WO2021014883A1 - Film de stratification et feuille de transfert de moule l'utilisant - Google Patents

Film de stratification et feuille de transfert de moule l'utilisant Download PDF

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Publication number
WO2021014883A1
WO2021014883A1 PCT/JP2020/025213 JP2020025213W WO2021014883A1 WO 2021014883 A1 WO2021014883 A1 WO 2021014883A1 JP 2020025213 W JP2020025213 W JP 2020025213W WO 2021014883 A1 WO2021014883 A1 WO 2021014883A1
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Prior art keywords
layer
laminated film
less
film
resin
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PCT/JP2020/025213
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English (en)
Japanese (ja)
Inventor
北村豊
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東レ株式会社
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Priority to JP2020536825A priority Critical patent/JPWO2021014883A1/ja
Publication of WO2021014883A1 publication Critical patent/WO2021014883A1/fr

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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
    • 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
    • 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
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer

Definitions

  • the present invention relates to a laminated film suitable for molding and decoration, and a molding transfer foil using the same.
  • a film containing a polyolefin resin as a main component is used, but when applied to a decoration application, there is a problem that the surface appearance is lacking in quality and deep drawability.
  • Patent Document 1 provides a method for achieving excellent surface appearance, processability, and deep drawability by applying a film containing a cyclic olefin resin as a main component. It is disclosed. Further, Patent Document 2 discloses a method of achieving both processability and moldability by laminating a polyurethane resin on a polypropylene resin.
  • the present invention was found to be solved by the following, and the present invention was reached. That is, the laminated film and the molded transfer foil of the present invention have the following configurations.
  • a layer containing polypropylene-based and polyethylene-based resins in a total amount of more than 50% by mass and 100% by mass or less was designated as layer A, and a layer containing a cyclic olefin-based resin as a main component and a thermoplastic elastomer was designated as layer B.
  • thermoplastic elastomer is an olefin-based elastomer.
  • both the heat shrinkage rate at 80 ° C. in the X1 direction and the Y1 direction are ⁇ .
  • the young rate at 25 ° C. in both the X2 direction and the Y2 direction is 50 MPa or more and 500 MPa.
  • the laminated film and the molded transfer foil of the present invention can be suitably used for decorating members such as building materials, automobile parts, mobile phones, electric appliances, and game machine parts.
  • the layer containing polypropylene-based and polyethylene-based resins in a total amount of more than 50% by mass and 100% by mass or less is the A layer, and the main component is the cyclic olefin resin and the layer containing the thermoplastic elastomer.
  • This is a laminated film having an A layer and a B layer when the B layer is used, and the B layer is located on the outermost surfaces on both sides.
  • the laminated film of the present invention has the A layer when the layer containing polypropylene-based and polyethylene-based resins in a total amount of more than 50% by mass and 100% by mass or less is defined as the A layer. is there.
  • Polypropylene-based and polyethylene-based resins have excellent toughness when made into a film. Therefore, since the laminated film has the A layer, it is possible to reduce edge defects, breakage, breakage, etc. in the process of cutting the laminated film and the process of winding while slitting the end while maintaining moldability. Can be done.
  • the layer A preferably contains a total of 75% by mass or more and 100% by mass or less of polypropylene-based and polyethylene-based resins.
  • the "layer containing polypropylene-based and polyethylene-based resins in a total amount of more than 50% by mass and 100% by mass or less” includes polypropylene-based resin and polyethylene-based resin, and the total content thereof constitutes the layer.
  • the polypropylene resin content shall be calculated by adding up all the polypropylene-based resins. The same applies when a plurality of types of polyethylene-based resins are contained in the layer.
  • Whether or not the laminated film has a layer (layer A) that satisfies the definition shall be determined by evaluating whether or not at least one layer constituting the laminated film satisfies the above requirements. That is, even if the total content of the polypropylene-based and polyethylene-based resins in the laminated film is 50% by mass or less, if there is even one layer satisfying the above requirements, the layer A is provided.
  • the ratio and combination of the two are not particularly limited as long as the effects of the present invention are not impaired.
  • the polypropylene-based resin refers to a resin containing 50 mol% or more and 100 mol% or less of propylene units in 100 mol% of all the constituent units constituting the resin.
  • the polypropylene-based resin in the A layer is not particularly limited as long as the effect of the present invention is not impaired.
  • a homopolypropylene resin which is a homopolymer of propylene, a random polypropylene resin copolymerized with ethylene, and both ethylene and propylene during polypropylene polymerization.
  • Block polypropylene resin or the like blended with the elastomer component of the polymer can be used alone or in combination of two or more.
  • the random polypropylene resin and the block polypropylene resin alone or in combination, and it is more preferable to use the random polypropylene resin alone.
  • a polyethylene-based resin is a resin containing 50 mol% or more and 100 mol% or less of ethylene units in 100 mol% of all constituent units constituting the resin (however, ethylene units in 100 mol% of all constituent units constituting the resin). And propylene units (excluding those containing 50 mol%).
  • the polyethylene-based resin in the A layer is not particularly limited as long as the effect of the present invention is not impaired.
  • low-density polyethylene LDPE: density measured by the high-pressure method (hereinafter, may be simply referred to as density) is 900 to 945 kg.
  • high density polyethylene polyethylene with a density greater than 945 kg / m 3
  • linear low density polyethylene LLDPE: manufactured by the low pressure method using a single site or multisite catalyst
  • At least one polyethylene-based resin selected from the group consisting of polyethylene having a density of 900 to 945 kg / m 3 ) can be preferably used.
  • high-density polyethylene and linear low-density polyethylene alone or in combination it is more preferable to use linear low-density polyethylene alone.
  • the laminated film of the present invention is mainly composed of a cyclic olefin resin from the viewpoint of improving toughness, quality, interlayer adhesion, dimensional stability in the processing process, and releasability from the design layer after the molding process. Moreover, when the layer containing the thermoplastic elastomer is the B layer, it is important that the B layer is provided and the B layer is located on the outermost surfaces on both sides.
  • the cyclic olefin resin can realize excellent surface appearance, processability, and moldability when made into a film, but has a problem in that it is highly brittle and the film itself becomes brittle.
  • the thermoplastic elastomer has excellent toughness, the above-mentioned properties of the cyclic olefin resin can be improved by adding it to the B layer. That is, by adopting such an embodiment, it is possible to realize excellent surface appearance, dimensional stability in the processing process, and moldability while suppressing a decrease in toughness of the laminated film. Further, when the laminated film has a structure in which the A layer and the B layer are directly laminated, the adhesion between the A layer and the B layer is also improved by containing the thermoplastic elastomer in the B layer.
  • the main component is the cyclic olefin resin
  • the cyclic olefin resin is contained in an amount of more than 50% by mass and 99% by mass or less when all the components constituting the layer are 100% by mass. ..
  • layers (layer B) satisfying the definition on both outermost surfaces
  • the laminated film of the present invention has the B layer located on the outermost surfaces on both sides, it has at least two B layers, but as long as the main component is a cyclic olefin resin and contains a thermoplastic elastomer.
  • the composition of the B layer constituting the laminated film may be the same as or different from each other. However, from the viewpoint of productivity, curl resistance, etc., it is preferable that the B layers constituting the laminated film have the same composition.
  • the cyclic olefin resin is a resin having an alicyclic structure in the main chain and contains 50 mol% or more and 100 mol% or less of cyclic olefin units in total in 100 mol% of all the constituent units of the resin.
  • the cyclic olefin refers to a hydrocarbon compound having a cyclic structure formed of carbon atoms and having a carbon-carbon double bond in the ring structure
  • the cyclic olefin unit is a configuration derived from the cyclic olefin. The unit.
  • the monomer for obtaining the cyclic olefin resin is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of productivity and surface appearance when the laminated film is used for decoration, bicyclo [2,2,1] ] Hept-2-ene (hereinafter referred to as norbornene), cyclopentadiene, 1,3-cyclohexadiene, and derivatives thereof are preferably used, and norbornene is more preferably used.
  • a resin containing only one type of cyclic olefin unit a resin containing a plurality of types of cyclic olefin units, one type or a plurality of types of cyclic olefin units, and one type or a plurality of types It may be any resin containing a chain olefin unit.
  • the chain olefin is a hydrocarbon compound having a carbon-carbon double bond and does not have a cyclic structure formed by carbon atoms, and the chain olefin unit is derived from a chain olefin. Refers to the structural unit of.
  • Examples of the chain olefin include ethylene and propylene, and examples of the chain olefin unit include ethylene unit and propylene unit.
  • the combination of the cyclic olefin unit and the chain olefin unit is not particularly limited as long as the effects of the present invention are not impaired.
  • the cyclic olefin resin in the B layer may be only one type or a plurality of types as long as the effects of the present invention are not impaired.
  • the content of the cyclic olefin resins shall be calculated by summing up all the cyclic olefin resins.
  • the cyclic olefin resin of the B layer includes polynorbornene, polycyclopentadiene, polycyclohexadiene, and norbornene and ethylene from the viewpoints of productivity, moldability, and surface appearance when a laminated film is used for decoration. It is preferable to use at least one or more of the polymers, and it is more preferable to use at least one of polynorbornene and a copolymer of norbornene and ethylene.
  • a method for obtaining a cyclic olefin resin will be described with an example.
  • a method for producing a resin obtained by polymerizing only a cyclic olefin monomer a known method such as addition polymerization of a cyclic olefin monomer or ring-opening polymerization can be used. More specific examples include a method in which norbornene is subjected to ring-opening metathesis polymerization and then hydrogenated, or a method in which norbornene is addition-polymerized to obtain polynorbornene. Further, polycyclopentadiene and polycyclohexadiene can be obtained by a method of adding 1,2-, 1,4-addition polymerization of cyclopentadiene and cyclohexadiene and then hydrogenating them.
  • a method for producing a resin obtained by copolymerizing a cyclic olefin monomer and a chain olefin monomer a known method such as addition polymerization of the cyclic olefin monomer and the chain olefin monomer can be used.
  • a copolymer of norbornene and ethylene can be obtained by a method of addition polymerization of norbornene and ethylene.
  • the content of the cyclic olefin resin in the B layer is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of mold releasability, dimensional stability in the processing process, and moldability, all the components constituting the B layer can be used. When it is 100% by mass, it is more preferably 60% by mass or more and 90% by mass or less.
  • thermoplastic elastomer in the B layer is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of improving the adhesion and toughness of the A layer and the B layer when the A layer and the B layer are directly laminated. From the viewpoint of compatibility with the cyclic olefin resin, it is preferable to use the olefin elastomer, the styrene elastomer, and the polyester elastomer alone or in combination of two or more.
  • the thermoplastic elastomer is more preferably an olefin elastomer, and ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene It is more preferable to use a copolymer ( ⁇ -olefin-based elastomer) or the like, ethylene- ⁇ -olefin-based elastomer and propylene- ⁇ -olefin-based elastomer are particularly preferably used, and ethylene- ⁇ -olefin-based elastomer is most preferably used.
  • the content of the thermoplastic elastomer in the B layer is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of improving the interlayer adhesion and toughness of the laminated film and reducing the difference in brittleness between the A layer and the B layer. Therefore, at least one of the B layers preferably contains 1% by mass or more and 40% by mass or less of the thermoplastic elastomer, more preferably 1% by mass or more and 39% by mass or less, and 3% by mass or more and 30% by mass or less. Is more preferable, and it is particularly preferable that the content is 5% by mass or more and 25% by mass or less.
  • the content of the thermoplastic elastomer in the B layer is calculated assuming that all the components constituting each B layer are 100% by mass. Further, from the viewpoint of productivity, curl resistance, etc., it is preferable that the difference in the content of the thermoplastic elastomer in the B layer on both surfaces is small, and the content of the thermoplastic elastomer in the B layer on both surfaces is equal. preferable.
  • the B layer contains a polyethylene resin.
  • the content of the polyethylene-based resin in the B layer is 1% by mass or more and 40% by mass or less when all the components constituting the B layer are 100% by mass from the viewpoint of improving the quality of the laminated film. It is more preferable that it is 1% by mass or more and 39% by mass or less, and further preferably 3% by mass or more and 20% by mass or less.
  • the polyethylene-based resin in the B layer the same ones that can be preferably used in the A layer described above can be preferably used.
  • the laminated film of the present invention contains 5% by mass or more and 40% by mass or less of a cyclic olefin resin when all the components constituting the laminated film are 100% by mass. Is preferable.
  • the moldability of the laminated film is improved by containing 5% by mass or more of the cyclic olefin resin, and the amount of the cyclic olefin resin is kept at 40% by mass or less. As a result, the decrease in toughness is reduced.
  • the laminated film of the present invention preferably contains a cyclic olefin resin of 10% by mass or more and 35% by mass or less, when all the components constituting the laminated film are 100% by mass, and the cyclic olefin resin. Is more preferably contained in an amount of 20% by mass or more and 30% by mass or less.
  • the amount of the cyclic olefin resin in the laminated film can be adjusted, for example, by adjusting the content of the cyclic olefin resin in the B layer and the relative thickness of the B layer in the laminated film.
  • the layer structure of the laminated film of the present invention has A layer and B layer, and is not particularly limited as long as the B layer is located on the outermost surfaces on both sides.
  • it may have a configuration of four or more layers having another layer between the A layer and the B layer.
  • the thickness of the laminated film of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 50 ⁇ m or more and 200 ⁇ m or less from the viewpoint of achieving both production stability and moldability.
  • the laminated film of the present invention has a storage elastic modulus of 101 MPa or more and less than 1,000 MPa at 75 ° C. and a storage elastic modulus of 100 MPa or less at 120 ° C. from the viewpoint of achieving both dimensional stability and moldability in the processing process. It is preferable to have.
  • the storage elastic modulus is an index that expresses the viscoelastic property by focusing on the phase delay of the stress and strain property of the substance.
  • the storage elastic modulus can be measured by a known dynamic viscoelasticity measuring device.
  • DVE-V4 FT Leospectra manufactured by Rheology
  • it is measured by the following method. be able to.
  • the storage elastic modulus (MPa) at 120 ° C. which will be described later, can also be measured in the same manner.
  • the storage elastic modulus at 75 ° C. is 101 MPa or more and less than 1,000 MPa means that the storage elastic modulus at 75 ° C. in the longitudinal direction and the width direction is 101 MPa or more and less than 1,000 MPa, and is hereinafter at 120 ° C. It can be interpreted in the same way including the storage elastic modulus.
  • the longitudinal direction refers to the direction in which the laminated film advances in the manufacturing process (corresponding to the winding direction of the roll when wound in a roll shape), and the width direction is parallel to the film surface. The direction orthogonal to the longitudinal direction.
  • the longitudinal direction and the width direction can be easily specified, but in the case of a sheet-shaped laminated film which is not wound on the roll, the longitudinal direction and the width direction can be easily specified.
  • the width direction cannot be easily specified.
  • the laminated film is rotated 5 ° to the right to perform the same measurement. It shall be repeated until the angle formed by the measurement direction and the first measurement direction reaches 175 °, and the direction having the largest value shall be treated as the longitudinal direction.
  • the storage elastic modulus at 75 ° C. is more preferably 200 MPa or more and less than 1,000 MPa, further preferably 300 MPa or more and less than 1,000 MPa, and 410 MPa or more. It is particularly preferably less than 1,000 MPa.
  • the storage elastic modulus of the laminated film can be suitably used not only for molding a member having a relatively high melting point such as metal, but also for molding a member having a relatively low melting point such as a resin.
  • the storage elastic modulus of the laminated film at 120 ° C. is more preferably 50 MPa or less, and even more preferably 30 MPa or less.
  • the lower limit of the storage elastic modulus at 120 ° C. is not particularly limited as long as the effect of the present invention is not impaired, but 0.5 MPa is sufficient from the viewpoint of moldability of the laminated film.
  • the method of setting the storage elastic modulus at 75 ° C. to 101 MPa or more and less than 1,000 MPa or the above-mentioned preferable range and the storage elastic modulus at 120 ° C. to 100 MPa or less or the above-mentioned preferable range is the method of the present invention.
  • the present invention is not particularly limited as long as the effect is not impaired, and examples thereof include a method in which the cyclic olefin resin is contained in an amount of 5% by mass or more and 40% by mass or less when all the components constituting the laminated film are 100% by mass. ..
  • the glass transition temperature of the B layer is set to 80 ° C. or higher, and the entire laminated film is formed.
  • the total thickness ratio of the B layer to 100% of the thickness ratio is preferably 20% or more and less than 50%.
  • the "total thickness ratio of the B layer” means the total thickness ratio of all the corresponding B layers in the entire laminated film.
  • the thickness of the laminated film can be measured by a dial gauge, and the layer thickness of each layer can be measured by observing a cross-sectional photograph when the film is cut perpendicularly to the film surface.
  • the laminated film of the present invention has the direction in which the heat shrinkage rate at 80 ° C. is the largest is the X1 direction, the X1 direction and the direction orthogonal to the film surface in the Y1 direction.
  • the heat shrinkage rate at 80 ° C. in both the X1 direction and the Y1 direction is preferably ⁇ 0.50% or more and 0.50% or less, and both is ⁇ 0.40% or more and 0.40% or less. It is preferable that both are ⁇ 0.29% or more and 0.29% or less.
  • the method of setting both the heat shrinkage rate at 80 ° C. in the X1 direction and the Y1 direction to ⁇ 0.50% or more and 0.50% or less or the above-mentioned preferable range is not particularly limited, but for example, in the A layer.
  • examples thereof include a method of adjusting the content of the polypropylene-based and polyethylene-based resins of the above and the content of the cyclic olefin-based resin in the B layer. More specifically, by reducing the content of the polypropylene-based resin and the polyethylene-based resin in the layer A and increasing the content of the cyclic olefin-based resin in the layer B, at 80 ° C. in the X1 direction and the Y1 direction. The heat shrinkage rate can be reduced.
  • the X1 direction and the Y1 direction can be determined by the following method. First, the heat shrinkage rate of the film at 80 ° C. is measured in one direction arbitrarily selected by the method described later. Subsequently, the film is rotated 5 ° to the right to perform the same measurement, and this is repeated until the angle formed by the measurement direction and the first measurement direction reaches 175 °. After that, the maximum value of the obtained measured value is specified, and the direction in which the maximum value is obtained is defined as the X1 direction, and the direction orthogonal to the X1 direction and the film plane is defined as the Y1 direction.
  • the laminated film of the present invention has the direction in which the Young's modulus at 25 ° C. is the largest in the X2 direction, the X2 direction and the direction orthogonal to the film plane in the Y2 direction.
  • the Young's modulus at 25 ° C. in the X2 and Y2 directions is preferably 50 MPa or more and 500 MPa or less, more preferably 100 MPa or more and 450 MPa, and further preferably 200 MPa or more and 400 MPa. Since the Young's modulus at 25 ° C.
  • the self-retaining property of the film is improved, so that wrinkles and the like are formed in the processing process (particularly the process of film coating, laminating, printing, vapor deposition, etc.). Processing defects can be suppressed.
  • the Young's modulus at 25 ° C. in both the X2 direction and the Y2 direction is 500 MPa or less, the toughness of the laminated film is improved, so that the edge is used in the step of cutting the laminated film or the step of winding while slitting the end. Problems such as defective parts, breaks, and breaks can be suppressed.
  • the method of setting the Young's modulus in both the X2 direction and the Y2 direction at 25 ° C. to 50 MPa or more and 500 MPa or less is not particularly limited, but for example, the content of the polypropylene-based and polyethylene-based resin of the A layer is adjusted. There is a way to do it. More specifically, by increasing the contents of the polypropylene-based resin and the polyethylene-based resin in the A layer, the Young's modulus at 25 ° C. in both the X2 direction and the Y2 direction can be reduced.
  • the X2 direction and the Y2 direction can be determined by the following method.
  • Young's modulus can be measured by the following procedure. First, a rectangular sample of 100 mm (measurement direction) ⁇ 10 mm is prepared, and a marked line having a length of 50 mm parallel to the measurement direction is marked in the center to prepare a measurement sample. The Young's modulus (MPa) of the obtained measurement sample is measured with a tensile tester at a tensile speed of 200 mm / min in an atmosphere of room temperature of 23 ° C. and relative humidity of 65%. The tensile tester can be appropriately selected as long as it can measure, and for example, "TENSILON" (registered trademark) UCT-100 (manufactured by Orientec) can be preferably used.
  • TENSILON registered trademark
  • UCT-100 manufactured by Orientec
  • the laminated film of the present invention is at least one of the best from the viewpoint of achieving both the adhesion between the laminated film and the design layer in the processing process for the molded transfer foil and the releasability between the laminated film and the design layer after the molding process.
  • the surface free energy of the surface is preferably 35 mN / m or more and 45 mN / m or less, more preferably 35 mN / m or more and 40 mN / m or less, and further preferably 35 mN / m or more and 38 mN / m or less.
  • the surface free energy of at least one of the outermost surfaces is 35 mN / m or more, the releasability between the laminated film and the design layer after the molding step can be improved.
  • the surface free energy of at least one of the outermost surfaces is 45 mN / m or less, the adhesion between the laminated film and the design layer in the process of processing the molded transfer foil can be improved.
  • the side where the design layer or the like is laminated is in the above range, and the opposite side may be an arbitrary value regardless of whether it is inside or outside the above range.
  • the method of setting the surface free energy to 35 mN / m or more and 45 mN / m or less is not particularly limited, but for example, the surface free energy can be increased by increasing the content of the cyclic olefin resin in the B layer. It can be made larger.
  • Surface free energy can be measured by the following procedure. First, with respect to a laminated film whose temperature and humidity were controlled for 24 hours under the conditions of room temperature of 23 ° C. and relative humidity of 65%, four kinds of measuring solutions of water, ethylene glycol, formamide, and methylene iodide were measured with a contact angle meter. Obtain a static contact angle with respect to the surface. Subsequently, the static contact angles obtained for each liquid and Panzer: J. et al. Colloid Interface Sci. , 44, 142 (1973).
  • the contact angle meter can be selected from known ones, and for example, the contact angle meter CA-D type manufactured by Kyowa Interface Chemistry Co., Ltd. can be preferably used.
  • the laminated film of the present invention is preferably a non-oriented film from the viewpoint of improving moldability.
  • the non-aligned film means a film having a plane orientation coefficient (fn) of 0.00 or more and 0.05 or less, and the plane orientation coefficient (fn) is a refractive index (fn) in the direction in which the refractive index is the largest in the film plane.
  • Nx), the refractive index (Ny) in the direction orthogonal to the direction having the largest refractive index in the film plane, and the refractive index (Nz) in the thickness direction of the film which are values calculated by the following equations.
  • the refractive index (Nx, Ny, Nz) in each direction can be measured by an Abbe refractive index meter using a sodium D line (wavelength 589 nm) as a light source.
  • the plane orientation coefficient (fn) is measured on both sides, and if at least one value satisfies the above requirements, it can be regarded as an unaligned film. From the above viewpoint, the plane orientation coefficient (fn) of the laminated film is more preferably 0.00 or more and 0.03 or less, and further preferably 0.00 or more and 0.02 or less.
  • the Abbe refractometer for example, NAR-4T (manufactured by Atago Co., Ltd.) can be used.
  • Planar orientation coefficient (fn) ⁇ (Nx + Ny) / 2 ⁇ -Nz.
  • the method for setting the plane orientation coefficient of the laminated film of the present invention to 0.00 or more and 0.05 or less is not particularly limited, but the film is formed by a known method such as an inflation method, a tubular method, or a T die casting method. , A method in which stretching is not performed in either direction can be mentioned. Above all, the T die casting method is preferably used in order to easily reduce the thickness of the laminated film to 50 ⁇ m or more and 200 ⁇ m or less.
  • the use of the laminated film of the present invention is not particularly limited, but it has toughness, quality, adhesion to the design layer in the processing process to the molded transfer foil, dimensional stability, and the design layer after the molding process. Since it is excellent in releasability and moldability, it is preferably a film for molding, and more preferably a film for molding transfer foil.
  • the molding film refers to a support film for transferring a design layer or the like formed on the surface to a molding member (adhesive body), and a molding transfer foil transfers to the molding member on the surface of the molding film.
  • the film, the design layer, and the adhesive layer of the present invention are located in this order from the viewpoint of facilitating the addition of decoration to the molded member.
  • the design layer refers to a layer for adding decorations such as coloring, pattern, wood grain, metal tone, and pearl tone to the molded member
  • the adhesive layer means adhesion between the molded member and the design layer. The layer that bears it.
  • the laminated film, the design layer, and the adhesive layer of the present invention are located in this order regardless of whether or not there is another layer between the laminated film and the design layer of the present invention and the design layer and the adhesive layer.
  • the protective layer is located between the laminated film of the present invention and the design layer from the viewpoint of protecting the surface of the product member.
  • the protective layer means a layer that plays a role of protecting the design layer transferred to the product member.
  • the resin used for the protective layer in the molded transfer foil of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is preferably a highly transparent resin from the viewpoint of not impairing the appearance of the product member.
  • a polyester resin, a polyolefin resin, an acrylic resin, a urethane resin, a fluorine resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer and the like are preferably used. Can be done.
  • thermosetting resin an ultraviolet curable resin, an electron beam curable resin, and a heat ray curable resin
  • an ultraviolet curable resin an electron beam curable resin, or the like.
  • an ultraviolet curable acrylic resin and an electron beam curable acrylic resin.
  • the method for forming the design layer is not particularly limited as long as the effect of the present invention is not impaired, and for example, coating, printing, metal deposition and the like can be used.
  • Resins used in the design layer include polyester resins, polyolefin resins, acrylic resins, urethane resins, fluororesins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate. Examples thereof include copolymers. These resins may be used alone or in combination as long as the effects of the present invention are not impaired.
  • the colorant in the design layer is not particularly limited as long as the effect of the present invention is not impaired, and is appropriately selected from known dyes, inorganic pigments, organic pigments, etc. in consideration of dispersibility in the resin used in the design layer. Can be done.
  • the thickness thereof is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 2 ⁇ m or more and 50 ⁇ m or less, from the viewpoint of color tone retention and designability of the product member, and 5 ⁇ m. It is more preferably 40 ⁇ m or less.
  • the method of forming the design layer by metal vapor deposition is not particularly limited as long as the effect of the present invention is not impaired, and a vacuum vapor deposition method, an EB vapor deposition method, a sputtering method, an ion plating method and the like can be used.
  • the metal in the metal vapor deposition is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of moldability of the design layer, indium or tin is preferable, and indium is more preferable.
  • the thickness thereof is preferably 0.001 ⁇ m or more and 100 ⁇ m or less, and 0.01 ⁇ m or more and 50 ⁇ m or less, from the viewpoint of achieving both moldability and design property of the design layer. Is more preferable, and 0.02 ⁇ m or more and 30 ⁇ m or less is further preferable.
  • the material of the adhesive layer provided on the design layer for the purpose of imparting adhesiveness to the molded member is not particularly limited as long as the effect of the present invention is not impaired, but a heat-sensitive type resin or a pressure-sensitive type resin can be used.
  • a heat-sensitive type resin for example, polyester-based resin, polyolefin-based resin, acrylic-based resin, polyamide-based resin, polyurethane resin and the like are preferably used.
  • the pressure-sensitive type resin include acrylic resin, polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, polystyrene resin, polyamide resin, chlorinated polyolefin resin, and chlorinated ethylene-acetic acid.
  • Vinyl copolymer resin, cyclized rubber, Kumaron inden resin, polyurethane resin, polyvinyl ether resin, polyvinyl acetate resin and the like are preferably used. These may be used alone or in combination as long as the effects of the present invention are not impaired.
  • the method for forming the adhesive layer is not particularly limited as long as the effect of the present invention is not impaired.
  • a coating method such as a roll coating method, a gravure coating method, or a comma coating method, and a printing method such as a gravure printing method or a screen printing method can be used. Can be used.
  • the molding member to be decorated by using the molding transfer foil using the molding film of the present invention is not particularly limited as long as the effect of the present invention is not impaired, and for example, polypropylene, acrylic, polystyrene, polyacrylonitrile-styrene, and Examples thereof include members mainly composed of resins such as polyacrylonitrile, butadiene and styrene, and members mainly composed of metals such as aluminum, magnesium, iron, titanium, copper and zinc.
  • the method for producing a laminated film of the present invention will be specifically described by taking as an example a film having a B layer / A layer / B layer having a two-kind three-layer structure and having the same composition of the B layers on both sides.
  • the method for producing the laminated film of the present invention is not limited to this.
  • a molten resin composition for obtaining the A layer of the laminated film that is, a molten resin composition containing a total of more than 50% by mass of polypropylene-based and polyethylene-based resins when all the components are 100% by mass.
  • a melt-kneading method in which each component is melt-kneaded.
  • the melt-kneading method is not particularly limited, and a known mixer such as a kneader, a roll mill, a Banbury mixer, and a single-screw or twin-screw extruder can be used. Above all, from the viewpoint of productivity, it is preferable to use a single-screw extruder.
  • the temperature of the raw material supply unit and thereafter can be appropriately set in consideration of the melting point of the resin and the like. For example, in either extruder, these temperatures may be set to 200 ° C. or higher and 300 ° C. or lower. preferable.
  • the feed block is melted so as to form a B layer / A layer / B layer.
  • the resin composition is laminated and discharged from a T-die into a sheet.
  • the thickness of the laminated film can be adjusted by adjusting the size of the lip gap of the T-die.
  • the laminated film of the present invention can be obtained by cooling and solidifying the molten sheet-like product thus obtained on a cast roll whose temperature is controlled to 0 ° C. or higher and 100 ° C. or lower, and the laminated film of the present invention is wound into a roll shape. It can also be taken as a film roll.
  • the surface roughness of the cast roll can be appropriately adjusted, and the molten sheet is made of rubber at the stage of cooling and solidifying on the cast roll. Niping with a shaping roll can also be preferably performed. At this time, by increasing the SRa of the cast roll or the rubber shaping roll, the SRa of the laminated film to which the SRa is transferred can also be increased.
  • the laminated film thus obtained is excellent in quality, productivity, dimensional stability in the processing process, and moldability, it can be suitably used as, for example, a film for molding, preferably a molding transfer foil.
  • a film for molding preferably a molding transfer foil.
  • the method for producing the molded transfer foil will be specifically described with reference to an example in which the design layer is an acrylic / urethane-based black ink layer, but the molded transfer foil of the present invention is not limited thereto.
  • the film is unwound from the film roll of the laminated film obtained by the above method, and an acrylic / urethane-based black ink is applied to one surface using an applicator to form a design layer. Further, an adhesive is applied to the surface of the design layer using an applicator and dried to form an adhesive layer. As long as the effect of the present invention is not impaired, an adhesive appropriately selected from known ones can be used, and specific examples thereof include 892L manufactured by Nippon Chemical Co., Ltd.
  • the molded transfer foil thus obtained is excellent not only in moldability but also in releasability from the design layer after the molding process.
  • the film thickness ( ⁇ m) was determined by measuring the thickness of a film sample at an arbitrary location (5 locations) using a dial gauge and averaging the obtained values.
  • a cross-sectional photograph of the laminated film was taken at a magnification of 100 times using a metallurgical microscope LeicaDMLM manufactured by Leica Microsystems, Inc. It was obtained by measuring the thickness of the film and calculating the average value of the obtained values.
  • Young's modulus A rectangular sample of 100 mm (measurement direction) ⁇ 10 mm was arbitrarily cut out from the laminated film, and a marked line having a length of 50 mm parallel to the measurement direction was marked in the center to prepare a measurement sample. Using a tensile tester (“TENSILON” (registered trademark) UCT-100 manufactured by Orientec), the obtained measurement sample was used in an atmosphere of room temperature of 23 ° C. and relative humidity of 65% at a tensile speed of 200 mm / min and Young's modulus ( MPa) (JIS K 7161-1: 2014) was measured.
  • TENSILON registered trademark
  • the same measurement was performed by rotating the measurement direction to the right by 5 °, and the same measurement was repeated until the measurement direction reached the direction rotated by 175 ° to the right from the first measurement direction.
  • the direction in which the obtained measured values are maximized was defined as the X2 direction
  • the X2 direction and the direction orthogonal to the film plane were defined as the Y2 direction
  • the measured values in the X2 direction and the Y2 direction were defined as Young's modulus in each direction.
  • Slit property of laminated film is an index for evaluating the degree of occurrence of defects such as edge defects, breakage, and breakage of the film in the processing process, in other words, toughness.
  • a method for measuring the slit property of the laminated film will be described with reference to FIG. Using a biaxial slitter set with a single-edged blade (FAS-10) manufactured by Feather Safety Razor Co., Ltd., a laminated film having a length of 200 m in the longitudinal direction 1 is subjected to conditions of a tension of 15 kg / m and a speed of 30 m / min. , The slit was made parallel to the longitudinal direction 1 and perpendicular to the width direction 2 by an aerial cut.
  • the presence or absence of unevenness is confirmed by visually observing the widthwise end 3 after the slit from the direction perpendicular to the film surface, and if there is unevenness, the period 4 in the longitudinal direction and the amplitude 5 in the width direction are measured by a metal scale (JIS1). Class scale).
  • JIS1 metal scale
  • Class scale The slit property of the film was evaluated according to the following criteria, and B or higher was regarded as acceptable.
  • A No unevenness was observed, or unevenness with a period of less than 0.5 mm and an amplitude of less than 5 mm was observed.
  • B Unevenness with a period of 0.5 mm or more and an amplitude of less than 5 mm was observed.
  • C The film broke in the slit. However, unevenness with an amplitude of 5 mm or more was observed.
  • Adhesion between Layer A and Layer B A rectangular sample of 15 mm ⁇ 110 mm was arbitrarily cut out from the laminated film to prepare a test piece. Next, using a MIT folding resistance tester (MID-D, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the test piece was placed in the short side direction under the conditions of a rotation speed of 175 cpm, a measurement load of 25 N (2.6 kgf), and a bending angle of 135 °. Ten evaluation samples were prepared by repeating bending 10 times in parallel, and evaluated according to the following criteria. As for the adhesion between the A layer and the B layer, B or higher was regarded as acceptable.
  • Planar Orientation Index A rectangular sample of 50 mm (longitudinal direction) x 50 mm (width direction) is arbitrarily cut out from the laminated film to form a test piece, and the Sodium D line (wavelength 589 nm) is used as a light source, and the Abbe refractometer NAR-4T. (Manufactured by Atago Co., Ltd.) was used to measure the refractive index (nMD) in the longitudinal direction and the refractive index (nTD) in the width direction in any one B layer of the laminated film.
  • nMD refractive index
  • nTD refractive index
  • the B layer was cut using a microtome (manufactured by Leica), and the refractive index (nMD) in the longitudinal direction and the refractive index (nTD) in the width direction of the layer A were measured in the same manner as in the layer B. Further, the test piece was cut in the thickness direction using a microtome, the refractive index (nZD) in the thickness direction of each layer of the laminated film was measured, and the plane orientation coefficient (fn) was calculated from the following formula.
  • Fn (nMD + nTD) / 2-nZD.
  • the design layer is formed on the surface that was located on the mirror-like rubber shaping roll side at the time of film formation, and the dimensional change is measured by using a caliper to measure the length change in the width direction and the longitudinal direction of the film before and after drying. It was decided to calculate.
  • the processability at the time of forming the design layer was C or higher.
  • A The dimensional change in both the width direction and the longitudinal direction was less than 1 mm.
  • B There was a dimensional change of 1 mm or more and less than 5 mm in at least one of the width direction and the longitudinal direction, and both in the width direction and the longitudinal direction. No dimensional change of 5 mm or more
  • C There was a dimensional change of 5 mm or more and less than 10 mm in at least one of the width direction and the longitudinal direction, and there was no dimensional change of 10 mm or more in both the width direction and the longitudinal direction
  • D Width There was a dimensional change of 10 mm or more in at least one of the direction and the longitudinal direction.
  • Vacuum / pressure molding (pressing air: 0.2 MPa) is performed along a heated polypropylene resin mold (cylindrical shape with a bottom diameter of 150 mm), and the laminated film / design layer / adhesive layer / polypropylene resin mold is located in this order. I got a body.
  • the moldability of the molded transfer foil was evaluated based on the following criteria from the obtained molded body in a state where it could be molded along a polypropylene resin mold (drawing ratio: molding height / bottom diameter). The moldability of the molded transfer foil was C or higher.
  • the glass transition temperature For the obtained specific heat change, find the midpoint between the straight line equidistant from the extended straight line of each baseline in the vertical axis (axis indicating the heat flow) and the curve of the stepwise change part of the glass transition. , The glass transition temperature. When a plurality of glass transition temperatures exist, the glass transition temperature on the high temperature side was defined as the glass transition temperature of the B layer.
  • the surface appearance of the product member refers to the surface appearance of the product member after the design layer and the adhesive layer are transferred to the product member by a molded transfer foil and only the laminated film is peeled off. Since the surface appearance of the product member is affected by the quality of the laminated film, it is an index for evaluating the quality.
  • An acrylic / urethane-based black ink was applied to the surface of the laminated film unwound from the film roll using a die coater, and dried at 80 ° C. for 10 minutes to form a design layer having a coating film thickness of 30 ⁇ m. Further, 892L manufactured by Nippon Chemical Co., Ltd. was applied onto the design layer by an applicator and dried at 80 ° C.
  • a molded transfer foil was cut out from the obtained molded transfer foil roll to a size of 200 mm (longitudinal direction) ⁇ 300 mm (width direction) at an arbitrary position.
  • the molded transfer foil and the molded member were overlapped in the order of laminated film / design layer / adhesive layer / molded member (flat polypropylene resin mold) and vacuum / pneumatic molding was performed to obtain a molded body.
  • the adhesive layer was cured by irradiating ultraviolet rays so that the irradiation intensity was 2,000 mJ / cm 2 .
  • the surface of the product member obtained by peeling only the laminated film from the molded body was observed with a scanning white interference microscope (VS-1000 manufactured by Hitachi High-Technologies Corporation) at a magnification of 5 times, and the following criteria were used.
  • the surface appearance (waviness: maximum point height of product member-minimum point height) was evaluated.
  • the surface appearance of the product member was B or higher.
  • the swell was less than 0.01 mm
  • Polypropylene resin Random polypropylene resin ("Prime Polypro” (registered trademark) Y-2045GP manufactured by Prime Polymer Co., Ltd.)
  • Polyethylene resin Linear low-density polyethylene (Prime Polymer Co., Ltd.
  • Evolu (registered trademark) SP2540) (Cyclic olefin resin A) Copolymer of norbornene and ethylene (“TOPAS” (registered trademark) 8007F-04 manufactured by Polyplastics Co., Ltd.) (Cyclic olefin resin B) Copolymer of norbornene and ethylene (“TOPAS” (registered trademark) 6013F-04 manufactured by Polyplastics Co., Ltd.) (Thermoplastic elastomer) Ethylene- ⁇ -olefin elastomer (“Esplen” (registered trademark) SPO manufactured by Sumitomo Chemical Co., Ltd.).
  • a matte metal shaping roll (surface roughness Ra:) whose temperature is controlled to 40 ° C. from a T die (lip gap: 0.4 mm). 0.9 ⁇ m) was discharged in the form of a sheet.
  • a nip was made with a mirror-like rubber shaping roll whose temperature was controlled to 30 ° C. (surface roughness Ra: 0.05 ⁇ m, nip pressure: 0.2 MPa) to obtain a laminated film having a thickness of 100 ⁇ m. It was wound into a roll.
  • Examples 2 to 7, Comparative Examples 1 to 3 A laminated film and a molded transfer foil were produced in the same manner as in Example 1 except that the composition and the lamination ratio of each layer were as shown in Table 1, and evaluated in the same manner. The evaluation results are shown in Table 1.
  • the component amount (mass%) of each layer is calculated with all the components constituting each layer as 100% by mass, and the cyclic olefin resin amount (mass%) in the laminated film is calculated with all the components constituting the laminated film as 100% by mass. did. None of Comparative Examples 1 to 3 have the requirement of A layer or B layer, but in these Comparative Examples, both outer layers are described as B layer and the intermediate layer is described as A layer.
  • the laminated film and the molded transfer foil of the present invention it is possible to provide a laminated film having excellent quality, productivity, dimensional stability in a processing process, and moldability, and a molded transfer foil using the laminated film.
  • the laminated film and the molded transfer foil of the present invention it is possible to impart high designability to the product member (molded member after molding and decoration) in various molding methods such as vacuum forming, compressed air molding, and press molding. Therefore, the laminated film and the molded transfer foil of the present invention can be suitably used for decorating molded members such as building materials, automobile parts, mobile phones, electric appliances, and game machine parts.
  • Width direction 1 Longitudinal direction 2 Width direction 3 Width direction end 4 Longitudinal period 5 Width direction amplitude

Landscapes

  • Laminated Bodies (AREA)

Abstract

Ce film de stratification est caractérisé en ce qu'il possède une couche A qui contient un total de pas moins de 50 % en masse mais moins de 100 % en masse d'une résine à base de polypropylène et d'une résine à base de polyéthylène et une couche B qui contient une résine à base d'oléfine cyclique en tant que composant principal et un élastomère thermoplastique, la couche B étant positionnée sur les deux côtés les plus à l'extérieur. L'invention concerne : un film de stratification ayant d'excellentes propriétés en termes de qualité, de productivité et de stabilité dimensionnelle pendant un processus de fabrication, ainsi qu'une aptitude au moulage ; et une feuille de transfert de moule utilisant ledit film de stratification.
PCT/JP2020/025213 2019-07-24 2020-06-26 Film de stratification et feuille de transfert de moule l'utilisant WO2021014883A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022091900A1 (fr) * 2020-10-26 2022-05-05 東レ株式会社 Film stratifié et feuille de transfert de moulage utilisant celui-ci
WO2023027014A1 (fr) * 2021-08-25 2023-03-02 デンカ株式会社 Film de démoulage thermoplastique pour processus de scellement de semi-conducteur, et procédé de fabrication de composant électronique le mettant en œuvre
EP4174120A1 (fr) * 2021-10-29 2023-05-03 Brückner Maschinenbau GmbH & Co. Kg Film orienté biaxialement contenant des polymères de cyclo-oléfine et des polymères d'alpha-oléfine, procédé pour sa préparation et son utilisation dans un condensateur

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JP2009040982A (ja) * 2007-08-11 2009-02-26 Sumitomo Bakelite Co Ltd 離型フィルム
JP2011161880A (ja) * 2010-02-15 2011-08-25 C I Kasei Co Ltd 熱収縮性ポリオレフィン系フィルム
JP2011178953A (ja) * 2010-03-03 2011-09-15 Nippon Zeon Co Ltd 離型フィルムおよびその製造方法
WO2014061403A1 (fr) * 2012-10-17 2014-04-24 東レ株式会社 Film stratifié
JP2017137469A (ja) * 2016-01-28 2017-08-10 東レ株式会社 フィルムおよびそれを用いた成型転写箔

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Publication number Priority date Publication date Assignee Title
JP2009040982A (ja) * 2007-08-11 2009-02-26 Sumitomo Bakelite Co Ltd 離型フィルム
JP2011161880A (ja) * 2010-02-15 2011-08-25 C I Kasei Co Ltd 熱収縮性ポリオレフィン系フィルム
JP2011178953A (ja) * 2010-03-03 2011-09-15 Nippon Zeon Co Ltd 離型フィルムおよびその製造方法
WO2014061403A1 (fr) * 2012-10-17 2014-04-24 東レ株式会社 Film stratifié
JP2017137469A (ja) * 2016-01-28 2017-08-10 東レ株式会社 フィルムおよびそれを用いた成型転写箔

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022091900A1 (fr) * 2020-10-26 2022-05-05 東レ株式会社 Film stratifié et feuille de transfert de moulage utilisant celui-ci
WO2023027014A1 (fr) * 2021-08-25 2023-03-02 デンカ株式会社 Film de démoulage thermoplastique pour processus de scellement de semi-conducteur, et procédé de fabrication de composant électronique le mettant en œuvre
JP7235936B1 (ja) * 2021-08-25 2023-03-08 デンカ株式会社 半導体封止プロセス用熱可塑性離型フィルム、及びこれを用いた電子部品の製造方法
EP4174120A1 (fr) * 2021-10-29 2023-05-03 Brückner Maschinenbau GmbH & Co. Kg Film orienté biaxialement contenant des polymères de cyclo-oléfine et des polymères d'alpha-oléfine, procédé pour sa préparation et son utilisation dans un condensateur

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