U2-7) to (U2-16) and a methyl ethyl ketone solution containing 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropylmethyldimethoxysilane were used.
- a laminated film for decorative molding was obtained in the same manner as in No. 1.
- Example 23 From a reaction between a mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 50:50) as (a1) and ethylene carbonate in a simple pressure reactor equipped with a stirrer and a heating device. Obtained Mn900 polycarbonate diol 280.8 parts, ethylene glycol 21.5 parts as (a4), 1,6-hexanediol 26.9 parts, hydrogenated MD 138.4 parts as (B), HDI 29.6 And 470.5 parts of methyl ethyl ketone as a reaction solvent were added and stirred at 90 ° C.
- Comparative Example 3 A polyurethane resin having a carboxyl group in the molecule (U2′-3) and 3-glycidoxypropyltrimethoxy in the same manner as in Example 8 except that the type and amount used of the raw materials were changed to those shown in Table 2.
- a methyl ethyl ketone solution containing silane was obtained.
- a decorative molded laminated film was obtained in the same manner as in Example 1 except that a methyl ethyl ketone solution containing polyurethane resin (U2′-3) and 3-glycidoxypropyltrimethoxysilane was used.
- Comparative Example 4 Polyurethane resin having a carboxyl group in the molecule (U2′-4) in the same manner as in Example 8 except that the types and amounts used of the raw materials were changed to those shown in Table 2 and compound (X) was not added. A methyl ethyl ketone solution containing was obtained. Next, a decorative molded laminated film was obtained in the same manner as in Example 1 except that the polyurethane resin (U2′-4) was used.
- a polyurethane resin having a carboxyl group in the molecule (U2′-5) and 1,000 parts of a methyl ethyl ketone solution containing 3-glycidoxypropyltrimethoxysilane was obtained.
- a decorative molded laminated film was obtained in the same manner as in Example 1 except that the polyurethane resin (U2′-5) was used.
- Tables 1 and 2 show the results of the chemical resistance and the results of scratch resistance of the 0% molded product and 150% molded product evaluated by the following method for the decorative molded body produced by the following method.
- a sample film [unstretched polyethylene terephthalate film of 100 ⁇ m thickness (manufactured by Toray Industries, FL10) and urethane-based adhesive (manufactured by Shin-Nakamura Chemical Co., TR -7233) was applied with a bar coater to a thickness of 0.5 ⁇ m and applied to an unstretched polypropylene film having a thickness of 40 ⁇ m (manufactured by Tosero Co., Ltd., SC) and dry laminated] at 80 ° C. It dried for 10 minutes and obtained the dry film of the polyurethane resin or the polyurethane resin composition.
- the dry film of the polyurethane resin or polyurethane resin composition is peeled off from the molding film, it is cut into 10 mm width and 50 mm length to obtain a measurement sample, and a tensile tester (Shimadzu 100 kNG) is used to determine the distance between the tensile chucks.
- a tensile test was performed at a tension speed of 200 mm / min.
- the film sample was set in a thermostat set to a temperature of 100 ° C., preheated for 60 seconds, then subjected to a tensile test in the thermostat, and the elongation (%) when the film broke was obtained.
- the greater the breaking elongation the better the followability to the mold when used for the protective layer of the decorative molded laminated film.
- ⁇ Water resistance evaluation method> The sample was applied on a steel plate using an applicator so that the thickness after drying was 40 ⁇ m, and then dried at 90 ° C. for 10 minutes to obtain a test body having a dry film surface of a polyurethane resin or a polyurethane resin composition. It was. Ion-exchanged water is dropped on the dry film surface, and the dropping point is covered with a petri dish with a diameter of 5 cm to prevent evaporation of the droplet, and left at 25 ° C. for 24 hours, and then the droplet is absorbed and removed by a cloth and dried. The appearance of the film was visually evaluated according to the following criteria. In addition, when there is little change in the external appearance of the dry film after a test, when it uses for the protective layer of the laminated
- ⁇ Chemical resistance evaluation method> The sample was applied on a steel plate using an applicator so that the thickness after drying was 40 ⁇ m, and then dried at 90 ° C. for 10 minutes to obtain a test body having a dry film surface of a polyurethane resin or a polyurethane resin composition. It was. A 0.1N sodium hydroxide aqueous solution is dropped onto the dry film surface, the dropping point is covered with a petri dish with a diameter of 5 cm to prevent evaporation of the droplets, and the mixture is allowed to stand at 25 ° C. for 24 hours. The appearance of the dried film was visually evaluated according to the following criteria. In addition, when there is little change in the external appearance of the dry film after a test, when it uses for the protective layer of the laminated
- Molding temperature 110 ° C Heater output: 200% for rapid heating, 80% for normal heating Rapid heating time: 10 seconds Vacuum pressure: 0 kPa Air pressure: 300kPa Air pressure time: 15 seconds Minute release: 0 seconds (0% molding), 2 seconds (150% molding)
- Condition A and Condition B were implemented by adjusting the depth of the box-shaped hollow of a TOM molding machine. Specifically, the condition A was 15 mm from the set film to the bottom of the box-shaped depression, and the condition B was 85 mm.
- the decorated molded body a flat resin molded body having a length of 250 mm, a width of 100 mm, and a thickness of 3 mm made of a polyolefin resin (TSOP GP6BS, manufactured by Prime Polymer Co., Ltd.) was used.
- TSOP GP6BS polyolefin resin
- the scratch resistance on the protective layer side of the decorative molded body was evaluated according to JIS K 5600-5-5: 2008. However, in Examples 2, 3, 11, and 12, the scratch resistance on the protective layer side of the decorative molded body was evaluated without peeling off the molding film. Specifically, the evaluation was performed under the following conditions.
- HEIDON 14-DR manufactured by HEIDON
- Needle 1mmR sapphire needle
- Load 200g
- Speed 10mm / sec
- the decorative molded laminated film of the present invention can be preferably used when decorating automobile parts and electrical appliances, but is not limited thereto, and is not limited to these, such as mobile phones, notebook computers, IT equipment applications, etc. It can also be preferably applied to applications that require design properties and require functionality such as scratch resistance and durability.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
条件(1):ポリウレタン樹脂(U)が分子内にアルコキシシリル基および/またはシラノール基を有するポリウレタン樹脂(U1)である。
条件(2):前記保護層がグリシジルエーテル基ならびにアルコキシシリル基および/またはシラノール基を有する化合物(X)を含有し、ポリウレタン樹脂(U)がアミノ基またはカルボキシル基および/もしくはその塩を有するポリウレタン樹脂(U2)である。
条件(1):ポリウレタン樹脂(U)が分子内にアルコキシシリル基および/またはシラノール基を有する。
条件(2):前記保護層がグリシジルエーテル基ならびにアルコキシシリル基および/またはシラノール基を有する化合物(X)を含有し、ポリウレタン樹脂(U)がカルボキシル基および/またはその塩を有する。
(ii) 保護層/成形用フィルム/着色層/接着層(/被加飾体)
(iii) 保護層/着色層/成形用フィルム/接着層(/被加飾体)
/接着層)
(b) (ii)の形態を採った場合の複合層(保護層/成形用フィルム/着色層/接着層)
(c) (iii)の形態を採った場合の複合層(保護層/着色層/成形用フィルム/接着層)
成形用フィルムとしては、100℃における破断伸度が150%以上であり、ポリオレフィン、ポリエステル、ポリ塩化ビニル、ポリ(メタ)アクリル酸エステル、ポリアミド、ポリエステルアミド、ポリエーテル、ポリスチレン、ポリエーテルエステル、ポリカーボネート等の、熱可塑性樹脂を加工して得られるフィルムであれば特に限定されず、未延伸フィルム、1軸延伸フィルム、2軸延伸フィルムの何れであってもよい。
加飾成形用積層フィルムに用いられる保護層は、加飾成形体に適用される場合、最表層に位置することとなるため、加飾成形用積層フィルムの加飾成形時の型への追従性を損なわない樹脂であると共に、透明性や光沢性といった意匠特性、耐擦過性、耐衝撃性、耐水性、耐薬品性および耐候性といった塗膜特性を付与させることが好ましい。加飾成形体に適用されたときに保護層より被加飾体側に位置する着色層や接着層、成形用フィルム[加飾成形用積層フィルムが、(ii)および(iii)の形態の場合のみ保護層より被加飾体側に位置して使用される。]においては一般的に加飾成形時の型への追従性が重視され、耐傷付性は重視されない。保護層の耐傷付性が劣ると、加飾層全体に傷が入り、被加飾体が露出してしまうので、保護層が耐傷付性を有することが重要となる。かかる特性を有する保護層として、少なくとも活性水素成分(A)と有機イソシアネート成分(B)とから形成され、脂環式炭化水素基を有するポリカーボネート骨格を有するポリウレタン樹脂(U)を含有した保護層が用いられる。ポリウレタン樹脂が脂環式炭化水素基を有するポリカーボネート骨格を有することにより、結晶性が高く、耐傷付性や意匠特性が得られ易く、かつ加飾成形時の型への追従性を確保することができる。
装置:「HLC-8120GPC」[東ソー(株)製]
カラム:「Guardcolumn HXL-H」(1本)、「TSKgel GMHXL」(2本)[いずれも東ソー(株)製]
試料溶液:0.25重量%のテトラヒドロフラン溶液
溶液注入量:100μl
流量:1ml/分
測定温度:40℃
検出装置:屈折率検出器
基準物質:標準ポリスチレン
条件(1):ポリウレタン樹脂(U)が分子内にアルコキシシリル基および/またはシラノール基を有するポリウレタン樹脂(U1)である。
条件(2):保護層がグリシジルエーテル基ならびにアルコキシシリル基および/またはシラノール基を有する化合物(X)を含有し、ポリウレタン樹脂(U)がアミノ基またはカルボキシル基および/もしくはその塩を有するポリウレタン樹脂(U2)である。
加飾成形用積層フィルムに用いられる着色層としては、目的とする色や風合を加飾する被加飾体に与えることができる層であって、加飾成形体に成形したときに隠蔽性を有する層であれば特に制限はない。例えば、バインダー樹脂と顔料および染料を混合した着色樹脂層、金属薄膜層であってもよい。色の調整が容易なことや加飾成形時の型への追従性が良い点から、バインダー樹脂と顔料を混合した着色樹脂層がより好ましい。
加飾成形用積層フィルムは、成形フィルムまたは着色層上にさらに接着層を備える。接着層を有することにより、成形時に加飾成形用積層フィルムを延伸させると同時に被加飾体への貼り付けが可能となる。接着層としては、被加飾体との接着性を有するものであれば特に制限はなく、例えば、アクリル系接着剤、ウレタン系接着剤、ポリエステル系接着剤およびオレフィン系接着剤等の接着剤からなる層が挙げられる接着層厚みは、好ましくは5~50μmであり、さらに好ましくは、10~40μmである。該厚みが5μm以上であると、前記被加飾体への接着性を付与させることが容易となり好ましい。また、該厚みが50μm以下であると、適度な厚みとなり、接着層の表面が平坦となり、良好な外観が得られるため好ましい。該厚みの測定は、通常、JIS C 2151:2006に準じマイクロメータにて測定することができる。また、既に成形用フィルムに加飾層を積層した状態でも、微分干渉顕微鏡やレーザ顕微鏡、電子顕微鏡などで断面を観察することで、接着層の厚みを測定することができる。
加飾成形体の作製方法としては、真空成形法や圧空成形法など3次元形状の被加飾体に加飾可能な、公知の熱成形方法であれば特に限定されないが、加飾成形時の型への追従性や被加飾体との接着性の点から、減圧条件下において、加飾成形用積層フィルムを、加飾層のうち最も軟化点が高い層の軟化点以上の温度に加熱し、該フィルムの接着層を被加飾体の表面に接触せしめて熱成形にて被加飾体に貼り付ける方法が好ましい。
撹拌機および加熱装置を備えた簡易加圧反応装置に、(a1)としての1,4-シクロヘキサンジメタノールとエチレンカーボネートとの反応より得られたMn1,000のポリカーボネートジオール165.5部、(a2)としての1,4-ブタンジオールおよび1,6-ヘキサンジオールの混合物(モル比70:30)とエチレンカーボネートとの反応より得られたMn2,000のポリカーボネートジオール66.2部、(a3)としてのDMPA21.3部、(a4)としてのエチレングリコール0.26部、有機ポリイソシアネート成分(B)としてのIPDI104.4部および反応溶剤としてのアセトン153.3部を仕込んで85℃で15時間攪拌してウレタン化反応を行い、末端にイソシアネート基を有するウレタンプレポリマーのアセトン溶液を得た。さらに、40℃で撹拌しながら中和剤としてのトリエチルアミン12.9部および水623.9部を加えた。60rpmで3分間攪拌後、化合物(Y)としての3-アミノプロピルトリメトキシシラン1.5部、(a4)としてのエチレンジアミン3.6部を加え、減圧下に65℃で8時間かけてアセトンを留去し、分子内にシラノール基を有するポリウレタン樹脂(U1-1)の水分散体1,000部を得た。
成形用フィルム1として、厚さ100μmの未延伸ポリエチレンテレフタレートフィルム(東レ社製、FL10)を用いたこと以外は、実施例1と同様の方法で成形用フィルム1上に保護層2を形成した。次いで、成形用フィルム1の保護層2側とは反対の面に着色層3を形成すること以外は、実施例1と同様の方法で着色層3を形成した。次いで、着色層3上に実施例1と同様の方法で接着層4を形成して、図2に示す加飾成形用積層フィルムを得た。
始めに、実施例2と同様の成形用フィルム1を用い、実施例2と同様の着色層塗工条件により成形用フィルム1上に着色層3を形成した。次いで、成形用フィルム1上に形成した着色層3上に、実施例1と同様の塗工条件で、保護層2を形成した。次いで、成形用フィルム1上に形成した着色層3上にさらに形成した保護層2とは反対の面に接着層4を形成すること以外は、実施例1と同様の方法で接着層4を形成して、図3に示す加飾成形用フィルムを得た。
使用原料の種類と使用量を表1に記載のものに変更する以外は実施例1と同様にして、分子内にシラノール基を有するポリウレタン樹脂(U1-2)の水分散体を得た。次いで、ポリウレタン樹脂(U1-2)を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
撹拌機および加熱装置を備えた簡易加圧反応装置に、(a1)としての1,4-シクロヘキサンジメタノールおよび1,6-ヘキサンジオールの混合物(モル比50:50)とエチレンカーボネートとの反応より得られたMn900のポリカーボネートジオール147.7部、(a2)としての1,4-ブタンジオールおよび1,6-ヘキサンジオールの混合物(モル比70:30)とエチレンカーボネートとの反応より得られたMn2,000のポリカーボネートジオール65.6部、(a3)としてのDMPA21.3部、(a4)としてのエチレングリコール0.26部、有機ポリイソシアネート成分(B)としての水添MDI122.8部および反応溶剤としてのアセトン153.3部を仕込んで85℃で15時間攪拌してウレタン化反応を行い、末端にイソシアネート基を有するウレタンプレポリマーのアセトン溶液を得た。得られたウレタンプレポリマーのアセトン溶液511部を簡易加圧反応装置に仕込み、40℃で撹拌しながら中和剤としてのトリエチルアミン12.9部および水623.9部を加えた。60rpmで3分間攪拌後、(a4)としてのエチレンジアミン3.6部を加え、減圧下に65℃で8時間かけてアセトンを留去し、30℃で化合物(X)としての3-グリシドキシプロピルトリメトキシシラン15.3部を加えて10分間撹拌することで、分子内にカルボキシル基およびその塩を有するポリウレタン樹脂(U2-1)と3-グリシドキシプロピルシラントリオールを含有する水分散体1,000部を得た。次いで、ポリウレタン樹脂(U2-1)と3-グリシドキシプロピルシラントリオールを含有する水分散体を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
窒素雰囲気下で二軸混練機であるKRCニーダー[栗本鐵工(株)製]に、(a1)としての1,4-シクロヘキサンジメタノールおよび1,6-ヘキサンジオールの混合物(モル比50:50)とエチレンカーボネートとの反応より得られたMn900のポリカーボネートジオール13.1部、(a2)としての1,4-ブタンジオールおよび1,6-ヘキサンジオールの混合物(モル比70:30)とエチレンカーボネートとの反応より得られたMn1,000のポリカーボネートジオール116.8部、(a3)としてのDMPA34.4部、(a4)としてのエチレングリコール5.1部、(B)としての水添MDI119.6部を仕込み220℃で10分間混練してウレタン化反応を行った。反応物を取り出し、180℃に加熱した加圧プレス機で圧延後、角形ペレタイザー[(株)ホーライ製]にて裁断してポリウレタン樹脂を得た。続いて、温度制御可能な耐圧容器に得られたポリウレタン樹脂289部、中和剤としての25質量%アンモニア水14部および水660.5部を仕込み、クレアミックス[エムテクニック(株)製]を用いて150℃で12,000rpm、3分間分散処理することでポリウレタン樹脂水分散体を得た。続いて、得られたポリウレタン樹脂水分散体963.5部に、30℃で化合物(X)としての3-グリシドキシプロピルトリメトキシシラン36.5部を加えて10分間撹拌することで、分子内にカルボキシル基およびその塩を有するポリウレタン樹脂(U2-2)と3-グリシドキシプロピルシラントリオールを含有する水分散体1,000部を得た。次いで、ポリウレタン樹脂(U2-2)と3-グリシドキシプロピルシラントリオールを含有する水分散体を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
原料の種類と使用量を表1に記載のものに変更する以外は実施例4と同様にして、分子内にカルボキシル基およびその塩を有するポリウレタン樹脂(U2-3)~(U2-5)のいずれかと3-グリシドキシプロピルシラントリオールを含有する水分散体を得た。次いで、ポリウレタン樹脂(U2-3)~(U2-5)と3-グリシドキシプロピルシラントリオールを含有する水分散体を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
原料の種類と使用量を表1に記載のものに変更する以外は実施例6と同様にして、分子内にカルボキシル基およびその塩を有するポリウレタン樹脂(U2’-1)と3-グリシドキシプロピルシラントリオールを含有する水分散体を得た。次いで、ポリウレタン樹脂(U2’-1)と3-グリシドキシプロピルシラントリオールを含有する水分散体を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
原料の種類と使用量を表1に記載のものに変更し、化合物(X)を加えない以外は実施例6と同様にして、分子内にカルボキシル基およびその塩を有するポリウレタン樹脂(U2’-2)の水分散体を得た。次いで、ポリウレタン樹脂(U2’-2)の水分散体を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
撹拌機および加熱装置を備えた簡易加圧反応装置に、(a1)としての1,4-シクロヘキサンジメタノールおよび1,6-ヘキサンジオールの混合物(モル比50:50)とエチレンカーボネートとの反応より得られたMn900のポリカーボネートジオール184.7部、(a2)としての1,6-ヘキサンジオールとエチレンカーボネートとの反応より得られたMn2,000のポリカーボネートジオール68.4部、(a3)としてのDMPA29部、(a4)としての1,6-ヘキサンジオール26.9部、(B)としての水添MDI178.2部および反応溶剤としてのメチルエチルケトン487.3部を仕込んで90℃で24時間攪拌してウレタン化反応を行い、ポリウレタン樹脂のメチルエチルケトン溶液を得た。さらに、30℃で化合物(X)としての3-グリシドキシプロピルトリメトキシシラン25.5部を加えて10分間撹拌することで、分子内にカルボキシル基を有するポリウレタン樹脂(U2-6)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液1,000部を得た。次いで、ポリウレタン樹脂(U2-6)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
実施例10で得たポリウレタン樹脂(U2-6)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液を使用すること以外は実施例2と同様の方法にて加飾成形用積層フィルムを得た。
実施例10で得たポリウレタン樹脂(U2-6)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液を使用すること以外は実施例3と同様の方法にて加飾成形用積層フィルムを得た。
原料の種類と使用量を表2に記載のものに変更する以外は実施例8と同様にして、分子内にカルボキシル基を有するポリウレタン樹脂(U2-7)~(U2-16)のいずれかと3-グリシドキシプロピルトリメトキシシランまたは3-グリシドキシプロピルメチルジメトキシシランを含有するメチルエチルケトン溶液を得た。次いで、ポリウレタン樹脂(U2-7)~(U2-16)のいずれかと3-グリシドキシプロピルトリメトキシシランまたは3-グリシドキシプロピルメチルジメトキシシランを含有するメチルエチルケトン溶液を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
撹拌機および加熱装置を備えた簡易加圧反応装置に、(a1)としての1,4-シクロヘキサンジメタノールおよび1,6-ヘキサンジオールの混合物(モル比50:50)とエチレンカーボネートとの反応より得られたMn900のポリカーボネートジオール280.8部、(a4)としてのエチレングリコール21.5部、1,6-ヘキサンジオール26.9部、(B)としての水添MD138.4部、HDI29.6部および反応溶剤としてのメチルエチルケトン470.5部を仕込んで90℃で24時間攪拌してウレタン化反応を行い、末端にイソシアネート基を有するポリウレタン樹脂のメチルエチルケトン溶液を得た。 続いて(a5)としてのジエチレントリアミンとメチルイソブチルケトンの反応により得られたケチミン結合を有するモノアミン11.2部を仕込み、60℃で30分間攪拌した後に水28.2部を仕込んで60℃で10分間撹拌して、末端にアミノ基を有するポリウレタン樹脂を得た後、30℃で3-グリシドキシプロピルトリメトキシシラン19.8部を加えて10分間撹拌することで、分子内にシラノール基を有するポリウレタン樹脂(U1-3)を含有するメチルエチルケトン溶液を得た。次いで、ポリウレタン樹脂(U1-3)のメチルエチルケトン溶液を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
原料の種類と使用量を表2に記載のものに変更する以外は実施例8と同様にして、分子内にカルボキシル基を有するポリウレタン樹脂(U2’-3)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液を得た。次いで、ポリウレタン樹脂(U2’-3)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
原料の種類と使用量を表2に記載のものに変更し、化合物(X)を加えない以外は、実施例8と同様にして、分子内にカルボキシル基を有するポリウレタン樹脂(U2’-4)を含有するメチルエチルケトン溶液を得た。次いで、ポリウレタン樹脂(U2’-4)を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
撹拌機および加熱装置を備えた簡易加圧反応装置に、(a4)としてのエチレングリコール8.0部、ビスフェノールAのPO3モル付加物238.1部、(a3)としてのDMPA23.4部、(B)としてのMDI220.3部および反応溶剤としてのメチルエチルケトン489.6部を仕込んで80℃で12時間攪拌してウレタン化反応を行い、ポリウレタン樹脂のメチルエチルケトン溶液を得た。さらに、30℃で化合物(X)としての3-グリシドキシプロピルトリメトキシシラン20.6部を加えて10分間撹拌することで、分子内にカルボキシル基を有するポリウレタン樹脂(U2’-5)と3-グリシドキシプロピルトリメトキシシランを含有するメチルエチルケトン溶液1,000部を得た。次いで、ポリウレタン樹脂(U2’-5)を使用すること以外は実施例1と同様の方法にて加飾成形用積層フィルムを得た。
サンプルを乾燥後の厚さが40μmとなるようにアプリケーターを用いて成形用フィルム[厚さ100μmの未延伸ポリエチレンテレフタレートフィルム(東レ社製、FL10)にウレタン系接着剤(新中村化学社製、TR-7233)を0.5μmになるようにバーコーターで塗工して、厚さ40μmの未延伸ポリプロピレンフィルム(東セロ社製、SC)とドライラミネートしたもの]の上に塗布した後、80℃で10分間乾燥し、ポリウレタン樹脂またはポリウレタン樹脂組成物の乾燥フィルムを得た。ポリウレタン樹脂またはポリウレタン樹脂組成物の乾燥フィルムを成形用フィルムから剥離した後、10mm幅、50mm長に裁断して測定サンプルとし、引張試験機(島津製100kNG)を用いて、引張チャック間の距離が20mmになるようにセットし、引張速度を200mm/分で引張試験を行った。測定は100℃の温度に設定した恒温槽中にフィルムサンプルをセットし、60秒間予熱した後、恒温槽中で引張試験を行い、フィルムが破断したときの伸度(%)を求めた。破断伸度が大きい程、加飾成形用積層フィルムの保護層に用いた場合の型への追従性に優れる。
サンプルを乾燥後の厚さが40μmとなるようにアプリケーターを用いて成形用フィルム[厚さ100μmの未延伸ポリエチレンテレフタレートフィルム(東レ社製、FL10)にウレタン系接着剤(新中村化学社製、TR-7233)を0.5μmになるようにバーコーターで塗工して、厚さ40μmの未延伸ポリプロピレンフィルム(東セロ社製、SC)とドライラミネートしたもの]の上に塗布した後、90℃で10分間乾燥し、ポリウレタン樹脂またはポリウレタン樹脂組成物の乾燥フィルムを得た。JIS K 5600:2008に準じて、乾燥フィルム面に鉛筆を45度の角度でセットして、上から750gの荷重をかけて5mm程度引っかき、傷の付かない鉛筆の硬度で最も高いものを鉛筆硬度とした。結果を表1に示す。尚、鉛筆高度が高い程、加飾成型用積層フィルムの保護層に用いた場合に耐傷付性に優れる。
サンプルを乾燥後の厚さが40μmとなるようにアプリケーターを用いて鋼板の上に塗布した後、90℃で10分間乾燥し、ポリウレタン樹脂またはポリウレタン樹脂組成物の乾燥フィルム面を有する試験体を得た。乾燥フィルム面にイオン交換水を滴下し、液滴の蒸発を防ぐために滴下点を直径5cmのシャーレで覆い、25℃で24時間静置した後、液滴を布で吸収して除去し、乾燥フィルムの外観を次の基準で目視評価した。尚、試験後の乾燥フィルムの外観に変化が少ない程、加飾成形用積層フィルムの保護層に用いた場合に耐水性に優れる。
○:僅かに白化する
△:著しく白化する
×:鋼板から剥がれる
サンプルを乾燥後の厚さが40μmとなるようにアプリケーターを用いて鋼板の上に塗布した後、90℃で10分間乾燥し、ポリウレタン樹脂またはポリウレタン樹脂組成物の乾燥フィルム面を有する試験体を得た。乾燥フィルム面に0.1Nの水酸化ナトリウム水溶液を滴下し、液滴の蒸発を防ぐために滴下点を直径5cmのシャーレで覆い、25℃で24時間静置した後、液滴を布で吸収して除去し、乾燥フィルムの外観を次の基準で目視評価した。尚、試験後の乾燥フィルムの外観に変化が少ない程、加飾成形用積層フィルムの保護層に用いた場合に耐薬品性に優れる。
○:僅かに跡が残る
△:著しく跡が残る
×:鋼板が露出する
TOM成形機(布施真空株式会社製、NGF0406-T)を用いて、加飾成形用積層フィルムの接着層側と被加飾成形体の一番面積の大きい面とが相対するようにフィルムをセットし、以下の条件で成型を行い、加飾成形体を作製した。
ヒーター出力:急加熱時 200%、通常加熱時 80%
急加熱時間:10秒
真空圧力:0kPa
圧空圧力:300kPa
圧空時間:15秒
微量開放:0秒(0%成形時)、2秒(150%成形時)
次いで、得られた加飾成形体の成形用フィルムを剥離した後に加飾成形体の保護層側の耐傷付性をJIS K 5600-5-5:2008に準じて評価した。ただし、実施例2,3,11,12については、成形用フィルムを剥離せずに加飾成形体の保護層側の耐傷付性を評価した。具体的には、以下の条件で評価を行った。
針:1mmRのサファイア針
荷重:200g
速度:10mm/秒
2 保護層
3 着色層
4 接着層
Claims (19)
- 保護層と着色層と接着層とがこの順で配され、いずれかの層間に、または、保護層の着色層とは反対の面上に、成形用フィルムが配された積層構造を有する加飾成形用積層フィルムであって、少なくとも活性水素成分(A)と有機イソシアネート成分(B)とから形成され、脂環式炭化水素基を有するポリカーボネート骨格を有するポリウレタン樹脂(U)を前記保護層が含有してなり、少なくとも条件(1)および条件(2)のいずれかを満たすことを特徴とする加飾成形用積層フィルム。
条件(1):ポリウレタン樹脂(U)が分子内にアルコキシシリル基および/またはシラノール基を有するポリウレタン樹脂(U1)である。
条件(2):前記保護層がグリシジルエーテル基ならびにアルコキシシリル基および/またはシラノール基を有する化合物(X)を含有し、ポリウレタン樹脂(U)がアミノ基またはカルボキシル基および/もしくはその塩を有するポリウレタン樹脂(U2)である。 - 活性水素成分(A)が、脂環式炭化水素基を有するポリカーボネートポリオール(a1)を含有してなる、請求項1に記載の加飾成形用積層フィルム。
- ポリカーボネートポリオール(a1)の数平均分子量が500~5,000であり、かつ活性水素成分(A)と有機イソシアネート成分(B)の合計質量に対するポリカーボネートポリオール(a1)が有する脂環式炭化水素基の質量割合が1~30質量%である、請求項2に記載の加飾成形用積層フィルム。
- 活性水素成分(A)と有機イソシアネート成分(B)の合計質量に対する、ポリウレタン樹脂(U)が有するアルコキシシリル基および/またはシラノール基に由来するSi原子と化合物(X)が有するアルコキシシリル基および/またはシラノール基に由来するSi原子の合計質量の割合が0.05~2.0質量%である、請求項1~3のいずれかに記載の加飾成形用積層フィルム。
- 有機イソシアネート成分(B)が、炭素数6~18の脂環式ポリイソシアネート(b1)および/または炭素数4~22の脂肪族ポリイソシアネート(b2)である、請求項1~4のいずれかに記載の加飾成形用積層フィルム。
- 有機イソシアネート成分(B)が、イソホロンジイソシアネートおよび/または4,4-ジシクロヘキシルメタンジイソシアネートである、請求項1~4のいずれかに記載の加飾成形用積層フィルム。
- 少なくとも活性水素成分(A)および有機イソシアネート成分(B)から形成され、脂環式炭化水素基を有するポリカーボネート骨格と、アルコキシシリル基および/またはシラノール基とを有することを特徴とする加飾成形用積層フィルムに用いられるポリウレタン樹脂。
- 活性水素成分(A)が、脂環式炭化水素基を有するポリカーボネートポリオール(a1)を含有してなる、請求項7に記載のポリウレタン樹脂。
- ポリカーボネートポリオール(a1)の数平均分子量が500~5,000であり、かつ活性水素成分(A)と有機イソシアネート成分(B)の合計質量に対するポリカーボネートポリオール(a1)が有する脂環式炭化水素基の質量割合が1~30質量%である、請求項8に記載のポリウレタン樹脂。
- 活性水素成分(A)と有機イソシアネート成分(B)の合計質量に対する、ポリウレタン樹脂(U1)が有するアルコキシシリル基および/またはシラノール基に由来するSi原子の質量の割合が0.05~2.0質量%である、請求項7~9のいずれかに記載のポリウレタン樹脂。
- 有機イソシアネート成分(B)が、炭素数6~18の脂環式ポリイソシアネート(b1)および/または炭素数4~22の脂肪族ポリイソシアネート(b2)である、請求項7~10のいずれかに記載のポリウレタン樹脂。
- 有機イソシアネート成分(B)が、イソホロンジイソシアネートおよび/または4,4-ジシクロヘキシルメタンジイソシアネートである、請求項7~10のいずれかに記載のポリウレタン樹脂。
- 少なくとも活性水素成分(A)および有機イソシアネート成分(B)から形成され、脂環式炭化水素基を有するポリカーボネート骨格と、アミノ基またはカルボキシル基および/もしくはその塩とを有するポリウレタン樹脂(U2)と、グリシジルエーテル基ならびにアルコキシシリル基および/またはシラノール基を有する化合物(X)とを含有する加飾成形用積層フィルムに用いられることを特徴とするポリウレタン樹脂組成物。
- 活性水素成分(A)が、脂環式炭化水素基を有するポリカーボネートポリオール(a1)を含有してなる、請求項13に記載のポリウレタン樹脂組成物。
- ポリカーボネートポリオール(a1)の数平均分子量が500~5,000であり、かつ活性水素成分(A)と有機イソシアネート成分(B)の合計質量に対するポリカーボネートポリオール(a1)が有する脂環式炭化水素基の質量割合が1~30質量%である、請求項14に記載のポリウレタン樹脂組成物。
- 活性水素成分(A)と有機イソシアネート成分(B)の合計質量に対する、化合物(X)が有するアルコキシシリル基および/またはシラノール基に由来するSi原子の質量の割合が0.05~2.0質量%である、請求項13~15のいずれかに記載のポリウレタン樹脂組成物。
- 有機イソシアネート成分(B)が、炭素数6~18の脂環式ポリイソシアネート(b1)および/または炭素数4~22の脂肪族ポリイソシアネート(b2)である、請求項13~16のいずれかに記載のポリウレタン樹脂組成物。
- 有機イソシアネート成分(B)が、イソホロンジイソシアネートおよび/または4,4-ジシクロヘキシルメタンジイソシアネートである、請求項13~16のいずれかに記載のポリウレタン樹脂組成物。
- 加飾成形用積層フィルムを被加飾体に貼り付ける加飾成形体の製造方法であって、前記加飾成形用積層フィルムが、保護層と着色層と接着層とがこの順で配され、いずれかの層間に、または、保護層の着色層とは反対の面上に、成形用フィルムが配された積層構造を有し、少なくとも活性水素成分(A)と有機イソシアネート成分(B)とから形成され、脂環式炭化水素基を有するポリカーボネート骨格を有するポリウレタン樹脂(U)を前記保護層が含有してなり、少なくとも条件(1)および条件(2)のいずれかを満たすことを特徴とする加飾成形体の製造方法。
条件(1):ポリウレタン樹脂(U)が分子内にアルコキシシリル基および/またはシラノール基を有する。
条件(2):前記保護層がグリシジルエーテル基ならびにアルコキシシリル基および/またはシラノール基を有する化合物(X)を含有し、ポリウレタン樹脂(U)がカルボキシル基および/またはその塩を有する。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/362,277 US20140295181A1 (en) | 2011-12-28 | 2012-12-25 | Multilayer film for decorative moldnig, polyurethane resin, and method for producing decorative molded body |
RU2014123712A RU2617478C1 (ru) | 2011-12-28 | 2012-12-25 | Многослойная пленка для декоративного формования, полиуретановая смола и способ получения декоративного формованного изделия |
JP2013506374A JP5314216B1 (ja) | 2011-12-28 | 2012-12-25 | 加飾成形用積層フィルム、ポリウレタン樹脂および加飾成形体の製造方法 |
KR1020147014632A KR102070467B1 (ko) | 2011-12-28 | 2012-12-25 | 장식 성형용 적층 필름, 폴리우레탄 수지 및 장식 성형체의 제조 방법 |
MX2014007157A MX2014007157A (es) | 2011-12-28 | 2012-12-25 | Pelicula de multiples capas para el moldeado decorativo, resina de poliuretano, y metodo para la produccion de un cuerpo moldeado decorativo. |
CN201280061801.8A CN103998241B (zh) | 2011-12-28 | 2012-12-25 | 装饰成型用层叠膜、聚氨酯树脂和装饰成型体的制造方法 |
EP12861270.2A EP2799236B1 (en) | 2011-12-28 | 2012-12-25 | Multilayer film for decorative molding, polyurethane resin, and method for producing decorative molded body |
US15/479,436 US10000667B2 (en) | 2011-12-28 | 2017-04-05 | Multilayer film for decorative molding |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-288235 | 2011-12-28 | ||
JP2011288235 | 2011-12-28 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/362,277 A-371-Of-International US20140295181A1 (en) | 2011-12-28 | 2012-12-25 | Multilayer film for decorative moldnig, polyurethane resin, and method for producing decorative molded body |
US15/479,436 Division US10000667B2 (en) | 2011-12-28 | 2017-04-05 | Multilayer film for decorative molding |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013099829A1 true WO2013099829A1 (ja) | 2013-07-04 |
Family
ID=48697314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/083384 WO2013099829A1 (ja) | 2011-12-28 | 2012-12-25 | 加飾成形用積層フィルム、ポリウレタン樹脂および加飾成形体の製造方法 |
Country Status (8)
Country | Link |
---|---|
US (2) | US20140295181A1 (ja) |
EP (1) | EP2799236B1 (ja) |
JP (1) | JP5314216B1 (ja) |
KR (1) | KR102070467B1 (ja) |
CN (1) | CN103998241B (ja) |
MX (1) | MX2014007157A (ja) |
RU (1) | RU2617478C1 (ja) |
WO (1) | WO2013099829A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013151666A (ja) * | 2011-12-28 | 2013-08-08 | Sanyo Chem Ind Ltd | ポリウレタン樹脂 |
JP2015034266A (ja) * | 2013-08-09 | 2015-02-19 | 旭化成ケミカルズ株式会社 | ポリカーボネートジオール、熱可塑性ポリウレタン、コーティング組成物及び塗膜 |
KR20160132492A (ko) | 2015-01-29 | 2016-11-18 | 가부시키가이샤 프로토 기켄 | 열경화성 수지 성형품의 제조 방법 |
JPWO2014196516A1 (ja) * | 2013-06-04 | 2017-02-23 | 東レ株式会社 | 装飾成形用フィルムおよび装飾成形体 |
JP2018083950A (ja) * | 2017-12-21 | 2018-05-31 | 日本ペイント・オートモーティブコーティングス株式会社 | 3次元成型品加飾用積層フィルムのクリヤー塗膜層形成用塗料組成物 |
JP2019513848A (ja) * | 2016-03-10 | 2019-05-30 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッドMomentive Performance Materials Inc. | ポリカーボネートジオールから誘導された湿気硬化性シリル化樹脂並びにそれを含むコーティング、シーラント及び接着性組成物 |
JP2022066208A (ja) * | 2016-09-20 | 2022-04-28 | エントロテック・インコーポレーテッド | 欠陥を低減したペイントフィルムアップリケ、物品および方法 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6219557B2 (ja) * | 2012-05-16 | 2017-10-25 | スリーエム イノベイティブ プロパティズ カンパニー | 装飾シート及び構造体 |
EP2848404B1 (en) * | 2013-09-13 | 2017-11-29 | Faurecia Innenraum Systeme GmbH | Roller shutter and storage compartment comprising said roller shutter |
JP6537248B2 (ja) * | 2014-10-31 | 2019-07-03 | 株式会社康井精機 | 機能性物質薄膜素材の製造方法並びに機能性物質薄膜素材およびその積層体 |
WO2018044883A1 (en) * | 2016-08-29 | 2018-03-08 | Invista North America S.A R.L. | Multifunctional polyamine-based compounds |
KR102034640B1 (ko) * | 2017-03-17 | 2019-10-22 | 주식회사 엘지화학 | 열가소성 폴리 우레탄 필름 및 이의 제조 방법 |
US20220185973A1 (en) * | 2019-02-15 | 2022-06-16 | Avery Dennison Corporation | Polyurethane synthesis |
WO2021002342A1 (ja) * | 2019-07-02 | 2021-01-07 | 三洋化成工業株式会社 | 複層フィルム |
JP7369559B2 (ja) * | 2019-07-30 | 2023-10-26 | トヨタ自動車株式会社 | 3次元成型品加飾用積層フィルム |
JP2021020414A (ja) * | 2019-07-30 | 2021-02-18 | トヨタ車体株式会社 | 3次元成型品加飾用積層フィルム |
KR102097617B1 (ko) * | 2019-09-18 | 2020-04-10 | 주식회사 영우 | 곡면부에 대한 접착성이 우수한 데코레이션 필름 |
CN110698622A (zh) * | 2019-10-12 | 2020-01-17 | 北京长润化工有限公司 | 酮亚胺潜伏固化剂和具有其的反应型聚氨酯热熔胶及应用 |
JP2021088147A (ja) * | 2019-12-05 | 2021-06-10 | スリーエム イノベイティブ プロパティズ カンパニー | 装飾フィルム及びそれを用いた装飾物品、並びに表面保護組成物 |
JP6868083B1 (ja) * | 2019-12-06 | 2021-05-12 | 日本マタイ株式会社 | 多層フィルム |
TWI757148B (zh) * | 2019-12-13 | 2022-03-01 | 詮達化學股份有限公司 | 一種具有高拉伸強度的熱可塑性聚氨酯、其製備配方及製造方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002226775A (ja) * | 2001-02-02 | 2002-08-14 | Chugoku Marine Paints Ltd | 帯電防止用塗料組成物、その被膜および帯電防止方法 |
JP2002322415A (ja) * | 2001-04-26 | 2002-11-08 | Chugoku Marine Paints Ltd | 帯電防止用塗料組成物、その被膜および帯電防止方法 |
JP2003212938A (ja) | 2002-01-24 | 2003-07-30 | Mitsubishi Rayon Co Ltd | 活性エネルギー線硬化性組成物、及び転写シート |
JP2004002732A (ja) | 2002-03-28 | 2004-01-08 | Dainippon Ink & Chem Inc | ポリウレタンエマルジョンの製造法 |
JP2004299223A (ja) | 2003-03-31 | 2004-10-28 | Nippon Bee Chemical Co Ltd | メタル調積層フィルム及びそれを用いた加飾成形体 |
JP2009149095A (ja) * | 2009-01-19 | 2009-07-09 | Dainippon Printing Co Ltd | 転写シート |
WO2010122599A1 (ja) | 2009-04-22 | 2010-10-28 | 三洋化成工業株式会社 | ポリウレタン樹脂水分散体 |
JP2010260942A (ja) | 2009-05-01 | 2010-11-18 | Three M Innovative Properties Co | 表面保護フィルム及びそれを備える多層フィルム |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU1111880A1 (ru) * | 1983-01-26 | 1984-09-07 | Институт химии высокомолекулярных соединений АН УССР | Декоративный пленочный материал |
JPH024736A (ja) * | 1988-06-22 | 1990-01-09 | Hitachi Maxell Ltd | ポリカーボネートポリオール、芳香族ポリカーボネートポリウレタン樹脂、コーティング材、キャストフィルム、磁気記録媒体 |
JP2002226755A (ja) * | 2001-02-06 | 2002-08-14 | Daicel Chem Ind Ltd | 印刷インキ組成物 |
US7238745B2 (en) * | 2003-12-15 | 2007-07-03 | Bayer Materialscience Llc | Aqueous polyurethane/urea dispersions containing alkoxysilane groups |
WO2005092607A1 (ja) * | 2004-03-25 | 2005-10-06 | Mitsubishi Plastics, Inc. | ガスバリア性積層体 |
JP2006021531A (ja) * | 2004-06-11 | 2006-01-26 | Mitsubishi Chem Mkv Co | 積層体 |
US8524838B2 (en) * | 2004-09-21 | 2013-09-03 | Showa Denko K.K. | Heat-curable urethane resin composition |
TW200643059A (en) * | 2005-04-06 | 2006-12-16 | Showa Denko Kk | Polymer of polycarbonate diol having an alicyclic structure and production process thereof |
CA2610272A1 (en) * | 2005-06-14 | 2006-12-21 | Asahi Glass Company, Limited | Multilayer laminate of fluororesin |
TW200744851A (en) * | 2006-04-13 | 2007-12-16 | Toray Industries | Gas barrier film |
JP4799282B2 (ja) * | 2006-06-09 | 2011-10-26 | コニシ株式会社 | シリル化ウレタン系水性組成物 |
JP2009235257A (ja) * | 2008-03-27 | 2009-10-15 | Konishi Co Ltd | 水性シリル化ウレタン系樹脂組成物 |
KR101363238B1 (ko) * | 2008-05-26 | 2014-02-12 | 디아이씨 가부시끼가이샤 | 코팅제 및 그 제조 방법 |
US20110112245A1 (en) * | 2008-07-11 | 2011-05-12 | Taku Nakamura | Aqueous polyurethane resin dispersion, process for preparing the same and coating composition containing the same |
JP2010105385A (ja) * | 2008-09-30 | 2010-05-13 | Toyoda Gosei Co Ltd | 化粧シート及び化粧成形品 |
CN102959019B (zh) * | 2010-07-02 | 2015-05-13 | 关西涂料株式会社 | 形成多层涂膜的方法 |
-
2012
- 2012-12-25 JP JP2013506374A patent/JP5314216B1/ja not_active Expired - Fee Related
- 2012-12-25 CN CN201280061801.8A patent/CN103998241B/zh active Active
- 2012-12-25 WO PCT/JP2012/083384 patent/WO2013099829A1/ja active Application Filing
- 2012-12-25 US US14/362,277 patent/US20140295181A1/en not_active Abandoned
- 2012-12-25 KR KR1020147014632A patent/KR102070467B1/ko active IP Right Grant
- 2012-12-25 MX MX2014007157A patent/MX2014007157A/es unknown
- 2012-12-25 RU RU2014123712A patent/RU2617478C1/ru not_active IP Right Cessation
- 2012-12-25 EP EP12861270.2A patent/EP2799236B1/en active Active
-
2017
- 2017-04-05 US US15/479,436 patent/US10000667B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002226775A (ja) * | 2001-02-02 | 2002-08-14 | Chugoku Marine Paints Ltd | 帯電防止用塗料組成物、その被膜および帯電防止方法 |
JP2002322415A (ja) * | 2001-04-26 | 2002-11-08 | Chugoku Marine Paints Ltd | 帯電防止用塗料組成物、その被膜および帯電防止方法 |
JP2003212938A (ja) | 2002-01-24 | 2003-07-30 | Mitsubishi Rayon Co Ltd | 活性エネルギー線硬化性組成物、及び転写シート |
JP2004002732A (ja) | 2002-03-28 | 2004-01-08 | Dainippon Ink & Chem Inc | ポリウレタンエマルジョンの製造法 |
JP2004299223A (ja) | 2003-03-31 | 2004-10-28 | Nippon Bee Chemical Co Ltd | メタル調積層フィルム及びそれを用いた加飾成形体 |
JP2009149095A (ja) * | 2009-01-19 | 2009-07-09 | Dainippon Printing Co Ltd | 転写シート |
WO2010122599A1 (ja) | 2009-04-22 | 2010-10-28 | 三洋化成工業株式会社 | ポリウレタン樹脂水分散体 |
JP2010260942A (ja) | 2009-05-01 | 2010-11-18 | Three M Innovative Properties Co | 表面保護フィルム及びそれを備える多層フィルム |
Non-Patent Citations (1)
Title |
---|
See also references of EP2799236A4 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013151666A (ja) * | 2011-12-28 | 2013-08-08 | Sanyo Chem Ind Ltd | ポリウレタン樹脂 |
JPWO2014196516A1 (ja) * | 2013-06-04 | 2017-02-23 | 東レ株式会社 | 装飾成形用フィルムおよび装飾成形体 |
JP2015034266A (ja) * | 2013-08-09 | 2015-02-19 | 旭化成ケミカルズ株式会社 | ポリカーボネートジオール、熱可塑性ポリウレタン、コーティング組成物及び塗膜 |
KR20160132492A (ko) | 2015-01-29 | 2016-11-18 | 가부시키가이샤 프로토 기켄 | 열경화성 수지 성형품의 제조 방법 |
JP2019513848A (ja) * | 2016-03-10 | 2019-05-30 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッドMomentive Performance Materials Inc. | ポリカーボネートジオールから誘導された湿気硬化性シリル化樹脂並びにそれを含むコーティング、シーラント及び接着性組成物 |
JP6993345B2 (ja) | 2016-03-10 | 2022-01-13 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | ポリカーボネートジオールから誘導された湿気硬化性シリル化樹脂並びにそれを含むコーティング、シーラント及び接着性組成物 |
JP2022066208A (ja) * | 2016-09-20 | 2022-04-28 | エントロテック・インコーポレーテッド | 欠陥を低減したペイントフィルムアップリケ、物品および方法 |
US11827823B2 (en) | 2016-09-20 | 2023-11-28 | Ppg Advanced Surface Technologies, Llc | Paint film appliques with reduced defects, articles, and methods |
JP7392253B2 (ja) | 2016-09-20 | 2023-12-06 | ピーピージー・アドバンスト・サーフェス・テクノロジーズ・エルエルシー | 欠陥を低減したペイントフィルムアップリケ、物品および方法 |
US11884849B2 (en) | 2016-09-20 | 2024-01-30 | Ppg Advanced Surface Technologies, Llc | Paint film appliques with reduced defects, articles, and methods |
JP2018083950A (ja) * | 2017-12-21 | 2018-05-31 | 日本ペイント・オートモーティブコーティングス株式会社 | 3次元成型品加飾用積層フィルムのクリヤー塗膜層形成用塗料組成物 |
Also Published As
Publication number | Publication date |
---|---|
US20170204298A1 (en) | 2017-07-20 |
KR20140110846A (ko) | 2014-09-17 |
CN103998241A (zh) | 2014-08-20 |
EP2799236A4 (en) | 2015-08-19 |
EP2799236A1 (en) | 2014-11-05 |
MX2014007157A (es) | 2014-11-26 |
KR102070467B1 (ko) | 2020-01-29 |
JPWO2013099829A1 (ja) | 2015-05-07 |
JP5314216B1 (ja) | 2013-10-16 |
RU2617478C1 (ru) | 2017-04-25 |
US20140295181A1 (en) | 2014-10-02 |
EP2799236B1 (en) | 2016-11-09 |
US10000667B2 (en) | 2018-06-19 |
CN103998241B (zh) | 2016-11-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5314216B1 (ja) | 加飾成形用積層フィルム、ポリウレタン樹脂および加飾成形体の製造方法 | |
CN105829464B (zh) | 涂布剂及层叠体 | |
KR102033976B1 (ko) | 우레탄 수지 조성물, 프라이머, 적층체 및 화상 표시 장치 | |
JP2013155473A (ja) | 合成擬革の表皮層形成用塗料および合成擬革の製造方法 | |
JP6599654B2 (ja) | 真空成形用3次元成型品加飾用積層フィルム、3次元成型品加飾方法及び加飾成形体 | |
JP2008023854A (ja) | シート状積層体 | |
JP2008132654A (ja) | 熱成形用積層シート | |
JP5272232B2 (ja) | 化粧シート並びにそれを形成するためのポリカーボネート系ポリウレタン樹脂及びその樹脂を含む水性インキ | |
JP2003342344A (ja) | ポリウレタン樹脂 | |
JP2013142117A (ja) | 印刷インキ組成物 | |
JP2004010655A (ja) | 2液硬化型ポリウレタン樹脂組成物およびガスバリア性ラミネート用接着剤 | |
JP6361504B2 (ja) | 装飾成形用フィルムおよび装飾成形体 | |
JP2015182421A (ja) | 成型用積層フィルム | |
JP2014504322A (ja) | アミン系促進剤を含有する接着樹脂組成物及びそれを含む装飾フィルム | |
AU2015259178A1 (en) | Digitally printable topcoat | |
JP7213840B2 (ja) | 加飾シート、及び加飾成形品 | |
KR20220119028A (ko) | 3차원 성형품 가식용 적층 필름, 그 제조 방법 및 3차원 가식 방법 | |
JP4474841B2 (ja) | ラミネート用2液型接着剤組成物及びこれを用いて得られる積層シート、トレー容器 | |
JP2015223765A (ja) | 成型体の修復方法 | |
JP2017061136A (ja) | 成形用積層フィルム | |
JP2017177653A (ja) | 積層フィルム | |
JP2013116936A (ja) | 印刷インキ組成物 | |
JP7245381B1 (ja) | 積層体、及び包装体 | |
JP2023144899A (ja) | 包装材、及びその製造方法 | |
JP2023174286A (ja) | 装飾フィルム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013506374 Country of ref document: JP 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: 12861270 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147014632 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2012861270 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012861270 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14362277 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2014/007157 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2014123712 Country of ref document: RU Kind code of ref document: A |