WO2013027547A1 - 成型用フィルムおよびそれを用いた成型転写箔 - Google Patents
成型用フィルムおよびそれを用いた成型転写箔 Download PDFInfo
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- WO2013027547A1 WO2013027547A1 PCT/JP2012/069560 JP2012069560W WO2013027547A1 WO 2013027547 A1 WO2013027547 A1 WO 2013027547A1 JP 2012069560 W JP2012069560 W JP 2012069560W WO 2013027547 A1 WO2013027547 A1 WO 2013027547A1
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- film
- layer
- molding
- resin
- cyclic olefin
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Classifications
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
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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
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
-
- 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
- B32B2307/70—Other properties
- B32B2307/738—Thermoformability
-
- 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
- B32B2307/70—Other properties
- B32B2307/746—Slipping, anti-blocking, low friction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Definitions
- the present invention is a film for molding mainly composed of a cyclic olefin-based resin, and has a storage elastic modulus at 120 ° C. of 101 MPa or more and 3000 MPa or less, and a storage elastic modulus at 170 ° C. of 100 MPa or less. Further, the present invention relates to a film for molding that has both excellent dimensional stability during processing and moldability at high temperatures.
- Patent Document 3 a proposal has been made for an unstretched polyester film for molding using amorphous polyester that is excellent in moldability at low temperatures.
- Patent Document 4 a film in which a polyolefin film is bonded to at least one surface of an unstretched polyester film has been proposed (for example, Patent Document 4).
- Patent Document 5 a release film has been proposed (Patent Document 5).
- a cyclic olefin film for a decorative sheet a proposal has been made on a film obtained by blending polyethylene with a cyclic olefin (for example, Patent Document 6).
- Patent Document 1 and Patent Document 2 are biaxially stretched polyester films, they are excellent in heat resistance but are not sufficient in formability at low temperatures.
- Patent Document 3 has low solvent resistance and cannot withstand printing and coating.
- Patent Document 4 Since the film described in Patent Document 4 uses polypropylene as a polyolefin, it has a low surface appearance and is difficult to be developed for applications requiring high surface properties.
- Patent Document 5 and Patent Document 6 were not designed with sufficient consideration for processability and moldability.
- an object of the present invention is to eliminate the above-mentioned problems. In other words, it has excellent dimensional stability during processing and moldability at high temperature, and also has excellent surface appearance. Therefore, it can be used for various molded parts by applying molding processing. It is providing the film for a molding used suitably for a mold release use and a molding decoration use.
- the present invention employs the following means in order to solve such problems.
- the film for molding according to (1) wherein the A layer contains 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire A layer.
- (3) The film for molding according to (2) which has a three-layer structure of B layer / A layer / B layer.
- the glass transition temperature of the B layer is 115 ° C. or more and 170 ° C.
- the surface roughness SRa of one surface (X surface) of the film is 2 nm or more and less than 50 nm, and the surface roughness SRa of the other surface (Y surface) is 50 nm or more and 1,000 nm or less. ) Any one of the film for molding.
- the surface roughness SRmax of one surface (X surface) of the film is 20 nm or more and less than 500 nm, and the surface roughness SRmax of the other surface (Y surface) is 500 nm or more and 10,000 nm or less, (1) to (9 ) Any one of the film for molding.
- the film for molding of the present invention comprises a cyclic olefin-based resin as a main component, and has a storage elastic modulus at 120 ° C. of not less than 101 MPa and not more than 3000 MPa, and a storage elastic modulus at 170 ° C. of not more than 100 MPa. It exhibits excellent dimensional stability during processing such as vacuum molding, compressed air molding, and press molding, and can achieve good moldability by raising the molding temperature.
- the present invention can be applied to processes, and can be suitably used, for example, for decorating molded members such as building materials, automobile parts, mobile phones, electrical products, and gaming machine parts, and for imparting functionality.
- the film for molding of the present invention must contain a cyclic olefin resin as a main component.
- a film composed mainly of a cyclic olefin resin for molding it is possible to design both dimensional stability during processing such as coating, laminating, printing, vapor deposition, etc. and deep drawability. I found out.
- a cyclic olefin resin the surface appearance of the molded member is improved.
- having a cyclic olefin-based resin as a main component means that the total of all components of the film is 100% by mass and that the cyclic olefin-based resin is contained in an amount of 50% by mass to 100% by mass.
- the preferable aspect of this invention is a laminated
- all the layers which comprise a laminated film are used. It means that the total of all components is 100% by mass, and the total of cyclic olefin-based resins present in all layers is 50% by mass or more and 100% by mass or less.
- the total of all the components of the film is 100% by mass
- the embodiment includes 70 to 100% by mass of the cyclic olefin resin
- the mode includes 80 to 100% by mass of the cyclic olefin resin. If it is an aspect containing 90 mass% or more and 100 mass% or less of cyclic olefin resin, it is the most preferable.
- the cyclic olefin-based resin refers to a resin having an alicyclic structure in the main chain of a polymer obtained by polymerization from a cyclic olefin as a monomer.
- cyclic olefins examples include monocyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclopentadiene, and 1,3-cyclohexadiene, bicyclo [2,2,1] hept-2-ene, and 5-methyl-bicyclo [2].
- cyclic olefin monomers bicyclo [2,2,1] hept-2-ene (hereinafter referred to as norbornene), tricyclo [4,3,0,12. 5] Tricyclic olefins having 10 carbon atoms (hereinafter referred to as tricyclodecene) such as deca-3-ene, tetracyclo [4,4,0,12.5,17.10] dodec-3-ene, etc.
- tricyclodecene Tricyclic olefins having 10 carbon atoms
- tetracyclo [4,4,0,12.5,17.10] dodec-3-ene etc.
- tetracyclic olefins having 12 carbon atoms hereinafter referred to as tetracyclododecene
- cyclopentadiene 1,3-cyclohexadiene
- bicyclo [2,2,1] hept-2-ene is particularly preferably used from the viewpoint of productivity and surface properties.
- a resin obtained by copolymerizing a cyclic olefin resin and a chain olefin may be used.
- preferred chain olefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene.
- bicyclo [2,2,1] hept-2-ene hereinafter referred to as norbornene
- norbornene cyclopentadiene
- 1,3-cyclohexadiene 1,3-cyclohexadiene, and derivatives thereof are Preferably used.
- the cyclic olefin-based resin may be either a resin obtained by polymerizing only the cyclic olefin or a resin obtained by copolymerizing the cyclic olefin and a chain olefin.
- Examples of the method for producing a resin obtained by polymerizing only a cyclic olefin include known methods such as addition polymerization of a cyclic olefin monomer or ring-opening polymerization.
- hydrogenation is performed after ring-opening metathesis polymerization of norbornene and its derivatives.
- a method of addition polymerization of norbornene and its derivatives a method of hydrogenating cyclopentadiene and cyclohexadiene after 1,2- and 1,4-addition polymerization.
- a resin obtained by hydrogenating norbornene and its derivatives after ring-opening metathesis polymerization is most preferable.
- preferred chain olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3- Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.
- ethylene can be particularly preferably used from the viewpoint of productivity and cost.
- examples of a method for producing a resin obtained by copolymerizing a cyclic olefin and a chain olefin include known methods such as addition polymerization of a cyclic olefin and a chain olefin.
- addition polymerization of norbornene and its derivatives with ethylene are mentioned.
- a copolymer of norbornene and ethylene is most preferable.
- the cyclic olefin-based resin may contain a polar group from the viewpoint of improving the adhesion between the film and the coating film when formed into a film.
- the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group.
- a polar group is used as a method for adding a polar group to a cyclic olefin-based resin. Examples thereof include a method of grafting and / or copolymerizing the unsaturated compound possessed.
- Examples of the unsaturated compound having a polar group include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1 to 10) ester, maleic acid Examples thereof include alkyl (having 1 to 10 carbon atoms) esters, (meth) acrylamides, and 2-hydroxyethyl (meth) acrylate.
- the cyclic olefin resin in the present invention means a polymer having an aspect in which the total of cyclic olefin monomer-derived components is 50% by mass or more and 100% by mass or less in 100% by mass of the polymer of the cyclic olefin resin. .
- the molding film of the present invention is composed of only a cyclic olefin resin as long as the total content of all components of the film is 100% by mass and the cyclic olefin resin is contained in an amount of 50% by mass to 100% by mass. Even if it contains, other olefin resin may be contained or resin other than olefin resin may be contained.
- olefin resins other than cyclic olefin resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and ethylene- ⁇ / olefin copolymers polymerized using a metallocene catalyst (however, In the case where propylene is included as a monomer unit, a polypropylene resin is used, and in the case where propylene is not included as a monomer unit, a polyethylene resin is used.), Various polyethylene resins such as polypropylene, ethylene-propylene copolymer, ethylene -Polypropylene resins such as propylene-butene copolymer and polyolefin resins such as methylpentene polymer can be used.
- polymers comprising ⁇ -olefin monomers such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1 and octene-1, and random copolymers comprising the ⁇ -olefin monomers
- a block copolymer composed of the ⁇ -olefin monomer can be used.
- various polyethylene resins and various polypropylene resins are preferably used as the olefin resin other than the cyclic olefin resin.
- the film for molding mainly composed of the cyclic olefin-based resin of the present invention contains a polyethylene-based resin and a polypropylene-based resin, so that the shear stress in the extrusion process can be reduced and the generation of foreign matters due to crosslinking is suppressed. This is preferable because it is possible to improve the toughness.
- the content of polyethylene resin or polypropylene resin increases, the self-holding property tends to decrease.
- the content of the polyethylene resin and / or polypropylene resin is preferably 1 to 40% by mass with respect to 100% by mass in total of all components of the film.
- polyethylene resins and polypropylene resins are preferably used from the viewpoint of compatibility with cyclic olefin resins, and high density polyethylene and linear low density polyethylene are particularly preferably used. Density polyethylene is most preferably used.
- the film contains both a polyethylene resin and a polypropylene resin, the total amount of the polyethylene resin and the polypropylene resin is 1 to 40 with respect to the aforementioned range, that is, the total of 100% by mass of all the components of the film.
- the content is preferably 1% by mass, more preferably 1 to 30% by mass, and most preferably 1 to 20% by mass.
- the polyethylene-type resin in this invention means the polymer of the aspect whose sum total of an ethylene origin component is 50 to 100 mass% in 100 mass% of polymers of a polyethylene-type resin.
- the polypropylene resin of the present invention means a polymer having an aspect in which the total of propylene-derived components is 50% by mass or more and 100% by mass or less in 100% by mass of the polymer of the polypropylene resin.
- the film for molding of the present invention is required to have a storage elastic modulus at 120 ° C. of from 101 MPa to 3000 MPa from the viewpoint of dimensional stability during processing and moldability.
- a storage elastic modulus at 120 ° C. of from 101 MPa to 3000 MPa from the viewpoint of dimensional stability during processing and moldability.
- very excellent dimensional stability can be achieved in processing steps such as coating, laminating, printing, and vapor deposition.
- by setting the drying temperature after coating and printing to a higher temperature it is possible to increase the line speed during drying and to reduce the processing cost. Since the molding film of the present invention exhibits a high storage elastic modulus of 101 MPa or higher even at a high temperature of 120 ° C., the drying temperature after coating and printing can be set higher.
- the higher the storage elastic modulus at 120 ° C. the better the dimensional stability, which is preferable. However, if it is higher than 3000 MPa, the moldability may be lowered. In order to achieve both higher dimensional stability and moldability, the storage elastic modulus at 120 ° C. is more preferably 500 MPa to 3000 MPa, and most preferably 1000 MPa to 3000 MPa.
- the total thickness of the layers having a glass transition temperature of 120 ° C. or more is set to 50% with the total thickness of the film being 100%. % Or more is preferable.
- the total thickness of the layers having a glass transition temperature of 120 ° C. or higher means the thickness of the layer when the glass transition temperature is 120 ° C. or higher, and the glass transition temperature is 120 ° C. or higher. When there are a plurality of layers, this is the total thickness of those layers.
- the method for controlling the glass transition temperature is not particularly limited.
- the glass transition temperature is increased by increasing the content of norbornene. It is possible to raise the temperature. Further, it is possible to adjust the glass transition temperature of the film by blending two kinds of cyclic olefin resins having different norbornene contents.
- the glass transition temperature can be increased by using a bicyclic structure.
- the glass transition temperature of the layer can also be adjusted by blending two kinds of norbornene derivatives having different glass transition temperatures and then hydrogenating resins after ring-opening metathesis polymerization.
- the glass transition temperature can be lowered by adding a polyethylene resin or a polypropylene resin. More preferably, the total thickness of the layers having a glass transition temperature of 125 ° C.
- the glass transition temperature on the high temperature side is set as the glass transition temperature of that layer.
- the film for molding of the present invention is required to have a storage elastic modulus at 170 ° C. of 100 MPa or less from the viewpoint of moldability.
- the storage elastic modulus at 170 ° C. is 100 MPa or less, it is preferable that at least the molding temperature is set to 170 ° C. or higher so that excellent moldability can be achieved.
- the storage elastic modulus at 170 ° C. is preferably 50 MPa or less, and most preferably 20 MPa or less.
- the lower limit of the storage elastic modulus is preferably 0.5 MPa or more from the viewpoint of suppressing partial deformation during molding.
- the total thickness of the layers having a glass transition temperature of 170 ° C. or less is set to 50% or more when the total film thickness is 100%. It is preferable to use a thickness.
- the glass transition temperature on the high temperature side is set as the glass transition temperature of that layer.
- the storage elastic modulus at 120 ° C. of 101 MPa or more and 3000 MPa or less and the storage elastic modulus at 170 ° C. of 100 MPa or less satisfy the above numerical values in any one direction of the film and the direction orthogonal to the direction. It is.
- the molding film of the present invention preferably has a storage elastic modulus at 130 ° C. of 101 MPa or more and 3000 MPa or less when the dimensional stability during processing is emphasized. It is preferable to set the storage elastic modulus at 130 ° C. to 101 MPa or more because the temperature can be set higher in processing steps such as coating, laminating, printing, and vapor deposition.
- the storage elastic modulus at 130 ° C. is more preferably 500 MPa or more and 3000 MPa or less, and further preferably 1000 MPa or more and 3000 MPa or less.
- the total thickness of the layers having a glass transition temperature of 130 ° C. or more is set to 50% or more with the total film thickness being 100%. preferable.
- the molding film of the present invention is a molding film that places importance on dimensional stability during processing, but the molding temperature is as low as possible in order to shorten the preheating time during molding and shorten the tact time of molding. Is preferred.
- the film for molding of the present invention preferably has a storage elastic modulus at 160 ° C. of 100 MPa or less, and more preferably has a storage elastic modulus at 150 ° C. of 100 MPa or less.
- the total thickness of the layers having a glass transition temperature of 160 ° C. or less is set to 50% or more when the total thickness of the film is 100%.
- the total thickness of the layers having a glass transition temperature of 150 ° C. or less is set to 50% or more when the total thickness of the film is 100%. More preferably.
- the molding film of the present invention has a cyclic olefin resin as a main component on at least one side of a cyclic olefin layer (A layer) having a cyclic olefin resin as a main component in order to achieve both toughness, quality and surface appearance.
- a laminated film formed by laminating a cyclic olefin layer (B layer), and the A layer preferably contains 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire A layer. .
- the content of the polyethylene resin or the polypropylene resin is 1 to 40% by mass with respect to 100% by mass of the entire A layer.
- the total amount of the polyethylene resin and the polypropylene resin is in the above range, that is, 1 to 40% by mass with respect to 100% by mass of the entire A layer. It is preferable to include.
- the main component in the cyclic olefin layer (A layer) which has cyclic olefin resin as a main component is 50 mass% or more and 100 mass% or less of cyclic olefin resin by making the sum total of all the components of A layer into 100 mass%. It means to contain.
- the main component in the cyclic olefin layer (B layer) which has a cyclic olefin resin as a main component is 50 mass% or more and 100 mass% or less of cyclic olefin resin by making the sum total of all the components of B layer into 100 mass%. It means to contain.
- Cyclic olefin resins have low toughness compared to polyethylene resins and polypropylene resins, but the toughness can be improved by including polyethylene resins and polypropylene resins.
- the surface appearance tends to be lowered.
- the layer A includes 1 to 40% by mass of a polyethylene resin and / or a polypropylene resin with respect to 100% by mass of the entire A layer.
- the polyethylene resin and / or the polypropylene resin in the A layer is preferably 1 to 30% by mass, with the entire A layer being 100% by mass, and preferably 1 to 20% by mass. % Is most preferred.
- the content of the polyethylene resin and / or the polypropylene resin in the cyclic olefin layer (B layer) containing the cyclic olefin resin as a main component is 0% relative to 100% by mass of the entire B layer.
- the content is preferably from 10% by mass to 10% by mass, more preferably from 0% by mass to 5% by mass, and most preferably 0% by mass of polyethylene resin and / or polypropylene resin.
- the lamination ratio (total thickness of B layer / total thickness of A layer) is preferably 0.25 to 1 from the viewpoint of toughness, self-holding property, and surface appearance.
- the “total thickness of the B layer” is the total thickness of the B layer when there is only one B layer, and the total thickness when there are two or more B layers.
- the “total thickness” is the thickness of the A layer when there is only one A layer, and the total thickness when there are two or more A layers.
- the lamination ratio (total thickness of layer B / total thickness of layer A) is more preferably 0.4 to 0.8.
- the lamination ratio of the film can be measured by observing the cross section of the film with a scanning electron microscope, a transmission electron microscope, an optical microscope, or the like at a magnification of 500 to 10,000 times.
- the molding film of the present invention may have a three-layer structure of B layer / A layer / B layer rather than a two-layer structure of A layer / B layer in order to further improve the handleability. preferable.
- the glass transition temperature of the B layer is preferably higher than the glass transition temperature of the A layer from the viewpoints of dimensional stability during processing and moldability.
- the glass transition temperature (TgA) of the A layer is 111 ° C. or higher and 165 ° C. or lower from the viewpoint of dimensional stability during processing and moldability. Is preferred. It is preferable to set the glass transition temperature of the A layer to 111 ° C. or more because dimensional changes in processing steps such as coating, laminating, printing, and vapor deposition can be suppressed. Further, it is preferable to set the glass transition temperature of the A layer to 165 ° C. or lower because excellent moldability can be achieved while maintaining dimensional stability. In order to achieve both higher dimensional stability and moldability, the glass transition temperature of the A layer is more preferably 115 ° C.
- the glass transition temperature of the A layer here means the glass transition temperature on the highest temperature side.
- the glass transition temperature of the A layer In order to set the glass transition temperature of the A layer to 111 ° C. or more and 165 ° C. or less, for example, when a copolymer of norbornene and ethylene is used as the cyclic olefin resin, the content of norbornene is increased. It is possible to increase the glass transition temperature. Further, it is possible to adjust the glass transition temperature of the film by blending two kinds of cyclic olefin resins having different norbornene contents.
- the glass transition temperature can be increased.
- the glass transition temperature of the layer can also be adjusted by blending two kinds of norbornene derivatives having different glass transition temperatures and then hydrogenating resins after ring-opening metathesis polymerization.
- glass transition temperature can be made low by containing a polyethylene-type resin and a polypropylene-type resin.
- the glass transition temperature (TgB) of the B layer is 115 ° C. or more and 170 ° C. or less, and is higher than the glass transition temperature of the A layer. It is preferable. It is preferable to set the glass transition temperature of the B layer in the above range because dimensional changes during processing can be further suppressed without impairing moldability. From the viewpoint of moldability and dimensional stability, the glass transition temperature of the B layer is more preferably 120 ° C. or higher and 155 ° C. or lower, and most preferably 125 ° C. or higher and 145 ° C. or lower. In addition, when there exist multiple glass transition temperatures of B layer, the glass transition temperature of a high temperature side is employ
- the glass transition temperature of the B layer In order to set the glass transition temperature of the B layer to 115 ° C. or more and 170 ° C. or less and at the same time higher than the glass transition temperature of the A layer, for example, when a copolymer of norbornene and ethylene is used as the cyclic olefin resin Since the glass transition temperature can be increased by increasing the norbornene content, the norbornene content of the cyclic olefin resin used in the B layer is the same as that of the cyclic olefin resin used in the A layer. A method of increasing the content of the norbornene is increased.
- the molecular weight of the norbornene derivative is increased (for example, the molecular weight of the side chain is increased or Since the glass transition temperature can be increased by forming a ring structure), a method of increasing the molecular weight of the norbornene derivative of the cyclic olefin resin used in the B layer, and further, a polyethylene resin and a polypropylene resin are used. Since the glass transition temperature can be lowered by the inclusion, a method of containing a polyethylene resin or a polypropylene resin in the A layer is also preferably used.
- the film for molding of the present invention has a temperature at which the storage elastic modulus is 1000 MPa (T1: ° C.) and a temperature at which the storage elastic modulus is 100 MPa (T2: T2) in order to widen the processing process condition range and enhance the process stability.
- ° C) preferably satisfies the following formula (I).
- T1 (° C.) is the average value of the storage elastic modulus t1 (MPa) in any one direction of the film and the storage elastic modulus t2 (MPa) in the direction orthogonal to the direction (that is, (t1 + The temperature at which t2) / 2) is 1000 MPa.
- T2 (° C.) is the average value of the storage elastic modulus t3 (MPa) in any one direction of the film and the storage elastic modulus t4 (MPa) in the direction orthogonal to the direction (that is, (t3 + t4)).
- / 2) is a temperature at which 100 MPa is achieved.
- satisfying the formula (I) means that the temperature (T1: ° C.) is 1000 MPa at which the storage modulus can achieve very high dimensional stability, and the storage modulus at which the dimensional stability is reduced is 100 MPa. Since the temperature difference (T2 ⁇ T1) of the temperature (T2: ° C.) is 10 ° C. or more, the condition range of the processing step can be widened, and the film becomes very easy to process. It is preferable to set the drying temperature as high as possible because the drying temperature after coating and printing has the merit that the line speed during drying can be increased and the processing cost can be reduced by setting it to a higher temperature.
- the drying temperature is set to T1 where the storage elastic modulus is 1000 MPa, and even if the drying temperature unevenness occurs, the storage elastic modulus is reduced to T2 where the dimensional stability is reduced to 100 MPa. Since there is a difference of 10 ° C. or more, it is possible to suppress a sudden decrease in dimensional stability, wrinkles and shrinkage.
- the upper limit of T2-T1 is preferably 50 ° C, more preferably 40 ° C, and most preferably 30 ° C.
- a cyclic olefin resin is a main component on at least one side of a cyclic olefin layer (A layer) having a cyclic olefin resin as a main component.
- a method of adjusting the content of norbornene A method of blending two types of cyclic olefin resins having different norbornene contents, and when using a hydrogenated resin after ring-opening metathesis polymerization of a norbornene derivative as the cyclic olefin resin, a derivative of norbornene
- the upper limit of TgB-TgA is preferably 100 ° C., more preferably 80 ° C., and most preferably 50 ° C.
- the stacking ratio of the A layer and the B layer (total thickness of B layer / total thickness of A layer) is preferably 0.1 to 2.
- a laminated film structure is formed by laminating a cyclic olefin layer (B layer) containing a cyclic olefin resin as a main component on at least one surface of a cyclic olefin layer (A layer) containing a cyclic olefin resin as a main component.
- the film for molding of the present invention has a surface roughness SRa on one surface (X surface) of the film from the viewpoint of improving the surface appearance of the molded member (member of the product after decoration) when the film is used for decoration.
- X surface surface roughness of one surface of the film from the viewpoint of improving the surface appearance of the molded member (member of the product after decoration) when the film is used for decoration.
- the surface roughness SRa of the other surface (Y surface) is preferably 50 nm or more and 1,000 nm or less.
- the surface roughness SRa of the surface suitable for decorating the film is 2 nm or more and less than 50 nm.
- a surface having a surface roughness SRa of 2 nm or more and less than 50 nm is hereinafter referred to as an X surface.
- the surface smoothness of the decorative surface applied on the film is inferior, and the surface appearance of the molded member is impaired.
- the lower limit of SRa is better from the surface appearance of the decorative surface, the roughness of the film that can be produced industrially with good yield is 2 nm or more.
- the preferable range of the surface roughness SRa of the X plane is 2 to 20 nm, and more preferably 5 to 10 nm.
- the film for molding of the present invention has a surface opposite to the X surface (referred to as Y surface) suitable for decorating the film from the viewpoint of the processability of the decorative film and the surface appearance of the molded member.
- the surface roughness SRa is preferably 50 nm or more and 1,000 nm or less. When the surface roughness SRa of the Y surface exceeds 1,000 nm, the surface shape of the Y surface affects the decorative layer processed into the X surface, and the surface appearance of the molded member is impaired.
- a preferable range of the surface roughness SRa of the Y plane is 100 nm to 1,000 nm, and a more preferable range is 100 nm to 500 nm.
- the molding film of the present invention has a surface roughness SRmax on one surface (X surface) of 20 nm or more and less than 500 nm and a surface roughness SRmax on the other surface (Y surface) of 500 nm or more and 10 nm. , Preferably not more than 1,000 nm. More preferably, the surface roughness SRmax of the X plane is 20 nm or more and 200 nm or less, and the surface roughness SRmax of the Y plane is 1,000 nm or more and 5,000 nm or less.
- the molding film of the present invention in order to make the surface roughness SRa of the X plane in the range of 2 nm or more and less than 50 nm, or SRmax in the range of 20 nm or more and less than 500 nm, for example, a sheet-like melt extruded from a T-die
- a sheet-like melt extruded from a T-die There is a method of cooling and solidifying a polymer with a cast roll having a smooth surface. The smooth surface of the cast roll is transferred to the cast film, and the surface smoothness of the film on the cast roll contact surface side is improved.
- the arithmetic average roughness Ra of the cast roll surface is preferably 50 nm or less, more preferably 40 nm or less, More preferably, it is 20 nm or less.
- the lower limit of the arithmetic average roughness Ra of the cast roll is not particularly limited, but is preferably 2 nm or more in consideration of the roll winding property of the film.
- the surface roughness of the cast roll may be obtained by appropriately selecting the surface roughness from conventionally known grinding methods. However, in order to control the surface property with higher accuracy, a buffing process is performed after grinding. Is preferred.
- a method of measuring the surface roughness of the cast roll a sample obtained by transferring a roll surface shape by pressing and drying a solution obtained by dissolving triacetyl cellulose or the like in an organic solvent on the roll surface is created as a replica sample. And a method of measuring the surface roughness of the replica sample, a method of directly measuring the roll surface with a surface roughness meter, and the like.
- a method of improving the surface smoothness by strongly transferring the smoothness of the cast roll to the film a method in which the film is brought into close contact with the cast roll by electrostatic application using a wire-like electrode, an air knife, an air chamber is used.
- a method in which the sheet-like molten polymer extruded from the T-die is nipped by a pair of cooling rolls composed of a cast roll and a nip roll, and subsequently taken out while being in close contact with the cast roll. can be used.
- the film is laminated and particles are added to the layer on the Y plane side.
- the method of roughening the surface In a method of niping with a pair of cooling rolls, and then taking it out in close contact with the cast roll, there is a method of processing the surface of the nip roll to an appropriate surface roughness and transferring it to the film surface, etc.
- the sheet-like molten polymer extruded from the T-die is made up of a cast roll and a nip roll.
- the subsequent take-up Ru while in close contact with the casting roll method, advance by processing the surface of the nip roll on the appropriate surface roughness, a method of transferring the film surface is preferred.
- a metal material is preferred if you want to form a smooth surface, and if you want to roughen the surface to improve winding properties.
- a rubber material is preferred.
- the layer having the Y surface may contain more than 0% by mass and 1.0% by mass or less of particles.
- the content of particles in the Y plane is 1.0% by mass or less, the surface shape of the molded member is suppressed by suppressing the influence of the surface shape of the Y plane on the decorative layer processed into the X plane. It is preferable because there are many cases where it can be made.
- the content of the particles in the Y layer when the total component of the Y layer is 100% by mass is more preferably more than 0% by mass and 0.5% by mass or less, more preferably more than 0% by mass. It is 0.3 mass% or less.
- the particles to be contained in the layer having the Y surface are not particularly limited as long as they are inert to the resin constituting the layer having the Y surface, and examples thereof include inorganic particles, organic particles, and crosslinked polymer particles. it can. Two or more kinds of these particles may be added.
- the type of inorganic particles is not particularly limited, but various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, various composite oxides such as kaolin and talc, lithium phosphate
- various phosphates such as calcium phosphate and magnesium phosphate, various oxides such as aluminum oxide, silicon dioxide and titanium oxide, and various salts such as lithium fluoride can be used.
- terephthalate such as calcium, barium, zinc, manganese, magnesium, etc. are used.
- crosslinked polymer particles examples include homopolymers or copolymers of vinyl monomers such as divinylbenzene, styrene, acrylic acid, and methacrylic acid.
- organic particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.
- the molding film of the present invention comprises 0.005% by mass or more and 0.5% by mass or less of an antioxidant and / or a fatty acid metal salt with respect to 100% by mass in total of all components of the film. It is preferable to contain.
- an antioxidant and / or a fatty acid metal salt with respect to 100% by mass in total of all components of the film. It is preferable to contain.
- the film for molding of the present invention contains an antioxidant and / or a fatty acid metal salt with respect to a total of 100% by mass of the total components of the film, particularly for use in applications where the film quality and surface appearance are severe. It is preferable to contain 0.005 mass% or more and 0.5 mass% or less.
- an antioxidant and / or a fatty acid metal salt in an amount of 0.005% by mass or more and 0.5% by mass or less, generation of foreign matters due to crosslinking is caused in the same manner as when a polyethylene resin or a polypropylene resin is contained. It can be suppressed. For this reason, the surface appearance of the film for molding of the present invention is improved, and an excellent surface appearance can be obtained for the molded member after molding.
- the total amount of the antioxidant and the fatty acid metal salt is important, specifically, the total of all the components of the film It is important that the total amount of the antioxidant and the fatty acid metal salt is 0.005% by mass or more and 0.5% by mass or less with respect to 100% by mass.
- the antioxidant is not particularly limited, and phosphite antioxidants, organic sulfur antioxidants, hindered phenol antioxidants, and the like can be suitably used.
- phosphite antioxidants those containing phosphite in the chemical structural formula, specifically, Irgaphos 38, Irgaphos P-EPQ, Irgaphos 126 (all of which are manufactured by Ciba Specialty Chemicals), Sumilizer TNP, Sumilyzer TPP-P, Sumilyzer P-16 (all of which are manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB 11C, ADK STAB PEP-36, ADK STAB HP-11, ADK STAB 260, ADK STAB 522A, ADK STAB 329K, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010 (all manufactured by Asahi Denka Kogyo Co., Ltd.) and the like.
- organic sulfur-based antioxidants those containing thioether in the chemical structural formula, specifically, commercially available Irganox PS800FL, Irganox PS802FL (all of which are manufactured by Ciba Specialty Chemicals), Sumilizer TP-M, Examples thereof include Sumilizer TP-D, Sumilizer TL, Sumilizer MB (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stub AO-23 (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like.
- antioxidants those having a 2,6-alkylphenol in the chemical structural formula, specifically, as commercially available products, Irganox 245, Irganox 259, Irganox 565, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1222, Irganox 1330, Irganox 1425, Irganox 3114, Irganox 1520, Irganox 1135, Irganox 1141, Irganox HP2251 (all manufactured by Ciba Specialty Chemicals) ), Sumilizer BHT, Sumilizer MDP-S, Sumilizer GA-80, Sumilizer BBM-S, Sumilizer WX-R, Sumilizer GM, Sumire Over GS (all manufactured by both Sumitomo Chemical Co.), ADK STAB AO-30 (Asahi Denka Co., Ltd.).
- antioxidants may be used alone or in combination of two or more.
- fatty acid metal salts include acetates such as sodium acetate, potassium acetate, magnesium acetate, and calcium acetate, sodium laurate, potassium laurate, potassium hydrogen laurate, magnesium laurate, calcium laurate, and zinc laurate.
- Laurates such as silver laurate, lithium myristate, sodium myristate, potassium hydrogen myristate, magnesium myristate, calcium myristate, zinc myristate, silver myristate, myristate, lithium palmitate, palmitic acid Palmitates such as potassium, magnesium palmitate, calcium palmitate, zinc palmitate, copper palmitate, lead palmitate, thallium palmitate, cobalt palmitate, etc., sodium oleate Oleates such as potassium oleate, magnesium oleate, calcium oleate, zinc oleate, lead oleate, thallium oleate, copper oleate, nickel oleate, sodium stearate, lithium stearate, magnesium stearate, Stearates such as calcium stearate, barium stearate, aluminum stearate, thallium stearate, lead stearate, nickel stearate, beryllium stearate, sodium isostearate, potassium isostearate,
- fatty acid metal salt a salt of stearic acid or a salt of montanic acid is preferably used, and in particular, sodium stearate, calcium stearate, potassium stearate, zinc stearate, barium stearate, sodium montanate, etc. are suitably used. .
- the film for molding of the present invention is a laminated film having two or more layers having an A layer and a B layer
- the antioxidant and / or the fatty acid metal salt may be contained in either the A layer or the B layer.
- the film for molding of the present invention preferably has a breaking elongation at 160 ° C. in at least one direction of 300% or more from the viewpoint of moldability.
- the film for molding according to the present invention can be molded using various molding methods such as vacuum molding, pneumatic molding, vacuum pneumatic molding, press molding, etc., but it can be broken at the molding temperature in order to cope with deep drawing shapes.
- the elongation is preferably 300% or more.
- the molding temperature is preferably 160 ° C. or lower, and therefore, the elongation at break at 160 ° C. is 300. % Or more is preferable.
- the breaking elongation at 160 ° C. in at least one direction is 500% or more, and more preferably 800% or more. Moreover, when expanding to applications where deep drawability is required, it is particularly preferable that the breaking elongation at 160 ° C. in at least one direction is 1000% or more. From the viewpoint of moldability, it is preferable that the breaking elongation at 160 ° C. is high, but when considering dimensional stability, the preferable breaking elongation is 2000% or less.
- the total thickness of the layer whose glass transition temperature is 150 degrees C or less is 50% or more by making film total thickness 100%. It is preferable to use a thickness. More preferably, the total thickness of the layers having a glass transition temperature of 145 ° C. or lower is 50% or more with the total thickness of the film being 100%, and the total thickness of the layers having a glass transition temperature of 140 ° C. or lower is Most preferably, the total thickness is 100% and the thickness is 50% or more. When there are a plurality of glass transition temperatures, such as when a plurality of resins are mixed in one layer, the glass transition temperature on the high temperature side is set as the glass transition temperature of the layer.
- the film for molding of the present invention preferably has a thickness of 20 to 500 ⁇ m from the viewpoint of production stability, moldability and dimensional stability. More preferably, it is 50 to 400 ⁇ m, particularly preferably 70 to 300 ⁇ m.
- the thickness of the molding film of the present invention is preferably 10% or less from the viewpoint of moldability and processability.
- the thickness unevenness 10% or less uniform molding can be achieved, and furthermore, unevenness during processing such as coating, laminating, printing, and vapor deposition can be suppressed, which is preferable.
- the thickness unevenness is more preferably 8% or less, and most preferably 5% or less.
- the film for molding of the present invention (in the laminated film, each layer constituting the film) includes a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a plasticizer, and an adhesive as necessary.
- a flame retardant for molding of the present invention
- a heat stabilizer for stabilizes a heat stabilizer
- an antioxidant for antioxidant
- An appropriate amount of an imparting agent, an antifoaming agent such as polysiloxane, and a coloring agent such as a pigment or a dye can be contained.
- the molding film of the present invention contains a cyclic olefin resin as a main component, it has excellent surface appearance and releasability, and is preferably used for molding release and molding transfer foil among molding applications.
- examples of the mold release application include a release film used in a hot press molding process in the manufacture of FPC (Flexible printed circuits).
- FPC Flexible printed circuits
- the molding film of the present invention is provided between the press mold and the laminate film (press mold / molding of the present invention).
- a molding transfer foil use the following uses are mentioned, for example.
- a functional layer for example, a weather resistant layer, a scratch resistant layer, a conductive layer, a heat ray absorbing layer, a heat ray reflecting layer, etc.
- the molding film of the present invention is excellent in releasability from a mold, a laminate film, a decorative layer and a functional layer, a molded member having an excellent surface appearance can be obtained.
- the molding film of the present invention is preferably used for molding transfer foil applications, but in order to prevent the film and the coating film laminated on the film from being spontaneously peeled during molding, the surface of at least one surface is used.
- the free energy is preferably 33 mN or more and 45 mN / m, more preferably 35 mN or more and 40 mN / m.
- Various modification treatments can be used to bring the surface free energy of the film of the present invention into such a range, for example, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, laser treatment, flame treatment, high frequency treatment, glow Examples include discharge treatment and ozone oxidation treatment, and corona discharge treatment is preferably used from the viewpoint of cost and simplicity.
- the corona discharge treatment may be performed in air, nitrogen, carbon dioxide, and mixtures thereof.
- a method for measuring the surface free energy of the film four kinds of liquids of water, ethylene glycol, formamide, and methylene iodide are used as measurement liquids, and a contact angle meter CA-D (manufactured by Kyowa Interface Science) is used. Then, after obtaining the static contact angle of each liquid with respect to the film surface, the components of the contact angle obtained for each liquid and the surface tension of the measurement liquid are substituted into the following equations, respectively, and simultaneous equations consisting of four equations are obtained. It can be obtained by solving for ⁇ Sd, ⁇ Sp, and ⁇ Sh.
- the configuration of the molding transfer foil using the molding film of the present invention is not particularly limited, but a configuration in which a decorative layer is laminated on the molding film of the present invention is preferable.
- the decoration layer is a layer for adding decoration such as coloring, pattern, wood grain, metal tone, and pearl tone. From the viewpoint of scratch resistance, weather resistance, and designability of the molded member (adhered body) after transfer, it is preferable to further laminate a clear layer. In this case, the clear layer is preferably laminated on the molding film side. Moreover, it is preferable to laminate
- the molded transfer foil of the present invention preferably has a configuration in which a clear layer, a decorative layer, and an adhesive layer are sequentially provided on at least one surface of the molding film of the present invention.
- the clear layer is a layer located at the outermost layer of the molded member, and is a highly glossy and highly transparent layer for improving the appearance of the molded member.
- the decorative layer here is a layer for adding decoration such as coloring, unevenness, pattern, wood grain, metal tone, pearl tone and the like.
- the resin used as the clear layer is not particularly limited as long as it is a highly transparent resin.
- polyester resin, polyolefin resin, acrylic resin, urethane resin, fluorine resin, polyvinyl acetate resin, chloride resin Vinyl-vinyl acetate copolymer resins, ethylene-vinyl acetate copolymer resins, and the like are preferably used.
- a thermosetting resin, an ultraviolet curable resin, or a heat ray curable resin is preferably used.
- an ultraviolet absorber or an ultraviolet reflector may be added to the clear layer.
- the clear layer preferably has a thickness of 10 to 100 ⁇ m, more preferably 15 to 80 ⁇ m, and most preferably 20 to 60 ⁇ m from the viewpoint of scratch resistance and design.
- Examples of the method for forming the clear layer include a method for direct formation, a method for once forming on a carrier film, and a transfer method. In the case where the drying temperature after forming the clear layer needs to be high, a method of once forming it on a carrier film and then transferring it is preferably used.
- Examples of the method for forming the clear layer include a roller coating method, a brush coating method, a spray coating method, a dip coating method, and a method using a gravure coater, a die coater, a comma coater, a bar coater, and a knife coater.
- the molding film of the present invention has a cyclic olefin resin as a main component, the resistance to aromatic solvents such as toluene and xylene is low, and therefore, a structure that does not use an aromatic solvent as a solvent used in the clear layer It is preferable that
- a formation method of a decoration layer For example, it can form by a coating, printing, metal vapor deposition, etc.
- a coating method such as a gravure coating method, a roll coating method, or a comma coating method can be used.
- a printing method such as an offset printing method, a gravure printing method, or a screen printing method can be used.
- the resins used at this time are polyester resins, polyolefin resins, acrylic resins, urethane resins, fluorine resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, ethylene-vinyl acetate copolymers.
- Polymer based resin copolymers and the like are preferably used.
- a coloring agent to be used Considering dispersibility etc., it selects suitably from dye, an inorganic pigment, an organic pigment, etc.
- the thickness of the decorative layer formed by coating or printing is preferably 10 to 100 ⁇ m, more preferably 15 to 80 ⁇ m, and more preferably 20 to 60 ⁇ m from the viewpoints of color tone retention and design after molding. Most preferred.
- the deposition book film is not particularly limited, but a vacuum deposition method, an EB deposition method, a sputtering method, an ion plating method, or the like can be used.
- the vapor deposition surface is preferably pretreated by a method such as a corona discharge treatment or an anchor coating agent.
- the metal to be used it is preferable to deposit a metal compound having a melting point of 150 to 400 ° C. from the viewpoint of molding followability.
- a more preferable melting point of the metal compound is 150 to 300 ° C.
- the metal compound having a melting point of 150 to 400 ° C. is not particularly limited, but indium (157 ° C.) and tin (232 ° C.) are preferable, and indium can be particularly preferably used.
- the lamination thickness of the decorative layer is preferably 0.001 to 100 ⁇ m, more preferably 0.01 to 80 ⁇ m, and most preferably 0.02 to 60 ⁇ m.
- an adhesive layer can be designed according to the resin.
- an acrylic resin an acrylic resin, a polyphenylene oxide / polystyrene resin, a polycarbonate resin, a styrene copolymer resin, and in the case of a polystyrene resin, an acrylic resin having an affinity for these resins, a polystyrene resin, It is preferable to use a polyamide-based resin or the like.
- the molding resin is a polypropylene resin
- a coating method such as a roll coating method, a gravure coating method, a comma coating method, or a printing method such as a gravure printing method or a screen printing.
- the adherend to be decorated using the molded transfer foil using the molding film of the present invention is not particularly limited.
- resin or a metal member is used.
- the transmitted light was photographed under the condition of a magnification of 100 times, and each layer of the laminated film was photographed.
- the layer thickness arbitrary 5 points were measured for each layer, and the average value was defined as the layer thickness of each layer.
- the storage elastic modulus film was cut into a rectangular shape having a length of 60 mm and a width of 5 mm in one arbitrary direction and a direction orthogonal to the direction, and used as a sample.
- a dynamic viscoelasticity measuring device manufactured by Rheology, DVE-V4 FT Rheospectra
- the measurement was performed under the following conditions to determine the storage elastic modulus (E ′) in the measurement temperature range.
- the temperature T1 (° C.) at which the storage elastic modulus (E ′) is 1000 MPa is the average value of the storage elastic modulus t1 in any one direction of the film and the storage elastic modulus t2 in the direction orthogonal to the direction (that is, , (T1 + t2) / 2) is a temperature at which 1000 MPa.
- the temperature T2 (° C.) at which the storage elastic modulus (E ′) is 100 MPa is the average value of the storage elastic modulus t3 in any one direction of the film and the storage elastic modulus t4 in the direction orthogonal to the direction (that is, , (T3 + t4) / 2) is a temperature at which 100 MPa.
- the breaking elongation film was cut into a rectangular shape having a length of 100 mm and a width of 10 mm in an arbitrary direction and a direction orthogonal to the direction, and used as a sample.
- a tensile tester Orientec Tensilon UCT-100
- an initial tensile chuck distance was set to 20 mm
- a tensile speed was set to 200 mm / min.
- a film sample was set in a constant temperature layer set in advance at 160 ° C., and a tensile test was performed after preheating for 60 seconds.
- the elongation when the sample broke was defined as the breaking elongation.
- the measurement was performed 5 times for each sample and each direction, and the average value was evaluated.
- the thick spot film was cut into a size of 200 mm ⁇ 300 mm at an arbitrary position to prepare a sample.
- For the 200 mm direction measure the thickness at 11 points at 20 mm intervals from the end, 11 points at 30 mm intervals for the 300 mm direction, a total of 121 points, and determine the maximum value, minimum value, and average value. Asked.
- Thickness unevenness (%) ((maximum value ⁇ minimum value) / average value) ⁇ 100.
- a quality film was cut into a size of 200 mm ⁇ 300 mm at an arbitrary position to prepare a sample. Visual observation was performed by transmission under a three-wavelength fluorescent lamp, the number of foreign matters having a major axis of 100 ⁇ m or more was counted, and the number of foreign matters per A4 size was evaluated according to the following criteria.
- C The number of foreign matters was 20 or more and less than 30.
- D The number of foreign matters was 30 or more.
- the coatable film was cut into a size of 200 mm ⁇ 300 mm at an arbitrary position to prepare a sample.
- UF-TCI-1 manufactured by Kyoeisha Chemical Co., Ltd. was applied to the surface of the sample (B layer side in the case of a laminated film having an A layer and a B layer) using an applicator.
- the coatability was evaluated according to the following criteria. A: Coating unevenness did not occur and the coating property was good.
- B Coating unevenness hardly occurred, and there was no problem in coating properties.
- C Although coating unevenness slightly occurred, it was at a level where there was no practical problem.
- D Remarkable coating unevenness occurred.
- a moldable film was cut into a size of 200 mm ⁇ 300 mm at an arbitrary position to prepare a sample.
- 892L made by Nippon Chemical Co., Ltd. is applied to the surface of the sample (A layer side in the case of a laminated film having A and B layers), dried at 80 ° C. for 10 minutes, and the coating thickness A 20 ⁇ m adhesive layer was formed.
- the obtained adhesive layer laminated film was heated using a far-infrared heater at 400 ° C., and vacuum / pressure molding (pressure: air pressure) along a polypropylene resin mold (bottom diameter 150 mm) heated to 50 ° C. 0.2Ma), and a film / adhesive layer / polypropylene resin mold structure was obtained.
- the state (drawing ratio: shaping
- the surface temperature of the adhesive layer laminated film at the time of molding is as follows. 145 ° C .: Examples 1, 2, 12, 13 and Comparative Examples 1, 3, 5 155 ° C .: Examples 3, 4, 8 to 11, 14, 15, 19 to 25 160 ° C .: Examples 5 to 7, 16 to 18, 26 to 28, Comparative Examples 2 and 4
- S Molding was possible at a drawing ratio of 1.0 or more.
- C Molding was possible with a drawing ratio of 0.7 or more and less than 0.8.
- D Low followability, and could not be molded into a shape with a drawing ratio of 0.7.
- S to C are acceptable levels.
- a dimensional stability film is cut into a rectangular shape with a length of 50 mm and a width of 4 mm in one arbitrary direction and in a direction perpendicular to that direction, and a thermomechanical analyzer (manufactured by Seiko Instruments, TMA EXSTAR6000) is used. Then, when the temperature was raised under the following conditions, evaluation was performed according to the following criteria at a temperature at which the dimensional change rate exceeded 1%.
- Test length 15 mm, load: 19.6 mN, heating rate: 5 ° C./min, Measurement temperature range: 25-220 ° C
- Dimensional change rate (%) ⁇
- C 130 degreeC or more and less than 140 degreeC.
- D Less than 130 ° C.
- a releasable film was cut into a size of 200 mm ⁇ 300 mm at an arbitrary position to prepare a sample.
- an applicator Apply UF-TCI-1 manufactured by Kyoeisha Chemical Co., Ltd. to the surface of the sample (B layer side in the case of a laminated film having A and B layers), and dry at 80 ° C. for 10 minutes.
- a clear layer having a coating thickness of 50 ⁇ m was formed.
- an acrylic / urethane silver ink was applied on the clear layer using an applicator and dried at 80 ° C. for 10 minutes to obtain a decorative layer having a coating thickness of 30 ⁇ m.
- 892L made by Nippon Chemical Co., Ltd. was applied on the decorative layer using an applicator and dried at 80 ° C. for 10 minutes to form an adhesive layer having a coating thickness of 20 ⁇ m to obtain a molded transfer foil.
- the test was performed in an arbitrary direction of the film and a direction perpendicular to the direction at an initial chuck distance of 100 mm, a tensile speed of 300 mm / min, and 25 ° C. In addition, the measurement was performed 5 times for each sample and each direction, and the average value was evaluated.
- the film was cut into a rectangular shape with a length of 150 mm and a width of 15 mm in any one direction and in a direction perpendicular to the direction, using a MIT folding fatigue tester manufactured by Toyo Seiki as a JIS P8115 (1994).
- the number N of bendings until breakage was evaluated according to the following criteria.
- a film roll having a width of 400 mm and a length of 200 m (a film roll wound on a core having a diameter of 3 inches and a width of 550 mm) is prepared, and the film is wound from the film under the following conditions. And wound on a core 3 inches in diameter and 550 mm wide.
- the rolled form was evaluated according to the following criteria. A: No core defect was found and the winding shape was very good.
- B Nucleusless flaws were observed or the winding shape was poor (including a case where a flawless flaw was seen and the winding shape was poor).
- Molded surface appearance UF-TCI-1 manufactured by Kyoeisha Chemical Co., Ltd. is applied to the X side of the film roll with a die coater and dried at 80 ° C. for 10 minutes to form a clear layer with a coating thickness of 50 ⁇ m. did. Subsequently, using the same die coater on the clear layer, an acrylic / urethane silver ink was applied and dried at 80 ° C. for 10 minutes to form a decorative layer having a coating thickness of 30 ⁇ m. Furthermore, 892L made by Nippon Chemical Co., Ltd. was applied on the decorative layer using an applicator, dried at 80 ° C. for 10 minutes to form an adhesive layer having a coating thickness of 20 ⁇ m, and a molded transfer foil roll was produced.
- a film is cut into a size of 200 mm ⁇ 300 mm at an arbitrary position from the obtained molded transfer foil roll, and vacuum / pneumatic molding is performed in the same manner as in (11) to form a molding film / clear layer / decorative layer / adhesive layer /
- a polypropylene resin mold molded member was obtained.
- the obtained molding member was irradiated with ultraviolet rays so that the irradiation intensity was 2,000 mJ / cm 2 to cure the coating agent.
- the surface of the transfer body (clear layer / decorative layer / adhesive layer / polypropylene resin mold) where the film was peeled was observed from the clear layer side under a three-wavelength fluorescent lamp, and the surface appearance was evaluated according to the following criteria. .
- B Although the shape of the fluorescent lamp was reflected and observed, there was a portion that was slightly blurred.
- C The shape of the fluorescent lamp was unclear and totally blurred.
- Antioxidant “Irganox 1010” manufactured by Ciba Specialty Chemicals was used.
- L / D 30
- Example 2 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the composition and configuration shown in the table were used.
- Example 3 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the composition and configuration shown in the table were used.
- Example 4 The film for molding of the present invention having a film thickness of 100 ⁇ m was used in the same manner as in Example 1 except that the composition and composition shown in the table were used, and the temperature of the supply section was 260 ° C., the temperature thereafter was 270 ° C., and the mirror drum temperature was 110 ° C. Got.
- Example 5 A film for molding of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 4 except that the composition and configuration shown in the table were used.
- Example 6 The molding film of the present invention having a film thickness of 100 ⁇ m in the same manner as in Example 1 except that the composition and composition shown in the table were used, and the temperature of the supply section was 270 ° C., the temperature thereafter was 280 ° C., and the mirror drum temperature was 120 ° C. Got.
- Example 7 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 6 except that the composition and configuration shown in the table were used.
- Example 8 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the composition and configuration shown in the table were used.
- Example 9 A film for molding of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 4 except that the composition and configuration shown in the table were used.
- Example 10 A film for molding of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 4 except that the composition and configuration shown in the table were used.
- Example 11 A film for molding of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 4 except that the composition and configuration shown in the table were used.
- the sheet was discharged in the form of a sheet on a mirror drum (surface roughness 0.2 s) temperature-controlled at 100 ° C.
- a nip was made with an elastic metal roll (nip pressure: 0.2 MPa) to obtain a molding fat film of the present invention having a film thickness of 100 ⁇ m.
- Example 13 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 12 except that the composition and configuration shown in the table were used.
- Example 14 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 12 except that the composition and configuration shown in the table were used.
- Example 15 The film for molding of the present invention having a film thickness of 100 ⁇ m was used in the same manner as in Example 1 except that the composition and composition shown in the table were used, and the temperature of the supply section was 260 ° C., the temperature thereafter was 270 ° C., and the mirror drum temperature was 110 ° C. Got.
- Example 16 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 15 except that the composition and configuration shown in the table were used.
- Example 17 A film having a film thickness of 100 ⁇ m was prepared in the same manner as in Example 15 except that the composition and composition shown in the table were used, and the temperature of the supply part of the B layer extruder was 270 ° C., the temperature thereafter was 280 ° C., and the mirror drum temperature was 120 ° C. An inventive molding film was obtained.
- Example 18 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 17 except that the composition and configuration shown in the table were used.
- Example 19 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 15 except that the composition and configuration shown in the table were used.
- Example 20 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 15 except that the composition and configuration shown in the table were used.
- Example 21 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 15 except that the composition and configuration shown in the table were used.
- Example 22 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 15 except that the composition and configuration shown in the table were used.
- a feed block installed on the top of the die so as to be B layer / A layer / B layer (see the table for the lamination thickness ratio)
- from a T die lip gap: 1 mm
- the sheet was discharged in the form of a sheet on a mirror drum (surface roughness: 0.2 s) whose temperature was controlled to a predetermined level.
- a nip was made with an elastic metal roll (nip pressure: 0.2 MPa) to obtain a molding fat film of the present invention having a film thickness of 100 ⁇ m.
- the sheet was discharged in the form of a sheet on a mirror drum (surface roughness: 0.2 s) whose temperature was controlled to a predetermined level.
- a nip was made with an elastic metal roll (nip pressure: 0.2 MPa) to obtain a molding fat film of the present invention having a film thickness of 100 ⁇ m.
- Example 26 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 17 except that the composition and configuration shown in the table were used.
- Example 27 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 17 except that the composition and configuration shown in the table were used.
- Example 28 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 17 except that the composition and configuration shown in the table were used.
- Example 1 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 12 except that the composition and configuration shown in the table were used.
- Example 2 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 6 except that the composition and configuration shown in the table were used.
- Example 3 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the composition and configuration shown in the table were used.
- Example 4 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 17 except that the composition and configuration shown in the table were used.
- Example 5 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 1 except that the composition and configuration shown in the table were used.
- Example 29 A molding film of the present invention having a film thickness of 100 ⁇ m was obtained in the same manner as in Example 16 except that an elastic metal roll (surface roughness 0.2 s, Ra 0.01 ⁇ m) was used as the elastic metal roll.
- an elastic metal roll surface roughness 0.2 s, Ra 0.01 ⁇ m
- Example 30 Example 16 except that a rubber roll (surface roughness 0.8 s, Ra 0.1 ⁇ m) was used instead of an elastic metal roll as the nip for discharging the sheet onto a mirror drum (surface roughness 0.2 s). In the same manner as above, a molding film of the present invention having a film thickness of 100 ⁇ m was obtained.
- Example 31 Example 16 except that a rubber roll (surface roughness 6.3 s, Ra 0.6 ⁇ m) was used instead of an elastic metal roll as a nip for discharging the sheet onto a mirror drum (surface roughness 0.2 s). In the same manner as above, a molding film of the present invention having a film thickness of 100 ⁇ m was obtained.
- Example 32 The same as in Example 16 except that a rubber roll (surface roughness 18 s, Ra 1.6 ⁇ m) was used instead of an elastic metal roll as a nip for discharging the sheet onto a mirror drum (surface roughness 0.2 s). Thus, a molding film of the present invention having a film thickness of 100 ⁇ m was obtained.
- the film for molding of the present invention comprises a cyclic olefin-based resin as a main component, and has a storage elastic modulus at 120 ° C. of not less than 101 MPa and not more than 3000 MPa, and a storage elastic modulus at 170 ° C. of not more than 100 MPa. It exhibits excellent dimensional stability during processing such as vacuum molding, compressed air molding, and press molding, and can achieve good moldability by raising the molding temperature.
- the present invention can be applied to processes, and can be suitably used for decorating molded members such as building materials, automobile parts, mobile phones, electrical products, and gaming machine parts.
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Abstract
Description
(1) 環状オレフィン系樹脂を主成分とする成型用フィルムであって、120℃における貯蔵弾性率が101MPa以上3000MPa以下、170℃における貯蔵弾性率が100MPa以下である、成型用フィルム。
(2) 環状オレフィン系樹脂を主成分とする環状オレフィン層(A層)の少なくとも片面に、環状オレフィン系樹脂を主成分とする環状オレフィン層(B層)を積層してなる積層フィルムであって、前記A層は、A層全体100質量%に対して、ポリエチレン系樹脂及び/又はポリプロピレン系樹脂を1~40質量%含むことを特徴とする、(1)に記載の成型用フィルム。
(3) B層/A層/B層の3層構成である(2)に記載の成型用フィルム。
(4) 前記B層のガラス転移温度が、前記A層のガラス転移温度よりも高温であることを特徴とする、(2)または(3)に記載の成型用フィルム。
(5) 前記A層のガラス転移温度が、111℃以上165℃以下であることを特徴とする、(2)~(4)のいずれかに記載の成型用フィルム。
(6) 前記B層のガラス転移温度が、115℃以上170℃以下であり、かつA層のガラス転移温度よりも高温であることを特徴とする、(2)~(5)のいずれかに記載の成型用フィルム。
(7) 貯蔵弾性率が1000MPaである温度(T1:℃)、貯蔵弾性率が100MPaである温度(T2:℃)が、下記(I)式を満たす、(1)~(6)のいずれかに記載の成型用フィルム。
T2-T1≧10・・・(I)
(8) 前記A層の厚みと前記B層の厚みの積層比(B層の合計厚み/A層の合計厚み)が、0.25~1である(3)~(7)のいずれかに記載の成型用フィルム。
(9) フィルムの一面(X面)の表面粗さSRaが2nm以上50nm未満であり、他面(Y面)の表面粗さSRaが50nm以上1,000nm以下である、(1)~(8)のいずれかに記載の成型用フィルム。
(10) フィルムの一面(X面)の表面粗さSRmaxが20nm以上500nm未満であり、他面(Y面)の表面粗さSRmaxが500nm以上10,000nm以下である、(1)~(9)のいずれかに記載の成型用フィルム。
(11) フィルムの全成分の合計100質量%に対して、酸化防止剤および/または脂肪酸金属塩を0.005質量%以上0.5質量%以下含有する、(1)~(10)のいずれかに記載の成型用フィルム。
(12) 少なくとも一方向の160℃における破断伸度が300%以上である(1)~(11)のいずれかに記載の成型用フィルム。
(13) 前記成型用フィルムが、成型転写箔用フィルムであることを特徴とする、(1)~(12)のいずれかに記載の成型用フィルム。
(14) (1)~(13)のいずれかに記載の成型用フィルムの少なくとも片面に、クリア層、加飾層及び接着層を順次有する成型転写箔。
T2-T1≧10・・・(I)
本発明において、T1(℃)とは、フィルムの任意の一方向における貯蔵弾性率t1(MPa)と、その方向に直交する方向の貯蔵弾性率t2(MPa)の平均値(つまり、(t1+t2)/2)が1000MPaとなる温度である。また、T2(℃)とは、フィルムの任意の一方向における貯蔵弾性率t3(MPa)と、その方向に直交する方向の貯蔵弾性率t4(MPa)の平均値(つまり、(t3+t4)/2)が100MPaとなる温度である。
T2-T1≧12・・・(I’)
T2-T1≧15・・・(I”)
本発明の成型用フィルムにおいて、(I)式を満たす方法としては、例えば、環状オレフィン系樹脂を主成分とする環状オレフィン層(A層)の少なくとも片面に、環状オレフィン系樹脂を主成分とする環状オレフィン層(B層)を積層してなる積層フィルムであって、前記A層のガラス転移温度(TgA:℃)、前記B層のガラス転移温度(TgB:℃)が下記(II)式を満たすことが好ましい。(II’)式を満たすとより好ましく、(II”)式を満たせば最も好ましい。
TgB-TgA≧7・・・(II’)
TgB-TgA≧10・・・(II”)
各層のガラス転移温度(TgA、TgB)の制御方法は特に限定されないが、上記した通り、環状オレフィン系樹脂として、ノルボルネンとエチレンの共重合体を使用する場合、ノルボルネンの含有量を調整する方法、ノルボルネンの含有量の異なる2種類の環状オレフィン系樹脂をブレンドさせる方法、また、環状オレフィン系樹脂として、ノルボルネンの誘導体を開環メタセシス重合させた後に水素化させた樹脂を使用する場合、ノルボルネンの誘導体の分子量を大きくする方法、ガラス転移温度の異なる2種類のノルボルネンの誘導体を開環メタセシス重合させた後に水素化させた樹脂をブレンドさせる方法、ポリエチレン系樹脂、ポリプロピレン系樹脂を添加する方法などが挙げられる。
・本発明の成型用フィルムに加飾層を積層し、成型と同時に加飾層を部材へ転写させた後、本発明の成型用フィルムを剥離して、加飾部材を得る用途。
・本発明の成型用フィルムに機能層(例えば、耐候層、耐傷性層、導電性層、熱線吸収層、熱線反射層など)を積層し、成型と同時に機能層を部材へ転写させた後、本発明の成型用フィルムを剥離して、機能性部材を得る用途。
(γSdγLd )1/2 + (γSp γLp)1/2 +(γSh γLh )1/2 =γL(1+COS θ)/2
但し、γS =γSd +γSp +γSh
γL =γLd +γLp +γLh
γS 、γSd 、γSp 、γSh は、それぞれフィルム表面の表面自由エネルギー、分散力成分、極性力成分、水素結合成分を、またγL 、γLd 、γLp、γLhは用いた測定液のそれぞれ表面自由エネルギー、分散力成分、極性力成分、水素結合成分を表わすものとする。ここで、用いた各液体の表面張力は、Panzer(J.Panzer,J.Colloid Interface Sci.,44,142(1973)によって提案された値を用いている。
(1)フィルム厚みおよび層厚み
積層フィルムの全体厚みを測定する際は、ダイヤルゲージを用いて、フィルムから切り出した試料の任意の場所5ヶ所の厚みを測定し、平均値を求めた。
フィルムを任意の一方向および、その方向に直交する方向に長さ60mm×幅5mmの矩形に切り出しサンプルとした。動的粘弾性測定装置(レオロジ製、DVE-V4 FTレオスペクトラ)を用い、下記の条件下で測定を行い、測定温度範囲における貯蔵弾性率(E’)を求めた。
測定温度範囲:25℃~180℃、昇温速度:5℃/分。
示差走査熱量計(セイコー電子工業製、RDC220)を用い、JIS K7121-1987、JIS K7122-1987に準拠して測定および、解析を行った。
フィルムを任意の一方向および、その方向に直交する方向に長さ100mm×幅10mmの矩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20mmとし、引張速度を200mm/分としてフィルムの長手方向と幅方向にそれぞれ引張試験を行った。測定は予め160℃に設定した恒温層中にフィルム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。サンプルが破断したときの伸度を破断伸度とした。なお、測定は各サンプル、各方向に5回ずつ行い、その平均値で評価を行った。
フィルムを任意の位置で200mm×300mmの大きさに切り出してサンプルとした。200mmの方向について、端部から20mm間隔で11点、300mmの方向についても30mm間隔で11点、合計121点の厚みを測定し、最大値、最小値、平均値を求め、下記式より厚み斑を求めた。
フィルムの表面粗さSRaおよび表面粗さSRmaxは、小坂研究所製の3次元表面粗さ計ETB-30HKを用い、触針式で以下の条件で測定した。
触針加重 :10mg
測定長 :1mm送り
ピッチ :50μm
測定本数 :40本
カットオフ値:0.25mm
上記の条件で、粗さ曲面f(x,y)が得られたとき、SRa は下記の式(数1)で与えられる。
上記測定範囲の最大の山と最深の谷を平均面と平行な2面で挟み、その間隔を表面粗さSRmaxとする。
(7)ロールの表面粗さRa
ロール表面を、表面粗さ計(小坂研究所製、SE1700)を用いてロール表面の粗さを測定した。触針先端半径0.5μm、測定力100μN、測定長1mm、低域カットオフ0.200mm、高域カットオフ0.000mmの条件で測定し、JIS B-0601-2001に準拠して算術平均粗さRaを求めた。
フィルムを任意の位置で200mm×300mmの大きさに切り出してサンプルとした。3波長蛍光灯下で透過にて目視で観察を行い、長径が100μm以上の異物の個数をカウントし、A4サイズ当たりの異物の個数を以下の基準にて評価を行った。
A:異物の個数が10個未満であった。
B:異物の個数が10個以上20個未満であった。
C:異物の個数が20個以上30個未満であった。
D:異物の個数が30個以上であった。
フィルムストレッチャー(ブルックナー社製、KARO-IV)を用いて、下記の条件でフィルムを延伸した後のフィルム表面外観について、以下の基準にて評価を行った。
初期サンプル:100mm×100mm、予熱・延伸温度:各フィルムのTg+20℃、予熱時間:20s、延伸速度:20%/s、延伸倍率:2×2
A:表面光沢が非常に高く、ムラが全く観察されなかった。
B:表面光沢が高く、ほとんどムラが観察されなかった。
C:表面に若干のうねり状のムラが観察されたか、実用上問題ないレベルであった。
D:表面に顕著なうねり状のムラが観察された。
フィルムを任意の位置で200mm×300mmの大きさに切り出してサンプルとした。サンプルの表面(A層とB層を有する積層フィルムの場合は、B層側)に、アプリケーターを用いて、共栄社化学製UF-TCI-1を塗工した。塗工性について、以下の基準で評価を行った。
A:塗布ムラは発生せず、塗工性は良好であった。
B:塗布ムラはほとんど発生せず、塗工性は問題なかった。
C:塗布ムラが若干発生したが、実用上問題ないレベルであった。
D:顕著な塗布ムラが発生した。
フィルムを任意の位置で200mm×300mmの大きさに切り出してサンプルとした。サンプルの表面(A層とB層を有する積層フィルムの場合は、A層側)、に、アプリケーターを用いて、日本ケミカル製892Lを塗工し、80℃で10分間乾燥を行い、塗膜厚み20μmの接着層を形成した。得られた接着層積層フィルムを400℃の遠赤外線ヒーターを用いて、接着層積層フィルムを加熱し、50℃に加熱したポリプロピレン製樹脂型(底面直径150mm)に沿って真空・圧空成型(圧空:0.2Ma)を行い、フィルム/接着層/ポリプロピレン製樹脂型の構成体を得た。得られた構成体について、型に沿って成型できた状態(絞り比:成形高さ/底面直径)を以下の基準で評価した。すなわち、絞り比が異なる複数の型を用いてフィルムの成型性を確認し、成型できた型の絞り比の中で最も高い値を採用し、以下の基準で評価した。
145℃:実施例1、2、12、13、比較例1、3、5
155℃:実施例3、4、8~11、14、15、19~25
160℃:実施例5~7、16~18、26~28、比較例2、4
S:絞り比1.0以上で成形できた。
A:絞り比0.9以上1.0未満で成形できた。
B:絞り比0.8以上0.9未満で成形できた。
C:絞り比0.7以上0.8未満で成形できた
D:追従性が低く、絞り比0.7の形に成形できなかった。
S~Cであれば合格レベルである。
フィルムを任意の一方向方向および、その方向に直交する方向に長さ50mm×幅4mmの矩形に切り出しサンプルとし、熱機械分析装置(セイコ-インスツルメンツ製、TMA EXSTAR6000)を使用して、下記の条件下で昇温した際に、寸法変化率が1%を超える温度によって、以下の基準で評価した。
測定温度範囲:25~220℃
寸法変化率(%)
={|試長(mm)-保持後のフィルム長(mm)|/試長(mm)}×100 。
S:150℃以上
A:145℃以上150℃未満。
B:140℃以上145℃未満。
C:130℃以上140℃未満。
D:130℃未満。
フィルムを任意の位置で200mm×300mmの大きさに切り出してサンプルとした。サンプルの表面(A層とB層を有する積層フィルムの場合は、B層側)に、アプリケーターを用いて、共栄社化学製UF-TCI-1を塗工し、80℃で10分間乾燥を行い、塗膜厚み50μmのクリア層を形成した。また、クリア層の上にアプリケーターを用いて、アクリル/ウレタン系のシルバーインキを塗工し、80℃で10分間乾燥を行い、塗膜厚み30μmの加飾層を得た。さらに加飾層の上に、アプリケーターを用いて、日本ケミカル製892Lを塗工し、80℃で10分間乾燥を行い、塗膜厚み20μmの接着層を形成し、成型転写箔を得た。
A:0N/10mm以上0.2N/10mm未満
B:0.2N/10mm以上0.5N/10mm未満
C:0.5N/10mm以上1N/10mm未満
D:1N/10mm以上。
フィルムを任意の一方向方向および、その方向に直交する方向に長さ150mm×幅15mmの矩形に切り出しサンプルとし、東洋精機製のMIT耐折疲労試験機を用いて、JIS P8115(1994)に準拠する方法で実施した。破断までの折り曲げ回数N(各方向5回、計10回測定した平均値)を以下の基準で評価した。
折り曲げ角度:135±2°、折り曲げ回数 毎分175±10回
A:破断までの折り曲げ回数Nが10回以上
B:破断までの折り曲げ回数Nが10回未満。
各フィルムについて、幅400mm、長さ200mのフィルムロール(直径3インチ、幅550mmのコアに巻かれたフィルムロール)を準備し、下記条件にて、当該フィルムからフィルムを巻き出して、直径3インチ、幅550mmのコアに巻取った。
巻出張力:180N/m、巻取張力:120N/m
速度:20m/min
巻き姿を下記の基準で評価を行った。
A:核なしツブ欠点がみられず、かつ、巻き姿が非常に良好だった。
B:核なしツブ欠点がみられるか、巻き姿が不良であった(核なしツブ欠点がみられ、かつ、巻き姿が不良である場合を含む)。
500mm幅のフィルムロールを巻出し、予め温度をT1(貯蔵弾性率が1000MPaである温度)に設定した炉長2mのフローティング乾燥機内に1m/minの速度で通した際の炉内のフィルムを観察し、以下の基準で評価した。
A:フィルムのシワ、弛みの発生なし。
B:フィルムに若干のシワは見られるが弛みは発生なし。
C:フィルムにシワが発生。弛みは発生なし。
D:フィルムに弛みが発生。
フィルムロールのX面側に、ダイコーターにて共栄社化学製UF-TCI-1を塗工し、80℃で10分間乾燥を行い、塗膜厚み50μmのクリア層を形成した。続いて、クリア層の上に同じダイコーターを用いて、アクリル/ウレタン系のシルバーインキを塗工し、80℃で10分間乾燥を行い、塗膜厚み30μmの加飾層を形成した。さらに加飾層の上に、アプリケーターを用いて、日本ケミカル製892Lを塗工し、80℃で10分間乾燥を行い、塗膜厚み20μmの接着層を形成し、成型転写箔ロールを作製した。
A:蛍光灯の形状がはっきりと映って観察された。
B:蛍光灯の形状が映って観察されたが、若干ぼやけて見られる箇所があった。
C:蛍光灯の形状が不明瞭で全体的にぼやけていた。
(環状オレフィン系樹脂A)
ポリプラスチックス社製“TOPAS 8007F-04”を用いた。
ポリプラスチックス社製“TOPAS 6013F-04”を用いた。
ポリプラスチックス社製“TOPAS 6015S-04”を用いた。
日本ゼオン社製“ZEONOR 1060R”を用いた。
日本ゼオン社製“ZEONOR 1430R”を用いた。
ポリプラスチックス社製“TOPAS 6017S-04”を用いた。
プライムポリマー社製“エボリュー SP2540”を用いた。
※表中では、PEと表記。
プライムポリマー社製“P204”を用いた。
※表中では、PPと表記
(脂肪酸金属塩)
ナカライテスク社製のステアリン酸亜鉛を用いた。
チバ・スペシャルティ・ケミカルズ社製の“イルガノックス1010”を用いた。
表の組成、構成で樹脂を混合、単軸押出機(L/D=30)に供給し、供給部温度250℃、それ以降の温度を260℃で溶融し、濾過精度30μmのリーフディスクフィルターを通過させた後、Tダイ(リップ間隙:0.4mm)より、100℃に温度制御した鏡面ドラム(表面粗さ0.2s)上にシート状に吐出した。その際、弾性金属ロールにてニップをし(ニップ圧:0.2MPa)、フィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
(実施例4)
表の組成、構成とし、供給部温度260℃、それ以降の温度を270℃、鏡面ドラム温度を110℃に温度制御した以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例4と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
(実施例6)
表の組成、構成とし、供給部温度270℃、それ以降の温度を280℃、鏡面ドラム温度を120℃に温度制御した以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例6と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例4と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例4と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
(実施例11)
表の組成、構成とした以外は実施例4と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とし、それぞれ単軸押出機(L/D=30)に供給し、供給部温度250℃、それ以降の温度を260℃で溶融し、濾過精度30μmのリーフディスクフィルターを通過させた後、ダイの上部に設置したフィードブロック内にてB層/A層/B層(積層厚み比は表参照)となるように積層した後、Tダイ(リップ間隙:0.4mm)より、100℃に温度制御した鏡面ドラム(表面粗さ0.2s)上にシート状に吐出した。その際、弾性金属ロールにてニップをし(ニップ圧:0.2MPa)、フィルム厚み100μmの本発明の成型用脂フィルムを得た。
表の組成、構成とした以外は実施例12と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
(実施例14)
表の組成、構成とした以外は実施例12と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とし、供給部温度260℃、それ以降の温度を270℃、鏡面ドラム温度を110℃に温度制御した以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例15と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とし、B層押出機の供給部温度270℃、それ以降の温度を280℃、鏡面ドラム温度を120℃に温度制御した以外は実施例15と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例17と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例15と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例15と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例15と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例15と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とし、それぞれ単軸押出機(L/D=30)に供給し、供給部温度260℃、それ以降の温度を270℃で溶融し、濾過精度30μmのリーフディスクフィルターを通過させた後、ダイの上部に設置したフィードブロック内にてB層/A層/B層(積層厚み比は表参照)となるように積層した後、Tダイ(リップ間隙:1mm)より、100℃に温度制御した鏡面ドラム(表面粗さ0.2s)上にシート状に吐出した。その際、弾性金属ロールにてニップをし(ニップ圧:0.2MPa)、フィルム厚み100μmの本発明の成型用脂フィルムを得た。
表の組成、構成とし、それぞれ単軸押出機(L/D=30)に供給し、供給部温度260℃、それ以降の温度を270℃で溶融し、濾過精度30μmのリーフディスクフィルターを通過させた後、ダイの上部に設置したフィードブロック内にてB層/A層/B層(積層厚み比は表参照)となるように積層した後、Tダイ(リップ間隙:1mm)より、80℃に温度制御した鏡面ドラム(表面粗さ0.2s)上にシート状に吐出した。その際、弾性金属ロールにてニップをし(ニップ圧:0.2MPa)、フィルム厚み100μmの本発明の成型用脂フィルムを得た。
表の組成、構成とし、それぞれ単軸押出機(L/D=30)に供給し、供給部温度250℃、それ以降の温度を260℃で溶融し、濾過精度30μmのリーフディスクフィルターを通過させた後、ダイの上部に設置したフィードブロック内にてB層/A層/B層(積層厚み比は表参照)となるように積層した後、Tダイ(リップ間隙:1mm)より、40℃に温度制御した鏡面ドラム(表面粗さ0.2s)上にシート状に吐出した。その際、弾性金属ロールにてニップをし(ニップ圧:0.2MPa)、フィルム厚み100μmの本発明の成型用脂フィルムを得た。
表の組成、構成とした以外は実施例17と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例17と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例17と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例12と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例6と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例17と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
表の組成、構成とした以外は実施例1と同様にしてフィルム厚み100μmの本発明の成型用フィルムを得た。
弾性金属ロールとして、弾性金属ロール(表面粗さ0.2s、Ra0.01μm)を用いた以外は、実施例16と同様にして、フィルム厚み100μmの本発明の成型用フィルムを得た。
鏡面ドラム(表面粗さ0.2s)上にシート状に吐出する際のニップを、弾性金属ロールではなく、ゴムロール(表面粗さ0.8s、Ra0.1μm)を使用した以外は、実施例16と同様にして、フィルム厚み100μmの本発明の成型用フィルムを得た。
鏡面ドラム(表面粗さ0.2s)上にシート状に吐出する際のニップを、弾性金属ロールではなく、ゴムロール(表面粗さ6.3s、Ra0.6μm)を使用した以外は、実施例16と同様にして、フィルム厚み100μmの本発明の成型用フィルムを得た。
鏡面ドラム(表面粗さ0.2s)上にシート状に吐出する際のニップを、弾性金属ロールではなく、ゴムロール(表面粗さ18s、Ra1.6μm)を使用した以外は、実施例16と同様にして、フィルム厚み100μmの本発明の成型用フィルムを得た。
Claims (14)
- 環状オレフィン系樹脂を主成分とする成型用フィルムであって、
120℃における貯蔵弾性率が101MPa以上3000MPa以下、170℃における貯蔵弾性率が100MPa以下である、成型用フィルム。 - 環状オレフィン系樹脂を主成分とする環状オレフィン層(A層)の少なくとも片面に、環状オレフィン系樹脂を主成分とする環状オレフィン層(B層)を積層してなる積層フィルムであって、
前記A層は、A層全体100質量%に対して、ポリエチレン系樹脂及び/又はポリプロピレン系樹脂を1~40質量%含むことを特徴とする、請求項1に記載の成型用フィルム。 - B層/A層/B層の3層構成である請求項2に記載の成型用フィルム。
- 前記B層のガラス転移温度が、前記A層のガラス転移温度よりも高温であることを特徴とする、請求項2または3に記載の成型用フィルム。
- 前記A層のガラス転移温度が、111℃以上165℃以下であることを特徴とする、請求項2~4のいずれかに記載の成型用フィルム。
- 前記B層のガラス転移温度が、115℃以上170℃以下であり、かつA層のガラス転移温度よりも高温であることを特徴とする、請求項2~5のいずれかに記載の成型用フィルム。
- 貯蔵弾性率が1000MPaである温度(T1:℃)、貯蔵弾性率が100MPaである温度(T2:℃)が、下記(I)式を満たす、請求項1~6のいずれかに記載の成型用フィルム。
T2-T1≧10・・・(I) - 前記A層の厚みと前記B層の厚みの積層比(B層の合計厚み/A層の合計厚み)が、0.25~1である請求項3~7のいずれかに記載の成型用フィルム。
- フィルムの一面(X面)の表面粗さSRaが2nm以上50nm未満であり、他面(Y面)の表面粗さSRaが50nm以上1,000nm以下である、請求項1~8のいずれかに記載の成型用フィルム。
- フィルムの一面(X面)の表面粗さSRmaxが20nm以上500nm未満であり、他面(Y面)の表面粗さSRmaxが500nm以上10,000nm以下である、請求項1~9のいずれかに記載の成型用フィルム。
- フィルムの全成分の合計100質量%に対して、酸化防止剤および/または脂肪酸金属塩を0.005質量%以上0.5質量%以下含有する、請求項1~10のいずれかに記載の成型用フィルム。
- 少なくとも一方向の160℃における破断伸度が300%以上である請求項1~11のいずれかに記載の成型用フィルム。
- 前記成型用フィルムが、成型転写箔用フィルムであることを特徴とする、請求項1~12のいずれかに記載の成型用フィルム。
- 請求項1~13のいずれかに記載の成型用フィルムの少なくとも片面に、クリア層、加飾層及び接着層を順次有する成型転写箔。
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Also Published As
Publication number | Publication date |
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TW201318850A (zh) | 2013-05-16 |
US9649829B2 (en) | 2017-05-16 |
EP2749587A4 (en) | 2015-03-25 |
EP2749587A1 (en) | 2014-07-02 |
JPWO2013027547A1 (ja) | 2015-03-19 |
EP2749587B1 (en) | 2018-07-18 |
CN103717652A (zh) | 2014-04-09 |
JP5884734B2 (ja) | 2016-03-15 |
KR20140053035A (ko) | 2014-05-07 |
US20140170379A1 (en) | 2014-06-19 |
TWI546191B (zh) | 2016-08-21 |
KR102029486B1 (ko) | 2019-10-07 |
CN103717652B (zh) | 2016-05-18 |
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