WO2014196516A1 - 装飾成形用フィルムおよび装飾成形体 - Google Patents
装飾成形用フィルムおよび装飾成形体 Download PDFInfo
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- WO2014196516A1 WO2014196516A1 PCT/JP2014/064706 JP2014064706W WO2014196516A1 WO 2014196516 A1 WO2014196516 A1 WO 2014196516A1 JP 2014064706 W JP2014064706 W JP 2014064706W WO 2014196516 A1 WO2014196516 A1 WO 2014196516A1
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- decorative
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- 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
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
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- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
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- 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
Definitions
- the present invention relates to a decorative molding film used for decorating a decorative body used in building materials, mobile phones, electrical products, gaming machine parts, automobile parts, and the like, and a decorative molded body using the same.
- the present invention relates to a decorative molding film having a good shape following property even for a decorative object having a complicated shape such as deep drawing and having a surface that is hardly damaged, and a decorative molded body using the same.
- Patent Document 1 an easily moldable film using polyethylene terephthalate having a high melting point has been proposed.
- polyester films that selectively reflect wavelengths by laminating resin layers having different refractive indexes alternately in multiple layers.
- This film that selectively reflects a specific wavelength is characterized by having a metallic appearance depending on the number of layers and the reflection wavelength, and also has formability because it is very flexible.
- Patent Documents 6 and 7 propose a molding film having a protective layer mainly composed of an acrylic resin.
- Patent Document 8 a film for molding is proposed which has a urethane resin as a main and has a protective layer that is cured only by thermal curing.
- JP 2001-347565 A Japanese Patent Laid-Open No. 2005-97528 JP 2004-131546 A JP 2005-059332 A Japanese Patent Laid-Open No. 2004-249687 JP 2004-299223 A Japanese Patent Laid-Open No. 2003-212938 JP 2010-260942 A
- the protective layer which is the layer covering the outermost surface of the object to be decorated, must have scratch resistance (scratch resistance) and weather resistance. It plays an important role in the decoration of decorative bodies. If the size of the object to be decorated is increased in the decoration object 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 object to be decorated at one time. When it becomes complicated, it is necessary that the decorative molding film is deformed along the concavo-convex shape and the entire surface follows the shape. That is, the protective layer of the decorative molding film needs to have scratch resistance and followability to the object to be decorated as the decorative molding film, and demands for these properties are increasing. In addition, it is also demanded that the productivity is high, that is, the molding is completed with a small number of steps.
- Patent Documents 4 and 5 have a problem that when the film is applied to a decorative molded body, the surface hardness of the film is low, so that the decorative molded body has poor scratch resistance.
- Patent Document 8 has a problem in that the scratch resistance necessary for the protective layer and the followability to the object to be decorated are not compatible.
- An object of the present invention is to provide a film for decorative molding having a protective layer having good stretchability suitable for a film decoration method and good scratch resistance in view of the background of such a conventional technique. .
- the decorative molding film of the present invention has the following configuration. That is, A decorative molding film having a laminated structure in which a protective layer is disposed on at least one surface of a base film, wherein the base film is a resin PA and a resin PB having different in-plane average refractive indexes, The in-plane average refractive index is higher than the in-plane average refractive index of the resin PB, and the layer containing the resin PA (PA layer) and the layer containing the resin PB (PB layer) are alternately 50 layers or more.
- a decorative molding film comprising a polyurethane resin (U) having a polycarbonate skeleton containing a cyclic hydrocarbon group and satisfying at least one of the conditions (1) and (2).
- the polyurethane resin (U) contains an alkoxysilyl group and / or a silanol group in the molecule.
- the polyurethane resin (U) contains a carboxyl group and / or a salt thereof, and the protective layer further contains a compound (X) containing a glycidyl ether group and an alkoxysilyl group and / or a silanol group. .
- the decorative molded body of this invention has the following structure. That is, A decorative molded body using the decorative molding film.
- the difference between the in-plane average refractive index of the resin PA constituting the PA layer and the in-plane average refractive index of the resin PB constituting the PB layer is preferably 0.01 or more. .
- the absolute reflectance of the substrate film at any wavelength in the wavelength band of 400 to 800 nm is preferably 30% or more.
- the difference in glass transition temperature between the resin PA and the resin PB is preferably 20 ° C. or less.
- the decorative molding film of the present invention is excellent in followability to the object to be decorated, and further, the curing of the protective layer is sufficiently advanced and completed by heat during molding, so the decorative molding film of the present invention is used. As a result, it is possible to obtain a decorative molded body having high productivity and good followability to the object to be decorated and scratch resistance.
- the decorative molding film of the present invention is a decorative molding film having a laminated structure in which a protective layer is disposed on at least one surface of a base film, and the base film has a different in-plane average refractive index from a resin PA.
- a resin PB having an in-plane average refractive index of the resin PA that is relatively higher than the in-plane average refractive index of the resin PB, and a layer containing the resin PA (PA layer) and a layer containing the resin PB (PB layer) )
- the protective layer is at least an active hydrogen component (A) and an organic isocyanate component (B) and a polyurethane resin (U) having a polycarbonate skeleton containing an alicyclic hydrocarbon group, and containing at least the condition (1) [polyurethane resin (U) in the molecule
- the protective layer contains a compound (X) containing a glycidyl ether group and an alkoxysilyl group and / or a silanol group, and the polyurethane resin (U) contains a carboxyl group and / or a salt thereof. . ] Is satisfied.
- the decorative molding film of the present invention is laminated so that the base film is in contact with the surface of the object to be decorated, and is attached to the object to be decorated by thermoforming. Can be decorated.
- the decorative body is not a constituent element of the decorative molding film of the present invention, but is shown in parentheses in order to clearly show the application mode of the decorative molding film of the present invention.
- Protective layer / base film (/ decorated body) By decorating the object to be decorated using such a decorative molding film of the present invention, solventless coating, plating replacement, and the like can be achieved.
- the decorative molding film has a protective layer satisfying at least one of the above conditions (1) and (2), the protective layer is cured by heat during molding, and energy is separately obtained. Since no irradiation process is required, productivity is high, scratch resistance is good, and followability to the decoration is good. By using such a decorative molding film, it is possible to obtain a decorative molded body having a good appearance.
- the base film in the present invention includes a structure in which a layer containing a resin PA (PA layer) and a layer containing a resin PB (PB layer) are alternately laminated by 50 layers or more, and forms a PA layer and a PB layer.
- the resin to be used may be either a thermoplastic resin or a thermosetting resin, as long as the in-plane average refractive index of the PA layer is relatively higher than the in-plane average refractive index of the PB layer. It may be a copolymer or a blend of two or more. More preferably, it is a thermoplastic resin because of good moldability. The in-plane average refractive index will be described later.
- each resin various additives such as pigments, dyes, antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, thickeners, thermal stabilizers, lubricants, infrared absorbers, An ultraviolet absorber, a dopant for adjusting the refractive index, and the like may be added.
- additives such as pigments, dyes, antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, thickeners, thermal stabilizers, lubricants, infrared absorbers, An ultraviolet absorber, a dopant for adjusting the refractive index, and the like may be added.
- thermoplastic resin (resin PA, resin PB) constituting the PA layer and PB layer
- examples of the resin thermoplastic resin (resin PA, resin PB) constituting the PA layer and PB layer include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, nylon 6, nylon 66, and the like.
- Acrylic resin, methacrylic resin there can be used polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like.
- resins having excellent surface hardness are acrylic resin, methacrylic resin, and acetal resin, and polyester is particularly preferable from the viewpoint of strength, heat resistance, transparency, and moldability.
- the polyester that can be preferably used as the resin PA and the resin PB refers to a homopolyester or a copolyester that is a polycondensate of a dicarboxylic acid component skeleton and a diol component skeleton.
- typical examples of the homopolyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene diphenylate, and the like.
- polyethylene terephthalate is preferable because it is inexpensive and can be used in a wide variety of applications.
- the copolymer polyester that can be preferably used as the resin PA and the resin PB in the present invention is a polycondensate comprising at least three components selected from the following components having a dicarboxylic acid skeleton and components having a diol skeleton. Is defined as
- Components having a dicarboxylic acid skeleton include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid.
- Components having a glycol skeleton include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis (4′- ⁇ -hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol and the like.
- the substrate film when used as a decorative molding film, preferably has a high elongation.
- the elastic modulus at 150 ° C. is preferably from 80 MPa to 380 MPa, and the elongation at break is preferably from 120% to 400%.
- any polyester resin preferably used as the resin PA and the resin PB 50 to 90 mol% of the constituent glycol residue components are ethylene glycol residues, and 10 to 30 mol% are 1,4-moles. It is preferable that 0.1 to 10 mol% of butanediol residues are other glycol residue components.
- the content of 1,4-butanediol residues is more preferably 15 to 25 mol%, and the other glycol residue components are more preferably 1 to 5 mol%.
- each glycol residue component may be present by being copolymerized in the polyester, but if copolymerization is performed, the melting point is lowered and heat resistance may be deteriorated.
- polyester resins having a glycol residue component alone may be blended and contained in the film, or blending and copolymerization may be used in combination.
- Other glycol residue components are not particularly limited, but include diethylene glycol residues, 1,4-cyclohexanedimethanol residues, neopentyl glycol residues, 1,3-propanediol residues, etc. Can be preferably mentioned.
- the polyester film forming the base material has 95 to 99 mol% of dicarboxylic acid residue components constituting the polyester resin constituting the film, and terephthalic acid residues. It is preferable that mol% is other dicarboxylic acid residue components.
- the other dicarboxylic acid residue component is more preferably 1 to 3 mol%.
- the dicarboxylic acid residue component may use a dicarboxylic acid as a starting component or a dicarboxylic acid ester derivative as a starting component.
- the terephthalic acid residue and the other dicarboxylic acid residue may be present in the polyester by copolymerization.
- the melting point is lowered when the copolymerization is carried out, separate polyesters are used from the viewpoint of heat resistance.
- a method of existing in the resin and blending the polyester resin in the film is preferable.
- dicarboxylic acid residue components are not particularly limited, but 2,6-naphthalenedicarboxylic acid residue, isophthalic acid residue, 5-sodium sulfoisophthalic acid residue, adipic acid residue, sebacic acid residue Preferred examples include a group, dimer acid residue, 1,4-cyclohexanedicarboxylic acid residue and the like.
- the in-plane average refractive index of the resin PA constituting the PA layer is relatively higher than the in-plane average refractive index of the resin PB constituting the PB layer.
- the difference between the in-plane average refractive index of the constituting resin PA and the in-plane average refractive index of the resin PB constituting the PB layer is preferably 0.01 or more. More preferably, it is 0.03 or more, More preferably, it is 0.05 or more.
- the in-plane refractive index here refers to the refractive index in the direction parallel to the substrate film surface, and can be measured with a known refractometer.
- the in-plane average refractive index is parallel to the film surface.
- the average in-plane refractive index of the resin PA constituting the PA layer When the difference in refractive index in the thickness direction of the resin PA is 0.01 or more, the in-plane average refractive index of the resin PB constituting the PB layer and the refractive index difference in the thickness direction of the resin PB are 0.01 or less. Even if the incident angle is increased, it is more preferable because the reflectance in the reflection band is not easily lowered.
- the refractive index in the thickness direction here refers to the refractive index in the direction perpendicular to the substrate film surface, and can be measured with a known refractometer according to JIS K 7105 (1981).
- the thickness of one layer of the PA layer and the PB layer is 0.03 ⁇ m or more and 0.5 ⁇ m or less, preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less, and preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less. More preferable. By having such a configuration, the film exhibits an excellent gloss feeling due to interference reflection.
- the absolute value of the difference in SP value between the resin PA and the resin PB is preferably 1.0 or less.
- SP value here means the solubility parameter calculated
- the resin PA and the resin PB are preferably resins containing the same basic skeleton.
- the basic skeleton is a repeating unit constituting the resin.
- one resin is polyethylene terephthalate
- ethylene terephthalate is the basic skeleton.
- the resin PA and the resin PB are resins including the same basic skeleton because peeling between layers is less likely to occur.
- the difference in glass transition temperature between the resin PA and the resin PB is preferably 20 ° C. or less. More preferably, it is 10 degrees C or less, More preferably, it is 5 degrees C or less. Moreover, as a lower limit, 0 degreeC (There is no difference of the glass transition temperature of resin PA and resin PB) is preferable.
- the glass transition temperature is the temperature at the midpoint of the stepwise endothermic peak accompanied by a change in specific heat capacity, and can be calculated by a known differential calorimetry (DSC) according to JIS K 7122 (1987). it can.
- the resin PA is polyethylene terephthalate or polyethylene naphthalate
- the resin PB is a polyester comprising spiroglycol or cyclohexanedimethanol.
- the polyester comprising spiroglycol refers to a copolyester copolymerized with spiroglycol, a homopolyester, or a polyester blended with them.
- the polyester comprising cyclohexanedimethanol refers to a copolyester obtained by copolymerizing cyclohexanedimethanol, a homopolyester, or a polyester obtained by blending them.
- Polyesters containing spiroglycol or cyclohexanedimethanol are preferred because the difference in glass transition temperature between polyethylene terephthalate and polyethylene naphthalate is small, so that overstretching is difficult during molding and delamination does not occur easily.
- the resin PA is polyethylene terephthalate or polyethylene naphthalate and the resin PB is a polyester comprising spiroglycol
- the resin PB is a polyester comprising spiroglycol and cyclohexanedicarboxylic acid.
- the polyester in which the resin PB contains spiroglycol and cyclohexanedicarboxylic acid is a polyester copolymerized with spiroglycol and cyclohexanedicarboxylic acid (or an ester derivative of cyclohexanedicarboxylic acid), a homopolyester, or a polyester blended with the polyester.
- the resin PB is a polyester comprising spiroglycol and cyclohexanedicarboxylic acid
- the difference in the in-plane refractive index from polyethylene terephthalate or polyethylene naphthalate is increased, so that a high reflectance is easily obtained.
- the difference in glass transition temperature between polyethylene terephthalate and polyethylene naphthalate is small, it is difficult to be over-stretched during molding and also difficult to delaminate.
- the copolymerization amount of the cyclohexanedimethanol is 15 mol% or more and 60 mol%. It is the following ethylene terephthalate polycondensate. In this way, while having high reflection performance, the change in optical characteristics due to heating and aging is particularly small, and peeling between layers is less likely to occur.
- the cyclohexanedimethanol group has a cis or trans isomer as a geometric isomer, and a chair type or a boat type as a conformational isomer.
- the change in optical characteristics due to thermal history is even less, and blurring during film formation hardly occurs.
- Having a structure in which layers containing a resin PA (PA layer) and layers containing a resin PB (PB layer) are alternately laminated means that the layer has a structure in which PA layers and PB layers are alternately laminated in the thickness direction. Is defined to exist. That is, it is preferable that the order of arrangement in the thickness direction of the PA layer and the PB layer in the film of the present invention is not in a random state, and the order of arrangement of the third layer or more other than the PA layer and the PB layer is as follows. It is not particularly limited.
- the PA layer is denoted as A, the PB layer as B, and the PC layer as C.
- the base film includes 50 or more layers alternately including a layer containing a resin PA (PA layer) and a layer containing a resin PB (PB layer), and preferably 200 layers or more. More preferably, the total number of layers of the PA layer and the PB layer is 600 layers or more. If the structure in which 50 layers or more of the PA layer and the PB layer are laminated is not included, sufficient reflectance may not be obtained, and an appearance with low luminance may be obtained. Also, if 200 layers or more of the layers containing the resin PA (PA layer) and the layers containing the resin PB (PB layer) are alternately contained, the absolute reflectance in the wavelength band 400 nm to 800 nm should be 30% or more. Becomes easy.
- the upper limit value of the number of layers is not particularly limited, but considering the decrease in wavelength selectivity accompanying the decrease in stacking accuracy due to the increase in the size of the device and the increase in the number of layers, 1,500 layers or less It is preferable that
- the base film in which 50 layers or more of layers containing a resin PA (PA layer) and a layer containing a resin PB (PB layer) are alternately laminated in the wavelength band of 400 to 800 nm is used in the present invention.
- the absolute reflectance is preferably 30% or more.
- the absolute reflectance at any wavelength in the wavelength band of 400 nm to 800 nm is 30% or more, a high-quality metallic or half-mirror film can be obtained. More preferably, the absolute reflectance over the entire wavelength band of 400 nm to 1,000 nm is 30% or more. In this case, the metallic tone is maintained even after molding, and color change hardly occurs depending on the viewing angle, which is preferable.
- the absolute reflectance is 30% or higher on the higher wavelength side (700 nm or more) than visible light, so that even if the film thickness is reduced by stretching and the reflection band is shifted to the lower wavelength side by the viewing angle, This is because the absolute reflectance in the visible light region can be maintained at 30% or more. More preferably, the absolute reflectance over the entire wavelength band of 400 nm to 1,000 nm is 40% or more. More preferably, the absolute reflectance over the entire wavelength band of 400 nm to 1,000 nm is 60% or more. The higher the absolute reflectance, the higher the brightness of the metallic tone. It is more preferable that the absolute reflectance in the wavelength band of 400 nm to 1,200 nm is 30% or more.
- the absolute reflectance is an absolute reflectance at an incident angle of 5 °, and can be measured with a known spectrophotometer.
- the thickness of the base film is preferably 12 ⁇ m or more and 500 ⁇ m or less in terms of breaking strength and shape retention. More preferably, they are 25 micrometers or more and 300 micrometers or less, More preferably, they are 50 micrometers or more and 200 micrometers or less.
- the boundary with the protective layer is “ It can be obtained by observing at “the boundary between the PA layer and the PB layer”.
- the base film used in the present invention may be subjected to surface treatment such as corona discharge treatment, low temperature plasma treatment, glow discharge treatment, flame treatment, etching treatment, roughening treatment, and the like.
- Functional layers such as prevention layer, abrasion-resistant layer, antireflection layer, color correction layer, ultraviolet absorption layer, printing layer, transparent conductive layer, gas barrier layer, hologram layer, release layer, embossing layer, adhesive layer, adhesive layer It may be formed.
- the protective layer in the present invention comprises a polyurethane resin (U) having a polycarbonate skeleton containing at least an active hydrogen component (A) and an organic isocyanate component (B) and containing an alicyclic hydrocarbon group.
- the polyurethane resin (U) has a polycarbonate skeleton containing an alicyclic hydrocarbon group, the crystallinity is high, scratch resistance and design characteristics are easily obtained, and followability to the decorative body is ensured. be able to.
- Such a polyurethane resin (U) is a polyurethane resin formed from an active hydrogen component (A) containing a polycarbonate polyol (a1) containing an alicyclic hydrocarbon group and an organic isocyanate component (B). preferable.
- Examples of the polycarbonate polyol (a1) containing an alicyclic hydrocarbon group include an alicyclic polyvalent (2 to 3 or more) alcohol having 6 to 20 carbon atoms or an acyclic group having 2 to 20 carbon atoms.
- One or a mixture of two or more polyhydric (2 to 3 or more valent) alcohols preferably alkylene diols containing an alkylene group having 6 to 10 carbon atoms, more preferably 6 to 9 carbon atoms
- 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.
- a compound name such as “polycarbonate polyol (a1) containing an alicyclic hydrocarbon group” with a symbol may be simply represented by only a symbol such as “(a1)”.
- Examples of the alicyclic polyvalent (2 to 3 or more) alcohol having 6 to 20 carbon atoms include 1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol hydrogenated bisphenol A, hydrogenated Bisphenol F, spiroglycol, dihydroxymethyltricyclodecane, etc. are mentioned.
- 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
- the range of the number average molecular weight (hereinafter abbreviated as Mn) of the polycarbonate polyol (a1) containing an alicyclic hydrocarbon group is preferably 500 to 5,000, more preferably from the viewpoint of the flexibility of the protective layer obtained. Is from 750 to 3,000, more preferably from 1,000 to 2,000. Mn can be measured by gel permeation chromatography using tetrahydrofuran as a solvent and polystyrene as a standard sample.
- the content ratio of the skeleton derived from the polycarbonate polyol (a1) containing an alicyclic hydrocarbon group in the polyurethane resin (U) is determined from the viewpoint of scratch resistance and design characteristics of the protective layer.
- the mass ratio of the cyclic hydrocarbon group contained in (a1) to the total mass of the organic isocyanate component (B) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, especially 10 to 15%. It is preferable that it is the quantity used as the mass%.
- the active hydrogen component (A) other than the polycarbonate polyol (a1) containing an alicyclic hydrocarbon group those conventionally used in the production of polyurethane can be used.
- a polymer polyol (a2) having a Mn of 500 to 5,000 other than (a1), a carboxyl group-containing polyol and its salt (a3), a chain extender (a4), a reaction terminator (a5), etc. can do.
- the polymer polyol (a2) having an Mn of 500 to 5,000 other than (a1) the polymer polyols conventionally used in the production of polyurethane can be used, but the weather resistance and water resistance of the resulting protective layer can be used. From this viewpoint, the aliphatic polycarbonate polyol (a21) is preferred.
- (A21) includes linear diols having 4 to 10 carbon atoms (1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, etc.), branched diols having 4 to 10 carbon atoms ( 2-methylbutanediol, 2-ethylbutanediol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, etc.) and one or a mixture of two or more thereof are converted into low molecular carbonate compounds (for example, Condensation with a dealcoholization reaction with a dialkyl carbonate having 1 to 6 carbon atoms of an alkyl group, an alkylene carbonate having 2 to 6 carbon atoms, a diaryl carbonate having an aryl group having 6 to 9 carbon atoms, or the like. And polycarbonate polyol produced by the above method.
- the carboxyl group-containing polyol and its salt (a3) are particularly preferably used when the polyurethane resin (U) is used as an aqueous dispersion.
- (A3) is a dialkylol alkanoic acid 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-dimethyloloctanoic acid] and the like and salts thereof.
- DMPA 2,2-dimethylolpropionic acid
- 2-dimethylolbutanoic acid 2, 2-dimethylol. Heptanoic acid and 2,2-dimethyloloctanoic 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 (dimethylamine, diethylamine). And dibutylamine) salts and tertiary monoamines (aliphatic tertiary monoamines such as trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine) salts, and the like. Combined use is also possible.
- the basic compound constituting the salt has a boiling point of ⁇ 40 ° C. to 150 ° C. at normal pressure.
- Specific examples thereof include ammonium salts, triethylamine salts, N, N-dimethylethanolamine salts, and the like.
- the content of the skeleton derived from the carboxyl group-containing polyol and its salt (a3) in the polyurethane resin (U) is determined from the viewpoints of dispersion stability and water resistance of the protective layer obtained, and the active hydrogen component (A) and the organic isocyanate.
- the mass ratio of the carboxyl group contained in (a3) with respect to the total mass of component (B) is preferably 0.01 to 1.5 mass%, more preferably 0.05 to 0.
- the value is .75% by mass, more preferably the value is 0.08 to 0.50% by mass.
- the content of carboxyl groups in the polyurethane resin (U) after the formation of the polyurethane resin (U) is such that the residue obtained by heating and drying 3 to 10 g of the polyurethane resin (U) at 130 ° C. for 45 minutes is washed with water and then again 130 ° C. And dried for 45 minutes, dissolved in dimethylformamide, and calculated from the acid value measured by the method described in JIS K 0070 (1992) (potentiometric titration method).
- Examples of the chain extender (a4) include acyclic polyhydric (2 to trivalent or higher valent) alcohols having 2 to 20 carbon atoms, ethylene oxide and / or propylene oxide of these acyclic polyhydric alcohols.
- reaction terminator (a5) examples include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, butanol, cellosolves and carbitols), 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 in the production of polyurethane can be used.
- the alicyclic polyisocyanate (B1) having 6 to 17 carbon atoms and the aliphatic polyisocyanate having 4 to 21 carbon atoms (B1) can be used.
- B2), aromatic polyisocyanates having 8 to 25 carbon atoms (B3), aromatic aliphatic polyisocyanates having 10 to 17 carbon atoms (B4), modified products 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 17 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 21 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexahexane.
- aromatic polyisocyanate (B3) having 8 to 25 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 17 carbon atoms include m- or p-xylylene diisocyanate and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate.
- Modified polyisocyanates (B5) of (B1) to (B4) include modified polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups). Or a modified product containing oxazolidone group, etc .; the content of free isocyanate group is usually 8 to 33% by mass, preferably 10 to 30% by mass, particularly preferably 12 to 29% by mass).
- Examples thereof include modified products of polyisocyanates such as urethane-modified MDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI, urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.
- modified products of polyisocyanates such as 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), (B1) and (B2) are preferred from the viewpoint of the weather resistance of the protective layer obtained, and IPDI and hydrogenated MDI are more preferred.
- the polyurethane resin (U) is preferably one that can be used as a solvent solution or an aqueous dispersion from the viewpoint of coating properties when forming a decorative molding film, and is an environment that reduces volatile organic compounds (VOC). What can be made into a water dispersion from a corresponding viewpoint is further more preferable.
- 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.
- a solvent to be used a known organic solvent can be used. From the viewpoint of the solubility of the polyurethane resin (U) and the drying property when obtaining a protective layer, acetone, dimethyl ketone, methyl isobutyl ketone, tetrahydrofuran, isopropyl alcohol, and the like. It is preferable to use a polar solvent having a boiling point of 100 ° C. or lower.
- a prepolymer mixing method described in JP-A No. 2004-2732 or the like, or a urethane polymer dead polymer (isocyanate group) described in JP-A No. 2009-96998 are disclosed. (Polyurethane resin that hardly contains) and then dispersed in water.
- 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) may be applied to a molding film by a known application method (for example, , Bar coats, roll coats, gravure coats, curtain coats, spray coats, silk screen prints, etc.) to form a polycarbonate polyurethane layer by reacting in a hot air oven or the like. it can.
- the protective layer composed of the polycarbonate-based polyurethane resin thus formed may further contain a resin other than the above-mentioned reactant, for example, acrylic polyurethane, polyether-based polyurethane, polyester-based polyurethane, etc. Can be contained.
- a resin other than the above-mentioned reactant for example, acrylic polyurethane, polyether-based polyurethane, polyester-based polyurethane, etc. Can be contained.
- the polyurethane resin (U) contains an alkoxysilyl group and / or a silanol group in the molecule.
- the protective layer contains a compound (X) containing a glycidyl ether group and an alkoxysilyl group and / or a silanol group, and the polyurethane resin (U) contains a carboxyl group and / or a salt thereof.
- a method for producing a polyurethane resin (U) having an alkoxysilyl group and / or silanol group in the molecule defined in the above condition (1) for example, a urethane resin containing an amino group or a carboxyl group, And a compound (X) containing a glycidyl ether group and an alkoxysilyl group and / or silanol group-containing compound (X), a urethane resin containing an isocyanate group, an amino group and an alkoxysilyl group in the molecule, and And / or a method (1-2) of reacting with a compound (Y) containing a silanol group.
- the compound (X) used in the method (1-1) includes a 4 to 11 carbonidylalkyltrialkoxysilane, a 4 to 13 carbonidoxyalkyl (alkyl) dialkoxysilane, and a 4 to 15 carbon atom.
- hydrolysates thereof (one in which the alkoxy group in the above compound is converted to a hydroxyl group), such as 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc., and hydrolysates thereof (the alkoxy group in the above compound is converted to a hydroxyl group) Can be mentioned.
- Compound (X) may be used alone or in combination of two or more.
- Examples of a method for obtaining a urethane resin containing a carboxyl group used in the method (1-1) include a method of using the above carboxyl group-containing polyol and a salt thereof (a3) as an active hydrogen component (A) during the production of a urethane resin. Can be mentioned.
- a method for obtaining an amino group-containing urethane resin used in the method (1-1) a diamine having 2 to 10 carbon atoms and poly (poly ((2)) exemplified as the chain extender (a4) in the description of the production of the urethane resin.
- A active hydrogen component
- B organic isocyanate component
- an isocyanate group is introduced at the terminal with an excess of the molar amount of the isocyanate group with respect to the active hydrogen (hydroxyl group, amino group, etc.) that reacts with the isocyanate group, and then reacted with water to form a terminal amino group.
- the method based on this etc. is mentioned.
- Conditions such as temperature and time for the reaction between the glycidyl ether group and the carboxyl group or amino group 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 11 carbon atoms, aminoalkyl (alkyl) dialkoxysilane having 4 to 13 carbon atoms, and amino having 4 to 15 carbon atoms.
- Alkyl (dialkyl) alkoxysilanes and the like and hydrolysates thereof in which the alkoxy group in the above compound is converted to a hydroxyl group), specifically, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, etc. and their hydrolysates (the alkoxy group in the above compound is water Which has been converted to group).
- a compound (Y) may be used individually by 1 type, and may use 2 or more types together.
- active hydrogen hydroxyl group, amino group, etc.
- active hydrogen hydroxyl group, amino group, etc.
- organic isocyanate component (B) a method for introducing an isocyanate group at the terminal by making the molar amount of the isocyanate group excessive.
- Conditions such as temperature and time for the reaction between the glycidyl ether group and the carboxyl group or amino group may be the same as those usually used for the reaction of these groups.
- the polyurethane resin (U) contains an alkoxysilyl group and / or silanol group in the molecule, a crosslinked structure is formed by crosslinking the alkoxysilyl group and / or silanol group by heating at the time of decorative molding, etc. And a protective layer excellent in scratch resistance.
- the compound (X) used in the method (1-1) can be used.
- a method for obtaining a polyurethane resin (U) containing a carboxyl group a method for obtaining a urethane resin containing a carboxyl group used in Method (1-1) can be used.
- Conditions such as temperature and time for the reaction between the glycidyl ether group and the carboxyl group may be the same as those usually used for the reaction of these groups.
- the glycidyl ether group contained in the compound (X) reacts with the carboxyl group contained in the polyurethane resin (U), and the compound is further heated by heating during decorative molding.
- a crosslinked structure is formed by crosslinking the alkoxysilyl group and / or silanol group contained in (X), and a protective layer excellent in water resistance and scratch resistance is obtained.
- the amount of (X) and / or (Y) used is (X) and / or (X) with respect to a total of 100 parts by mass of (A) and (B).
- the proportion of the total mass of Si atoms derived from the alkoxysilyl group and / or silanol group contained in Y) is preferably 0.05 to 2.0 parts by mass, and more preferably 0.1 to 1.5
- the amount is preferably part by mass, particularly 0.2 to 1.0 part by mass.
- 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 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total mass of the polyurethane resin. preferable. If the amount of the resin other than the reactant is greater than 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 measured with a micrometer in accordance with JIS C 2151 (2006) when each layer is formed as long as it is in the process of producing a decorative molding film.
- the thickness of the protective 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 a decorative molded body using the decorative molding film of the present invention is not particularly limited as long as it is a thermoforming method capable of decorating a three-dimensional object to be decorated, and generally known molding methods, For example, it can be formed by a vacuum forming method, a vacuum / pressure forming method, a blow (blowing) forming method, a press forming method, an insert injection forming method, an in-mold (in-mold) forming method, an extrusion forming method, or the like.
- the evaluation method of the film for decorative molding produced by the Example and the comparative example is shown below.
- the decorative film is heated by using a vacuum forming machine “FORMECH300X” (manufactured by Seiko Sangyo Co., Ltd.) using a far-infrared heater for 1 minute so that the film surface temperature is 170 ° C.
- a film was formed by vacuum forming using a mold (bottom diameter 50 mm). The state of being molded along the mold was evaluated according to the following criteria according to the degree of molding (drawing ratio: molding height / bottom diameter).
- Class A Molding was possible with a drawing ratio of 1.0 or more.
- Class B Molding was possible at a drawing ratio of 0.6 or more and less than 1.0, but molding was not possible at 1.0 or more.
- Class C Molding was possible at a drawing ratio of 0.3 or more and less than 0.6, but molding was not possible at 0.6 or more.
- Class D Only curved surface molding with a drawing ratio of less than 0.3 was possible, and molding was impossible at 0.3 or higher.
- the evaluation was performed 5 times for each sample, and those having no E class evaluation were determined to have acceptable followability, and those having E class evaluation of 1 or more were determined to be unacceptable.
- Sctch resistance The surface on the protective layer side of the decorative molded body obtained by attaching the decorative molding film to the object to be decorated was evaluated for scratch resistance using a scratch tester (manufactured by HEIDON). As the type of test needle, 0.1 mmR (made of sapphire) was used, and the scratching speed was 300 mm / min. The load during measurement was 200 g.
- a tensile testing machine (Orientec Tensilon UCT-100) an initial tensile chuck distance was set to 50 mm, and a tensile speed was set to 300 mm / min.
- a sample was set in a constant temperature layer set in advance to a temperature of 150 ° C., and a tensile test was performed after preheating for 60 seconds. The elongation at break and elastic modulus were determined from the obtained load-strain curve.
- the measurement was performed 5 times for each sample, and evaluation was performed with an average value of 3 points excluding the calculated maximum value and the minimum value.
- the photographed image was captured at an image size of 720 dpi using a CanonScan D123U.
- the image is saved in the JPEG format, and then image processing software Image-Pro Plus ver. 4 (sales company Planetron Co., Ltd.) was used to open this JPG file and perform image analysis.
- image analysis process the relationship between the thickness in the thickness direction and the average brightness of the area sandwiched between the two lines in the width direction was read as numerical data in the vertical thick profile mode.
- the spreadsheet software (Excel2000)
- the position (nm) and brightness data were subjected to numerical processing of sampling step 6 (decimation 6) and 3-point moving average.
- the obtained data with periodically changing brightness was differentiated, the maximum value and the minimum value of the differential curve were read, and the layer thickness was calculated with the interval between these adjacent ones as the layer thickness.
- This operation was performed on arbitrary 10 images, and the average value of the calculated values was defined as the layer thickness.
- the sample was stained using known RuO 4 .
- [In-plane average refractive index] The surface of the film made of the PA layer and the PB layer alone by attaching a polarizing plate to the eyepiece using the Abbe refractometer “NAR-4T” manufactured by Atago Co., Ltd. The internal refractive index was measured.
- the in-plane average refractive index was obtained by averaging four in-plane refractive indices measured in a direction parallel to each line by drawing four lines at 45 ° intervals around one point in the plane parallel to the film surface.
- a spectrophotometer UV-3150 manufactured by Shimadzu Corporation is equipped with an absolute reflectance measurement device ASR-3105 with an incident angle of 5 °, and an absolute wavelength of 400 to 1,200 nm is obtained under the following conditions according to the attached instruction manual. The reflectance was measured.
- the urethanization reaction was carried out by kneading for 10 minutes.
- 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, 289.1 parts of the obtained polyurethane resin, 14 parts by weight of 25% by weight ammonia water and 660.4 parts by weight of water were charged in a pressure-controllable container capable of controlling the temperature, and an emulsifying disperser “CLEAMIX” [registered trademark, M The polyurethane resin aqueous dispersion was obtained by carrying out a dispersion treatment at 12,000 rpm for 3 minutes at 150 ° C. using a technique manufactured by Technic Co., Ltd.
- Example 1 As the resin PA, polyethylene terephthalate (hereinafter referred to as PET) having an intrinsic viscosity of 0.65 was used. As the resin PB, Easter PETG6763 [manufactured by Eastman Chemical] (hereinafter PETG) was used. These polyester resins PA and PB are dried and then melted at 280 ° C. with an extruder, passed through a gear pump and a filter, and alternately laminated in a feed block of 801 layers with a discharge ratio of 1.1 / 1. Then, they were discharged in the form of a sheet on a cooling drum whose temperature was controlled at 25 ° C. from a T die.
- PET polyethylene terephthalate
- PB Easter PETG6763 [manufactured by Eastman Chemical]
- a wire-like electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched film.
- the film temperature is raised with a heating roll before stretching in the longitudinal direction, and finally the film is stretched 3.2 times in the longitudinal direction at a film temperature of 96 ° C, and immediately cooled with a metal roll whose temperature is controlled at 40 ° C. did.
- Both surfaces of this uniaxially stretched film are subjected to corona discharge treatment in air, the substrate film has a wetting tension of 55 mN / m, and the following coating agents A, B, C and D are not aggregated on the treated surface.
- A Water-dispersed acrylic resin (acid group 2.8 mg / g)
- B Methylolated melamine (diluent: isopropyl alcohol / water)
- C Colloidal silica (average particle size 80 nm)
- D Fluorosurfactant (diluent: water)
- Solid content mass ratio: A / B / C / D 100 parts by mass / 25 parts by mass / 3 parts by mass / 0.2 parts by mass
- the film was stretched 3.2 times in the width direction at a preheating temperature of 85 ° C. and a stretching temperature of 95 ° C.
- the thickness of the PA layer of the base film calculated according to [Layer thickness] is 0.125 ⁇ m
- the thickness of the PB layer is 0.125 ⁇ m
- the in-plane average refractive index of the layer containing the resin PA (PA layer) is 1. 60
- the in-plane average refractive index of the layer containing the resin PB (PB layer) is 1.57
- the minimum absolute reflectance of the base film in the wavelength band of 400 to 800 nm is 88%
- the glass transition temperature of the resin PA was 80 ° C.
- the glass transition temperature of the resin PB was 81 ° C.
- the aqueous dispersion of the polyurethane resin (U1) obtained in Production Example 1 was applied to one side of the molding film by an applicator method so that the thickness after drying was 40 ⁇ m, and then dried at 100 ° C. for 10 minutes. Then, a protective layer was formed to obtain a decorative molding film. Using the obtained decorative molding film, vacuum molding was performed at a temperature of 170 ° C. to obtain a decorative molded body. Table 1 shows the results and physical properties at the time of vacuum forming.
- Example 2 The same procedure as in Example 1 was performed except that the aqueous dispersion of the polyurethane resin (U1) obtained in Production Example 1 was replaced with the aqueous dispersion of the polyurethane resin (U2) obtained in Production Example 2. The results are also shown in Table 1.
- Example 3 The same procedure as in Example 1 was performed except that the aqueous dispersion of the polyurethane resin (U1) obtained in Production Example 1 was replaced with a methyl ethyl ketone solution of the polyurethane resin (U3) obtained in Production Example 3. The results are also shown in Table 1.
- the decorative molding film of the present invention can be preferably used when decorating building materials, mobile phones, electrical products, game machine parts, automobile parts, etc., but is not limited to these, and design is required. In addition, it can be preferably applied to applications requiring functionality such as scratch resistance and weather resistance.
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Abstract
Description
基材フィルムの少なくとも片面に保護層が配された積層構造を有する装飾成形用フィルムであって、前記基材フィルムは、面内平均屈折率が異なる樹脂PAと樹脂PBであって、樹脂PAの面内平均屈折率は樹脂PBの面内平均屈折率より相対的に高いものを用い、樹脂PAを含む層(PA層)と樹脂PBを含む層(PB層)とを交互にそれぞれ50層以上積層した構造を有し、1層の厚みが0.03μm以上0.5μm以下であるフィルムであり、前記保護層が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含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装飾成形用フィルム、である。
上記装飾成形用フィルムを用いた装飾成形体、である。
(i)保護層/基材フィルム(/被装飾体)
このような本発明の装飾成形用フィルムを用いて被装飾体を装飾することにより、溶剤レス塗装やメッキ代替などが達成できる。その結果、従来多段階の工程が必要であった塗装による装飾方法と比べて、装飾層を形成する工程数を減らすことが可能となり、装飾層を有する成形品の生産効率が向上し、低コスト化が可能となる。また、揮発性有機化合物やCO2など環境負荷物質排出量を低下させることができる。更には、かかる装飾成形用フィルムは、少なくとも前記条件(1)および条件(2)のいずれかを満たす保護層を有しているため、成形時の熱により保護層の硬化が進行し、別途エネルギー線照射の工程を必要としないことから生産性が高く、また、耐引っかき傷性が良好で、かつ被装飾体への追従性が良い。このような装飾成形用フィルムを用いることによって、外観の良好な装飾成形体を得ることが可能となる。
[基材フィルム]
本発明における基材フィルムは、樹脂PAを含む層(PA層)と樹脂PBを含む層(PB層)を交互にそれぞれ50層以上積層した構造を含むものであり、PA層、PB層を形成する樹脂としては、PA層の面内平均屈折率はPB層の面内平均屈折率より相対的に高い樹脂であれば、それぞれ熱可塑性樹脂、熱硬化性樹脂のいずれでもよく、ホモ樹脂であってもよく、共重合または2種類以上のブレンドであってもよい。より好ましくは、成形性が良好であるため、熱可塑性樹脂である。面内平均屈折率については後述する。
さらに、PA層を構成する樹脂PAの面内平均屈折率と該樹脂PAの厚み方向屈折率の差が0.01以上であり、PB層を構成する樹脂PBの面内平均屈折率と該樹脂PBの厚み方向屈折率差が0.01以下であると、入射角が大きくなっても、反射帯域の反射率低下が起きにくいため、より好ましい。ここでいう厚み方向屈折率とは、基材フィルム面と垂直方向に対する屈折率を指し、JIS K 7105(1981)に従い、公知の屈折率計にて測定することができる。
[保護層]
本発明における保護層は、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含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)を含有する。ポリウレタン樹脂(U)が脂環式炭化水素基を含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、耐引っかき傷性や意匠特性が得られ易く、かつ被装飾体への追従性を確保することができる。
[装飾成形体の作製方法]
本発明の装飾成形用フィルムを用いた装飾成形体の作製方法としては、3次元形状の被装飾体に装飾可能な熱成形方法であれば特に限定されるものではなく、一般に公知の成形方法、例えば、真空成形法、真空・圧空成形法、ブロー(吹き込み)成形法、プレス成形法、インサートインジェクション成形法、インモールド(金型内)成形法、押し出し成形法などで成形することができる。
[被装飾体への追従性]
装飾成形用フィルムを、真空成形機「FORMECH300X」(成光産業(株)製)を用いて、遠赤外線ヒーターを用いて、フィルム表面温度が170℃になるように1分間加熱し円柱状の金型(底面直径50mm)を用いて真空成形してフィルムを成形した。金型に沿って成形できた状態を成形度合い(絞り比:成形高さ/底面直径)に応じて以下の基準で評価した。
[耐引っかき傷性]
装飾成形用フィルムを被装飾体に貼り付けて得られた装飾成形体の保護層側の面を引っかき試験機(HEIDON社製)を用いて耐引っかき傷性を評価した。試験針の種類としては、0.1mmR(サファイア製)を使用し、傷を付ける速度は300mm/分とした。また、測定時の荷重は200gとした。試験後に傷の状態を確認して、保護層が削れずに傷跡がつくものを欠点なし、保護層のみが削れたものを一部欠点あり、装飾成形用フィルムが削れて被装飾体が露出したものを欠点ありと評価した。測定は各サンプル5回ずつ行い、5回中、欠点ありが1回以下であるものを耐引っかき傷性が合格であると判定し、欠点ありが2回以上であるものを耐引っかき傷性が不合格であると判定した。
[150℃時の伸度・弾性率]
装飾成形用フィルムを長さ150mm×幅10mmの短形に切り出し、サンプルとした。引張試験機(オリエンテック製テンシロンUCT-100)を用いて、初期引張チャック間距離50mmとし、引張速度を300mm/分として引張試験を行った。測定は予め150℃の温度に設定した恒温層中にサンプルをセットし、60秒間の予熱の後で引張試験を行った。得られた荷重-歪曲線から破断伸度と弾性率を求めた。なお、測定は各サンプル5回ずつ行い、算出最大値、最小値を除く3点の平均値で評価を行った。
[固有粘度]
ポリエステル樹脂およびフィルムの固有粘度を、ポリエステルをオルソクロロフェノールに溶解し、オストワルド粘度計を用いて25℃にて測定した。
[層の厚み]
ミクロトームを用いて断面を切り出したサンプルについて、透過型電子顕微鏡H-7100FA型((株)日立製作所製)を用い、加速電圧75kVでフィルムの断面を40,000倍に拡大観察し、断面画像を撮影した。
[面内平均屈折率]
アタゴ(株)製アッベ屈折計「NAR-4T」を用いて、接眼レンズに偏光板を取り付け、偏光板の向きおよびフィルムの向きをそれぞれ調整し、PA層、PB層単独で作製したフィルムの面内屈折率を測定した。面内平均屈折率はフィルム面に平行な面内の1点を中心として45°間隔で4本の線を引き各線と平行な方向に測定した面内屈折率を平均した。
[絶対反射率]
(株)島津製作所製の分光光度計UV-3150に入射角5°の絶対反射率測定装置 ASR-3105を取り付け、付属の取扱説明書に従い、以下の条件にて400~1,200nmまでの絶対反射率を測定した。
・サンプリングピッチ:1nm
・測定モード:シングル
・スリット幅:30nm
・光源切り替え波長:360nm
・検出器切替波長:805nm
・S/R切り替え:標準
・検出器ロック:自動
・スリットプログラム:標準
[ガラス転移温度]
示差熱量分析(DSC)を用い、JIS K 7122(1987)に従って測定・算出した。なお、まず1st Runで、25℃から290℃まで20℃/分で昇温した後、290℃で5分間ホールドした後、25℃まで急冷した。また続く2nd Runでは、25℃から290℃まで20℃/分で昇温した。樹脂のガラス転移温度は2nd Runにおけるガラス転移温度を用いた。
・データ解析 ディスクセッションSSC/5200
・サンプル質量:5mg
次に、実施例および比較例に使用したポリウレタン樹脂の製造例を以下に示す。
〔製造例1〕ポリウレタン樹脂(U1)の製造例
撹拌機及び加熱装置を備えた簡易加圧反応装置に、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質量部、1,4-ブタンジオール及び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質量部、エチレングリコール0.26質量部、DMPA21.3質量部、IPDI104.4質量部およびアセトン153.3質量部を仕込んで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含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質量部を簡易加圧反応装置に仕込み、40℃で撹拌しながらトリエチルアミン(中和剤)12.9質量部及び水623.9質量部を加えた。60rpmで3分間攪拌後、3-アミノプロピルトリメトキシシラン1.5質量部、エチレンジアミン(鎖伸長剤)3.6質量部を加え、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)の水分散体1,000質量部を得た。
〔製造例2〕ポリウレタン樹脂(U2)の製造例
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、1,4-シクロヘキサンジメタノール及び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質量部、1,4-ブタンジオール及び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質量部、エチレングリコール5.1質量部、DMPA34.4質量部および水添MDI119.6質量部を仕込み、220℃で10分間混練してウレタン化反応操作を行った。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289.1部、25質量%アンモニア水14質量部および水660.4質量部を仕込み、乳化分散機“クレアミックス”[登録商標、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質量部に、30℃で3-グリシドキシプロピルトリメトキシシラン36.5質量部を加えて均一撹拌することで、分子内にカルボキシル基の塩を含有するポリウレタン樹脂(U2)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水分散体1,000質量部を得た。
〔製造例3〕ポリウレタン樹脂(U3)の製造例
撹拌機及び加熱装置を備えた簡易加圧反応装置に、1,4-シクロヘキサンジメタノール及び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質量部、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質量部、1,6-ヘキサンジオール26.9質量部、DMPA29質量部、水添MDI178.2質量部およびメチルエチルケトン487.3質量部を仕込んで90℃で24時間攪拌してウレタン化反応操作を行い、ポリウレタン樹脂のメチルエチルケトン溶液を得た。得られたポリウレタン樹脂のメチルエチルケトン溶液974.5質量部に、30℃で3-グリシドキシプロピルトリメトキシシラン25.5質量部を加えて均一撹拌することで、分子内にカルボキシル基の塩を含有するポリウレタン樹脂(U3)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質量部を得た。
〔比較製造例1〕ポリウレタン樹脂(U’1)の製造例
撹拌機及び加熱装置を備えた簡易加圧反応装置に、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239質量部、1,6-ヘキサンジオール41質量部、DMPA29質量部、水添MDI178.2質量部およびメチルエチルケトン487.3質量部を仕込んで90℃で24時間攪拌してウレタン化反応操作を行い、ポリウレタン樹脂のメチルエチルケトン溶液を得た。得られたポリウレタン樹脂のメチルエチルケトン溶液974.5質量部に、30℃で3-グリシドキシプロピルトリメトキシシラン25.5質量部を加えて均一撹拌することで、ポリウレタン樹脂(U’1)のメチルエチルケトン溶液1,000質量部を得た。
〔比較製造例2〕ポリウレタン樹脂(U’2)の製造例
撹拌機及び加熱装置を備えた簡易加圧反応装置に、1,4-シクロヘキサンジメタノール及び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189.6質量部、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70.2質量部、1,6-ヘサンジオール27.6質量部、DMPA29.8質量部、水添MDI182.9質量部およびメチルエチルケトン500質量部を仕込んで90℃で24時間攪拌してウレタン化反応操作を行い、ポリウレタン樹脂(U’2)のメチルエチルケトン溶液1,000質量部を得た。
(実施例1)
樹脂PAとして、固有粘度0.65のポリエチレンテレフタレート(以下PET)を用いた。樹脂PBとして、Easter PETG6763[イーストマンケミカル製](以下PETG)を用いた。これらポリエステル樹脂PAおよびPBは、それぞれ乾燥した後、押出機にて280℃の溶融状態とし、ギヤポンプおよびフィルターを介した後、吐出比1.1/1で801層のフィードブロックにて交互に積層するように合流させた後、Tダイより25℃に温度制御した冷却ドラム上にシート状に吐出した。その際、直径0.1mmのワイヤー状電極を使用して静電印加し冷却ドラムに密着させ未延伸フィルムを得た。次いで、長手方向への延伸前に加熱ロールにてフィルム温度を上昇させ、最終的にフィルム温度96℃で長手方向に3.2倍延伸し、すぐに40℃に温度制御した金属ロールで冷却化した。この一軸延伸フィルムの両面に空気中でコロナ放電処理を施し、基材フィルムの濡れ張力を55mN/mとし、その処理面に、以下の塗剤A、B、C、Dを凝集のないように混合して、#4のバーコーターにて均一に塗布し易接着層を形成した。
「易接着層」
A:水分散アクリル樹脂(酸基2.8mg/g)
B:メチロール化メラミン(希釈剤:イソプロピルアルコール/水)
C:コロイダルシリカ(平均粒径80nm)
D:フッ素系界面活性剤(希釈剤:水)
固形分質量比:A/B/C/D=100質量部/25質量部/3質量部/0.2質量部
次いでテンター式横延伸機にて予熱温度85℃、延伸温度95℃で幅方向に3.2倍延伸し、そのままテンター内にて幅方向に4%のリラックスを掛けながら温度230℃で2秒間の熱処理を行いフィルム厚み100μmの二軸配向フィルムを得た。前記二軸配向フィルムを基材フィルムとした。
製造例1で得られたポリウレタン樹脂(U1)の水分散体を製造例2で得られたポリウレタン樹脂(U2)の水分散体に代えた以外は、実施例1と同様の条件で行った。結果を表1に併せて示す。
(実施例3)
製造例1で得られたポリウレタン樹脂(U1)の水分散体を製造例3で得られたポリウレタン樹脂(U3)のメチルエチルケトン溶液に代えた以外は、実施例1と同様の条件で行った。結果を表1に併せて示す。
(比較例1)
製造例1で得られたポリウレタン樹脂(U1)の水分散体を比較製造例1で得られたポリウレタン樹脂(U’1)のメチルエチルケトン溶液に代えた以外は、実施例1と同様の条件で行った。結果を表1に併せて示す。
(比較例2)
製造例1で得られたポリウレタン樹脂(U1)の水分散体を比較製造例2で得られたポリウレタン樹脂(U’2)のメチルエチルケトン溶液に代えた以外は、実施例1と同様の条件で行った。結果を表1に併せて示す。
Claims (5)
- 基材フィルムの少なくとも片面に保護層が配された積層構造を有する装飾成形用フィルムであって、前記基材フィルムは、面内平均屈折率が異なる樹脂PAと樹脂PBであって、樹脂PAの面内平均屈折率は樹脂PBの面内平均屈折率より相対的に高いものを用い、樹脂PAを含む層(PA層)と樹脂PBを含む層(PB層)とを交互にそれぞれ50層以上積層した構造を有し、1層の厚みが0.03μm以上0.5μm以下であるフィルムであり、前記保護層が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含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装飾成形用フィルム。
条件(1):前記ポリウレタン樹脂(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含有する。
条件(2):前記ポリウレタン樹脂(U)がカルボキシル基および/またはその塩を含有し、前記保護層がさらに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含有する化合物(X)を含有する。 - PA層を構成する樹脂PAの面内平均屈折率とPB層を構成する樹脂PBの面内平均屈折率の差が0.01以上である請求項1に記載の装飾成形用フィルム。
- 波長帯域400~800nmのいずれかの波長における基材フィルムの絶対反射率が30%以上である請求項1または2に記載の装飾成形用フィルム。
- 樹脂PAと樹脂PBのガラス転移温度の差が20℃以下である請求項1~3のいずれかに記載の装飾成形用フィルム。
- 請求項1~4のいずれかに記載の装飾成形用フィルムを用いた装飾成形体。
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US14/893,597 US20160114559A1 (en) | 2013-06-04 | 2014-06-03 | Decorative molding film and decorative molding article |
JP2014530838A JP6361504B2 (ja) | 2013-06-04 | 2014-06-03 | 装飾成形用フィルムおよび装飾成形体 |
CN201480030889.6A CN105307863B (zh) | 2013-06-04 | 2014-06-03 | 装饰成型用膜及装饰成型体 |
EP14808035.1A EP3006211A4 (en) | 2013-06-04 | 2014-06-03 | Decorative moulding film, and decorative moulded article |
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EP (1) | EP3006211A4 (ja) |
JP (1) | JP6361504B2 (ja) |
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JP2018178000A (ja) * | 2017-04-14 | 2018-11-15 | 旭化成株式会社 | ポリカーボネートジオール組成物 |
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EP3406644A1 (de) * | 2017-05-23 | 2018-11-28 | Sika Technology Ag | Lösungsmittelbasierter primer mit langer offenzeit und verbesserter ahäsion |
CN111548750B (zh) * | 2020-06-06 | 2022-07-22 | 江苏澳盛复合材料科技有限公司 | 一种用于真空成型件的表面保护薄膜 |
CN113710035A (zh) * | 2021-09-09 | 2021-11-26 | Oppo广东移动通信有限公司 | 壳体、壳体组件及电子设备 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001347565A (ja) | 2000-06-12 | 2001-12-18 | Toray Ind Inc | 成形用ポリエステルフィルムおよびこれを用いた成形部材 |
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 |
JP2004131546A (ja) | 2002-10-09 | 2004-04-30 | Teijin Dupont Films Japan Ltd | 包装材料用ポリエステルフィルム |
JP2004249587A (ja) | 2003-02-20 | 2004-09-09 | Teijin Ltd | 二軸延伸多層積層ポリエステルフィルム |
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 |
JP2005059332A (ja) | 2003-08-11 | 2005-03-10 | Teijin Ltd | 二軸延伸多層積層フィルム |
JP2005097528A (ja) | 2003-09-02 | 2005-04-14 | Toyobo Co Ltd | 成型用ポリエステルフィルム及びそれを成型してなる成形部材 |
JP2007301982A (ja) * | 2006-04-12 | 2007-11-22 | Toray Ind Inc | 積層ポリエステルフィルム |
JP2009096998A (ja) | 2007-09-28 | 2009-05-07 | Sanyo Chem Ind Ltd | ポリウレタン樹脂水分散体の製造方法 |
JP2010184493A (ja) * | 2009-01-14 | 2010-08-26 | Toray Ind Inc | 積層フィルム |
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 |
WO2011136042A1 (ja) * | 2010-04-27 | 2011-11-03 | 東レ株式会社 | 積層フィルムおよび成型体 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6788463B2 (en) * | 1998-01-13 | 2004-09-07 | 3M Innovative Properties Company | Post-formable multilayer optical films and methods of forming |
JP4712199B2 (ja) * | 2001-02-02 | 2011-06-29 | 中国塗料株式会社 | 帯電防止用塗料組成物、その被膜および帯電防止方法 |
US6842288B1 (en) * | 2003-10-30 | 2005-01-11 | 3M Innovative Properties Company | Multilayer optical adhesives and articles |
CN101023112B (zh) * | 2004-09-21 | 2010-11-24 | 昭和电工株式会社 | 热固性聚氨酯树脂组合物 |
KR101354011B1 (ko) * | 2005-08-18 | 2014-01-22 | 도레이 카부시키가이샤 | 적층 필름 및 성형체 |
JP4963641B2 (ja) * | 2007-07-18 | 2012-06-27 | スリーエム イノベイティブ プロパティズ カンパニー | 装飾シート及び成形物の製造方法 |
CN102089342B (zh) * | 2008-07-11 | 2013-04-10 | 宇部兴产株式会社 | 水性聚氨酯树脂分散体、其制造方法及含有所述分散体的涂料组合物 |
JP4770971B2 (ja) * | 2009-08-05 | 2011-09-14 | 東洋紡績株式会社 | 光学用易接着性ポリエステルフィルム |
US8637157B2 (en) * | 2011-02-28 | 2014-01-28 | Momentive Performance Materials Inc. | Copolycarbonates, their derivatives and the use thereof in silicone hardcoat compositions |
JP2013151666A (ja) * | 2011-12-28 | 2013-08-08 | Sanyo Chem Ind Ltd | ポリウレタン樹脂 |
MX2014007157A (es) * | 2011-12-28 | 2014-11-26 | Toray Industries | Pelicula de multiples capas para el moldeado decorativo, resina de poliuretano, y metodo para la produccion de un cuerpo moldeado decorativo. |
-
2014
- 2014-06-03 WO PCT/JP2014/064706 patent/WO2014196516A1/ja active Application Filing
- 2014-06-03 US US14/893,597 patent/US20160114559A1/en not_active Abandoned
- 2014-06-03 JP JP2014530838A patent/JP6361504B2/ja not_active Expired - Fee Related
- 2014-06-03 EP EP14808035.1A patent/EP3006211A4/en not_active Withdrawn
- 2014-06-03 CN CN201480030889.6A patent/CN105307863B/zh not_active Expired - Fee Related
- 2014-06-03 KR KR1020157035880A patent/KR20160014654A/ko not_active Application Discontinuation
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001347565A (ja) | 2000-06-12 | 2001-12-18 | Toray Ind Inc | 成形用ポリエステルフィルムおよびこれを用いた成形部材 |
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 |
JP2004131546A (ja) | 2002-10-09 | 2004-04-30 | Teijin Dupont Films Japan Ltd | 包装材料用ポリエステルフィルム |
JP2004249587A (ja) | 2003-02-20 | 2004-09-09 | Teijin Ltd | 二軸延伸多層積層ポリエステルフィルム |
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 |
JP2005059332A (ja) | 2003-08-11 | 2005-03-10 | Teijin Ltd | 二軸延伸多層積層フィルム |
JP2005097528A (ja) | 2003-09-02 | 2005-04-14 | Toyobo Co Ltd | 成型用ポリエステルフィルム及びそれを成型してなる成形部材 |
JP2007301982A (ja) * | 2006-04-12 | 2007-11-22 | Toray Ind Inc | 積層ポリエステルフィルム |
JP2009096998A (ja) | 2007-09-28 | 2009-05-07 | Sanyo Chem Ind Ltd | ポリウレタン樹脂水分散体の製造方法 |
JP2010184493A (ja) * | 2009-01-14 | 2010-08-26 | Toray Ind Inc | 積層フィルム |
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 |
WO2011136042A1 (ja) * | 2010-04-27 | 2011-11-03 | 東レ株式会社 | 積層フィルムおよび成型体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3006211A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018178000A (ja) * | 2017-04-14 | 2018-11-15 | 旭化成株式会社 | ポリカーボネートジオール組成物 |
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JPWO2014196516A1 (ja) | 2017-02-23 |
CN105307863B (zh) | 2017-03-22 |
EP3006211A1 (en) | 2016-04-13 |
CN105307863A (zh) | 2016-02-03 |
KR20160014654A (ko) | 2016-02-11 |
JP6361504B2 (ja) | 2018-07-25 |
US20160114559A1 (en) | 2016-04-28 |
EP3006211A4 (en) | 2017-01-11 |
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