TW202108388A - Lamination film and mold transfer foil using same - Google Patents

Abstract

This lamination film is characterized by having layer A that contains a total of not less than 50 mass% but less than 100 mass% of a polypropylene-based resin and a polyethylene-based resin and layer B that contains a cyclic olefin-based resin as the main component and a thermoplastic elastomer, wherein the layer B is positioned on outermost surfaces on both sides. Provided are: a lamination film having excellent quality, productivity, dimensional stability during a manufacturing process, and moldability; and a mold transfer foil using said lamination film.

Description

Laminated film and forming transfer foil using it

The present invention relates to a laminated film suitable for molding and decoration purposes and a molding transfer foil using the laminated film.

In recent years, due to the rising awareness of environmental protection, in the fields of building materials, auto parts, mobile phones and electrical products, the demand for solvent-free coating or decorative methods that replace plating has increased, and film molding is being carried out. Import of decoration methods. As a method of decorating a three-dimensional shape member using a film, for example, a method of laminating a design layer etc. on a thermoplastic resin film and transferring the design layer etc. to the member while molding is known.

In such a decoration method, a film containing polyolefin resin as a main component is used, but when it is used for decoration purposes, the level of surface appearance and insufficient deep drawing formability become a problem.

As a method for improving the above-mentioned problems, Patent Document 1 discloses a method for achieving excellent surface appearance, processability, and deep drawing formability by using a film containing a cyclic olefin-based resin as a main component. In addition, Patent Document 2 discloses a method of laminating a polyurethane resin on a polypropylene resin to achieve both processability and moldability. [Prior Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2012/035956 Patent Document 2: Japanese Patent Application Publication No. 2014-198414

[The problem to be solved by the invention]

However, in the technique described in the aforementioned Patent Document 1, in the processing step (especially the step of cutting the film or the step of slitting the end while winding), the end of the film may be defective or folded due to insufficient toughness. Bending, breaking, etc., there are problems with grade or productivity. On the other hand, in the technology described in Patent Document 2, during the processing steps (especially the steps of film coating, lamination, printing, vapor deposition, etc.), the dimensional change of the film occurs, and the moldability is also poor, which becomes a problem.

In view of the background of the conventional technology, the subject of the present invention is to provide: a laminated film excellent in grade or productivity, dimensional stability and moldability in processing steps; and a molded transfer foil using the laminated film. [Means to solve the problem]

In order to solve the above-mentioned problems, the present invention has been intensively reviewed, and as a result, it has been found that the following solutions have been achieved, and the invention has been achieved. That is, the laminated film and the molded transfer foil of the present invention have the following constitutions.

(1) A laminated film characterized in that a layer containing a total of more than 50% by mass and 100% by mass or less of polypropylene and polyethylene resins is regarded as the A layer, and the main component is a cyclic olefin resin And when the layer containing the thermoplastic elastomer is regarded as the B layer, it has the A layer and the B layer, and the B layer is located on the outermost surface of both sides.

(2) The laminated film according to (1), wherein when all components constituting the laminated film are regarded as 100% by mass, the cyclic olefin resin is contained in an amount of 5% by mass or more and 40% by mass or less.

(3) The laminated film as in (1) or (2), which has a storage elastic modulus at 75°C of 101 MPa or more and less than 1,000 MPa, and a storage elastic modulus at 120°C of 100 MPa or less.

(4) The laminated film according to any one of (1) to (3), wherein at least one of the outermost surfaces has a surface free energy of 35 mN/m or more and 45 mN/m or less.

(5) The laminated film according to any one of (1) to (4), wherein at least one of the aforementioned B layers contains 1% by mass to 40% by mass of a thermoplastic elastomer.

(6) The laminated film according to any one of (1) to (5), wherein the aforementioned thermoplastic elastomer system olefin-based elastomer.

(7) The laminated film according to any one of (1) to (6), in which the direction with the largest heat shrinkage rate at 80°C is regarded as the X1 direction, and the direction orthogonal to the X1 direction in the film plane When regarded as the Y1 direction, the thermal shrinkage rates of both the X1 direction and the Y1 direction at 80°C are -0.50% or more and 0.50% or less.

(8) The laminated film according to any one of (1) to (7), wherein the direction in which the Young's modulus at 25°C is the largest is regarded as the X2 direction, and the direction perpendicular to the X2 direction in the film plane When the direction is regarded as the Y2 direction, the Young's modulus at 25°C in both the X2 direction and the Y2 direction is 50 MPa or more and 500 MPa or less.

(9) The laminated film according to any one of (1) to (8), wherein the aforementioned laminated film is a non-aligned film.

(10) The laminated film according to any one of (1) to (9), wherein the laminated film is a film for molding.

(11) The laminated film according to (10), wherein the aforementioned molding film is a film for molding transfer foil.

(12) A molded transfer foil, characterized in that the laminated film, the design layer and the adhesive layer of any one of (1) to (11) are arranged in this order.

(13) The molded transfer foil according to (12), wherein the protective layer is located between the laminated film and the design layer. [Effects of Invention]

According to the present invention, it is possible to provide: a laminated film excellent in grade or productivity, dimensional stability in processing steps, and moldability; and a molded transfer foil using the laminated film. In addition, by using the laminated film and the molded transfer foil of the present invention, high design can be imparted to the product member (molded and decorated member) in various molding methods such as vacuum molding, air pressure molding, and pressure molding. Therefore, the laminated film and the molded transfer foil of the present invention can be applied to, for example, decoration of building materials, automobile parts, mobile phones, electrical products, and game machine parts.

[Form to implement the invention]

The laminated film of the present invention is characterized in that a layer containing a total of more than 50% by mass and 100% by mass or less of polypropylene and polyethylene resins is regarded as layer A, and the main component is cyclic olefin resin and contains When the thermoplastic elastomer layer is regarded as the B layer, there are A layer and B layer, and the B layer is located on the outermost surface of both sides. Due to this aspect, the laminated film is excellent in grade or productivity, dimensional stability in processing steps, and moldability. Hereinafter, the laminated film of the present invention will be specifically explained.

(Level A) From the viewpoint of improving toughness, it is important for the laminated film of the present invention that when a layer containing a total of more than 50% by mass and 100% by mass or less of polypropylene and polyethylene resins is regarded as the A layer, it has A Floor. Polypropylene-based or polyethylene-based resins are excellent in toughness when used as a film. Therefore, since the laminated film has the A layer, the moldability can be maintained while reducing end defects, bends, and breaks in the step of cutting the laminated film or the step of cutting the ends while winding. From the above viewpoint, 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.

Here, the term "a layer containing more than 50% by mass and less than 100% by mass of polypropylene and polyethylene resins" refers to the total system containing polypropylene resin and polyethylene resin, and their contents A layer containing more than 50% by mass of the total components of the constituent layer; or a layer containing any one of a polypropylene resin and a polyethylene resin whose content is more than 50% by mass of the total components of the constituent layer. In addition, when the polypropylene resin in the layer is of plural types, the content of the polypropylene resin is calculated by adding up all the polypropylene resins. The same applies to the case where multiple types of polyethylene resins are included in the layer.

Whether the laminated film has a layer (layer A) that satisfies this definition is performed by evaluating whether or not at least one layer constituting the laminated film satisfies the above-mentioned requirements. That is, even if the total content of polypropylene-based and polyethylene-based resins in the entire laminated film is 50% by mass or less, if only one layer that satisfies the above-mentioned requirements is present, it is considered to have a layer A. In addition, when the polypropylene resin and the polyethylene resin are contained, the ratio or combination of the two is not particularly limited as long as the effects of the present invention are not impaired.

The so-called 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 structural units constituting the resin. The polypropylene resin in the A layer is not particularly limited as long as it does not impair the effects of the present invention. For example, it can be used alone or in combination with the following types: homopolypropylene resin which is a homopolymer of propylene, copolymerized resin Random polypropylene resin of ethylene, block polypropylene resin formed by blending elastomer component of ethylene-propylene copolymer during polypropylene polymerization. Among them, from the viewpoint of improving the adhesion between the layer A and the layer B described later, it is preferable to use 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.

The so-called polyethylene resin refers to a resin that contains ethylene units of 50 mol% or more and 100 mol% in 100 mol% of all the structural units of the resin (but not included in the 100 mol% of all the structural units of the resin). Ear% contains 50 mole% of both ethylene units and propylene units). The polyethylene resin in the A layer is not particularly limited as long as it does not impair the effect of the present invention. For example, it may be preferably selected from low-density polyethylene (LDPE: density measured by the high-pressure method (hereinafter also referred to as Density) is 900～945kg/m ³ polyethylene), high-density polyethylene (HDPE: polyethylene with a density greater than 945kg/m ³ ) and linear low-density polyethylene (LLDPE: using single-point or multi-point catalysts It is manufactured by a low-pressure method and has a density of 900-945 kg/m ³ polyethylene) at least one polyethylene resin in the group. Among them, it is preferable to use high-density polyethylene and linear low-density polyethylene alone or in combination, and it is more preferable to use linear low-density polyethylene alone.

(Layer B) From the viewpoint of making the toughness, grade, interlayer adhesion, dimensional stability during the processing step, and mold release from the design layer after the molding step good, it is important for the laminated film of the present invention that the main component is When the layer containing the cyclic olefin resin and the thermoplastic elastomer is regarded as the B layer, it has the B layer, and the B layer is located on the outermost surface of both sides.

Cyclic olefin-based resins can achieve excellent surface appearance, processability, and moldability when used as a film, but have problems in that the brittleness is high and the film itself becomes brittle. On the other hand, the thermoplastic elastomer has excellent toughness, so by adding it to the B layer, the above-mentioned properties of the cyclic olefin resin can be improved. That is, by adopting such a configuration, it is possible to achieve excellent surface appearance, dimensional stability and moldability during processing steps while suppressing the decrease in the toughness of the laminated film. In addition, when the laminated film has a structure in which the A layer and the B layer are directly laminated, since the B layer contains a thermoplastic elastomer, the adhesion between the A layer and the B layer is also improved.

Here, the term "cyclic olefin resin as a main component" refers to a cyclic olefin resin containing more than 50% by mass and 99% by mass when all components of the constituent layer are regarded as 100% by mass. The judgment of whether the laminated film has a layer (layer B) satisfying the definition on the outermost surface of both sides is performed by evaluating whether the outermost layer on both sides of the laminated film satisfies the above-mentioned requirements. In addition, the laminated film of the present invention has at least two B layers because the B layers are located on the outermost surfaces on both sides. However, 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 The lines can be the same or different. However, from the viewpoint of productivity, curl resistance, etc., the composition of the layer B constituting the laminated film is preferably the same as each other.

The so-called cyclic olefin resin refers to a resin having an alicyclic structure in the main chain, and a total of 50 mol% or more and 100 mol% or less of cyclic olefin units in 100 mol% of all constituent units of the resin . Here, the so-called 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 so-called cyclic olefin unit refers to a hydrocarbon compound derived from a cyclic olefin Constitutional unit.

The monomer used to obtain the cyclic olefin resin is not particularly limited as long as the effect of the present invention is not impaired. However, from the viewpoint of productivity and the surface appearance when the laminated film is used for decoration, it is preferable to use bicyclic [2,2,1]Hept-2-ene (hereinafter referred to as norbornene), cyclopentadiene, 1,3-cyclohexadiene, and derivatives thereof, and more preferably norbornene is used.

In addition, the cyclic olefin resin may be a resin containing one type of cyclic olefin unit, a resin containing multiple types of cyclic olefin units, a resin containing one type or multiple types of cyclic olefin units, and 1 type as long as the cyclic olefin resin meets the above requirements. Either one type or plural types of resins of chain olefin units. Here, the so-called chain olefin refers to a hydrocarbon compound having a carbon-carbon double bond and does not have a cyclic structure formed by carbon atoms; the so-called chain olefin unit refers to a structure derived from a chain olefin unit. Examples of chain olefins include ethylene or propylene, and examples of chain olefin units include ethylene units and propylene units. In addition, the combination of a cyclic olefin unit and a chain olefin unit is not particularly limited as long as the effect of the present invention is not impaired.

As long as the cyclic olefin resin in the B layer does not impair the effect of the present invention, it may be of only one type, or may be of plural types. In addition, when the cyclic olefin-based resin in the layer is of plural types, the content of the cyclic olefin-based resin is calculated by adding up all the cyclic olefin-based resins.

As the cyclic olefin resin of the B layer, it is preferable to use polynorbornene, polycyclopentadiene, and polycyclohexene from the viewpoints of productivity, moldability, and surface appearance when the laminated film is used for decoration. At least one of the diene and the copolymer of norbornene and ethylene is more preferably at least one of polynorbornene and the copolymer of norbornene and ethylene.

Next, the method for obtaining the cyclic olefin-based resin will be exemplified. As a method for producing a resin that polymerizes only cyclic olefin monomers, well-known methods such as addition polymerization or ring-opening polymerization of cyclic olefin monomers can be used. As a more specific example, a method of obtaining polynorbornene by subjecting norbornene to ring-opening metathesis polymerization followed by hydrogenation, or addition polymerization of norbornene. Furthermore, by subjecting cyclopentadiene and cyclohexadiene to 1,2-, 1,4-addition polymerization and then hydrogenating them, polycyclopentadiene and polycyclohexadiene can be obtained.

As a method for producing a resin that copolymerizes a cyclic olefin monomer and a chain olefin monomer, a well-known method such as addition polymerization of a cyclic olefin monomer and a chain olefin monomer can be used. For example, by the method of addition polymerization of norbornene and ethylene, a copolymer of norbornene and ethylene can be obtained.

The content of the cyclic olefin resin in the layer B is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoints of mold releasability, dimensional stability in the processing step, and moldability, it will constitute the layer B When all the components of ® are regarded as 100% by mass, it is more preferably 60% by mass or more and 90% by mass or less.

The thermoplastic elastomer in the B layer is not particularly limited as long as it does not impair the effects of the present invention. However, from the viewpoint of improving the adhesion and toughness between the A layer and the B layer when the A layer and the B layer are directly laminated, and From the viewpoint of the compatibility of the cyclic olefin resin, it is preferable to use an olefin elastomer, a styrene elastomer, and a polyester elastomer singly or in combination of two or more types.

Among them, from the viewpoint of compatibility with cyclic olefin resins, the thermoplastic elastomer is more preferably an olefin elastomer, and even more preferably ethylene, propylene, 1-butene, 1-hexene, and 4-methyl are used. -Copolymers of α-olefins such as pentene (α-olefin-based elastomers), etc., particularly preferably ethylene-α-olefin-based elastomers and propylene-α-olefin-based elastomers, and most preferably ethylene-α-olefin-based elastomers.

The content of the thermoplastic elastomer in the B layer is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of improving the interlayer adhesion or toughness of the laminated film, and reducing the difference between the brittleness of the A layer and the B layer In view, at least one of the layer B preferably contains 1% by mass or more and 40% by mass or less of thermoplastic elastomer, more preferably contains 1% by mass or more and 39% by mass or less, and still more preferably contains 3% by mass or more and 30% by mass or less It is particularly preferable to include 5% by mass or more and 25% by mass or less. In addition, the content of the thermoplastic elastomer in the B layer is calculated by taking all the components constituting each B layer as 100% by mass. Also, from the viewpoint of productivity or curl resistance, it is preferable that the difference in the content of the thermoplastic elastomer in the layer B on both surfaces is small, and it is more preferable that the content of the thermoplastic elastomer in the layer B on both surfaces is equal. .

Furthermore, from the viewpoint of improving the toughness of the laminated film, the layer B preferably contains a polyethylene-based resin. At this time, the content of the polyethylene resin in the layer B, from the viewpoint of improving the grade of the laminated film, when all the components constituting the layer B are regarded as 100% by mass, it is preferably 1% by mass or more and 40% by mass or less. More preferably, it is 1% by mass or more and 39% by mass or less, and still more preferably 3% by mass or more and 20% by mass or less. In addition, as the polyethylene-based resin in the B layer, the same as those applicable to the aforementioned A layer can be suitably used.

(Layer composition, composition, thickness of laminated film) From the viewpoint of improving toughness and moldability, the laminated film of the present invention preferably contains cyclic olefin resin in an amount of 5% by mass to 40% by mass when all components constituting the laminated film are regarded as 100% by mass. When all the components constituting the laminated film are regarded as 100% by mass, by containing 5 mass% or more of the cyclic olefin resin, the moldability of the laminated film is improved, and the amount of the cyclic olefin resin is kept at 40%. Mass% or less, and the decrease in toughness is reduced. Based on the above point of view, the laminated film of the present invention, when all components constituting the laminated film are regarded as 100% by mass, more preferably contains 10% by mass to 35% by mass of cyclic olefin resin, and more preferably contains 20% by mass % Or more and 30% by mass or less of cyclic olefin resin. 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 or the relative thickness of the B layer in the laminated film.

The layer structure of the laminated film of the present invention is not particularly limited as long as it has a layer A and a layer B, and the layer B is located on the outermost surfaces of both sides. For example, a three-layer structure of layer B/layer A/layer B can be mentioned. And there are 4 or more layers of other layers between the A layer and the B layer. Furthermore, 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 from the viewpoint of both production stability and moldability, it is preferably 50 μm or more and 200 μm or less.

(Storage modulus of elasticity) The laminated film of the present invention preferably has a storage elastic modulus of 101 MPa or more and less than 1,000 MPa at 75°C from the viewpoint of both dimensional stability and moldability in the processing step, and storage at 120°C The modulus of elasticity is 100 MPa or less. The so-called storage modulus of elasticity refers to the index of viscoelastic properties that focuses on the phase delay of the stress and strain properties of a substance.

The storage elastic modulus can be measured by a well-known dynamic viscoelasticity measuring device. For example, when DVE-V4 FT Rheospectra (manufactured by RHEOLOGY) is used as the dynamic viscoelasticity measuring device, it can be measured by the following method. First, prepare a measurement sample of 60mm (measurement direction) x 5mm in a rectangular shape, and use a dynamic viscoelasticity measuring device to measure under the following measurement conditions to obtain the storage elastic modulus in the measurement direction at 75°C ( MPa). In addition, the storage elastic modulus (MPa) at 120°C described later can also be measured in the same manner.

<Measurement conditions> Frequency: 10Hz Test length: 20mm Displacement amplitude: 10μm Measuring temperature range: 25℃～160℃ Heating rate: 5°C/min.

The so-called storage elastic modulus at 75°C is 101MPa or more and less than 1,000MPa, which means that the storage elastic modulus at 75°C in both the length and width directions is 101MPa or more and less than 1,000MPa, and the following is also included at 120°C The storage modulus of elasticity is included, and the same explanation can be made. Here, the so-called length direction refers to the direction in which the laminated film advances during the manufacturing process (it is equivalent to the winding direction of the roll when it is wound into a roll); the so-called width direction refers to the direction parallel to the film surface and to the length direction Orthogonal direction.

In addition, when the laminated film is wound into a roll, the length direction or the width direction can be easily defined, but when it is a sheet-like laminated film that is not wound into a roll, the length direction or the width direction cannot be easily defined. In such a case, the storage elastic modulus of the laminated film at 75°C is measured by the aforementioned method for a randomly selected direction, then the laminated film is rotated 5° to the right, the same measurement is performed, and this is repeated until Until the angle between the measurement direction and the first measurement direction reaches 175°, the direction with the largest value is regarded as the longitudinal direction.

By setting the storage elastic modulus at 75°C to 101 MPa or more, dimensional changes in processing steps such as coating, lamination, printing, and vapor deposition can be reduced. In addition, by setting the storage elastic modulus at 75°C to less than 1,000 MPa, it is possible to reduce the decrease in productivity while ensuring toughness. In addition, from the viewpoint of dimensional stability in the processability of the processing step, the storage elastic modulus at 75°C is preferably 200 MPa or more and less than 1,000 MPa, more preferably 300 MPa or more and less than 1,000 MPa, and particularly preferably 410MPa or more and less than 1,000MPa.

In addition, by setting the storage elastic modulus of the laminated film at 120°C to 100 MPa or less, not only does it have excellent moldability, but the molding temperature can also be set at a relatively low temperature of 150°C or less. Therefore, the laminated film is not only suitable for the molding of components with relatively high melting points such as metals, but also for molding components with relatively low melting points, such as resins. Furthermore, when high moldability is required, the storage elastic modulus of the laminated film at 120°C is more preferably 50 MPa or less, and still more preferably 30 MPa or less. In addition, 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 from the viewpoint of the moldability of the laminated film, 0.5 MPa is sufficient.

In the laminated film of the present invention, the storage elastic modulus at 75°C is 101 MPa or more and less than 1,000 MPa or the above-mentioned preferred range, and the storage elastic modulus at 120°C is 100 MPa or less or the above-mentioned preferable range. The method of the preferred range is not particularly limited as long as the effect of the present invention is not impaired. For example, it may be mentioned that when all the components constituting the laminated film are regarded as 100% by mass, the method is made to contain 5% by mass to 40% by mass. The method of forming olefin-based resins, etc.

In addition, from the viewpoint of making it easier to make the storage elastic modulus of the laminated film at 75°C of 101 MPa or more and less than 1,000 MPa or the above-mentioned preferred range, it is preferable to set the glass transition temperature of layer B to 80°C As described above, the total thickness ratio of the layer B is set to 20% or more and less than 50% with respect to the thickness ratio of the entire laminate film 100%. Here, the "total thickness ratio of the B layer" refers to the total thickness ratio of all the B layers that should be accounted for in the entire laminate film. In addition, the thickness of the laminated film can be measured with a dial gauge, and the layer thickness of each layer can be measured by observing the cross-sectional photograph when it is cut perpendicular to the film surface.

(Heat shrinkage) In the laminated film of the present invention, from the viewpoint of improving the dimensional stability in the processing step, the direction in which the thermal shrinkage rate at 80°C is the largest is the X1 direction, and the X1 direction is orthogonal to the film plane. When the direction of is regarded as the Y1 direction, the thermal shrinkage rate of the X1 direction and the Y1 direction at 80°C are preferably -0.50% or more and 0.50% or less, more preferably -0.40% or more and 0.40% or less, and even better are all -0.29% above 0.29%. By the heat shrinkage rate at 80 ℃ are all -0.50% or more and 0.50% or less, which can suppress the expansion and shrinkage when the laminated film is processed into a molded transfer foil.

In the laminated film of the present invention, there is no particular limitation on the method for making the heat shrinkage rates in both the X1 direction and the Y1 direction at 80°C to be -0.50% or more and 0.50% or less or the above-mentioned preferred range, but for example, A method of adjusting the content of polypropylene-based and polyethylene-based resins in layer A or the content of cyclic olefin-based resins in layer B. More specifically, by reducing the content of polypropylene resin and polyethylene resin in layer A, or increasing the content of cyclic olefin resin in layer B, the X1 direction and Y1 direction at 80°C can be reduced The heat shrinkage rate.

The X1 direction and Y1 direction can be determined by the following method. First, for one direction arbitrarily selected, the thermal shrinkage rate of the film at 80°C was measured by the method described later. Next, the film was rotated 5° to the right, and the same measurement was performed, and this was repeated until the angle formed by the measurement direction and the initial measurement direction reached 175°. Then, the maximum value of the measured value obtained is defined, the direction in which the maximum value can be obtained is regarded as the X1 direction, and the direction orthogonal to the X1 direction in the film plane is regarded as the Y1 direction.

The thermal shrinkage rate at 80°C can be determined by the following procedure. First, prepare a rectangular sample of 250 mm (measurement direction) × 10 mm, and mark the center with a 200 mm length parallel to the measurement direction as a measurement sample. A weight of 3g was applied to this measurement sample, and it was heat-treated at 80°C for 5 minutes in a hot-air circulating oven, and the thermal shrinkage rate of the laminated film at 80°C was calculated according to the following formula (the formula is the thermal shrinkage rate (%)). Thermal shrinkage (%)={1-(length of marking line after heat treatment)/(length of marking line before heat treatment)}×100.

(Young's modulus) In the laminated film of the present invention, from the viewpoint of improving toughness and dimensional stability during processing steps, the direction in which the Young's modulus at 25°C is the largest is regarded as the X2 direction, and the X2 direction is on the film surface. When the inner orthogonal direction is taken as the Y2 direction, the Young's modulus of the X2 and Y2 directions at 25°C is preferably 50MPa or more and 500MPa or less, more preferably 100MPa or more and 450MPa or less, and even more preferably 200MPa or more and 400MPa the following. Since the Young's modulus in both the X2 direction and the Y2 direction at 25°C is above 50 MPa, the self-retaining property of the film is increased, so it is necessary for the processing steps (especially the steps of coating, lamination, printing, vapor deposition, etc.) ) Can suppress processing defects such as wrinkles. On the other hand, since the Young's modulus in both the X2 direction and the Y2 direction at 25°C is 500 MPa or less, the toughness of the laminated film is increased, so in the step of cutting the laminated film or the step of cutting the end while winding, etc. It can suppress defects such as poor ends, bends and breaks.

In the laminated film of the present invention, the method of making the Young's modulus in both the X2 direction and the Y2 direction at 25° C. 50 MPa or more and 500 MPa or less is not particularly limited, but for example, a polypropylene system for adjusting the aforementioned A layer can be mentioned. And the method of the content of polyethylene resin. More specifically, by increasing the content of polypropylene resin and polyethylene 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 Y2 direction can be determined by the following method. First, for one direction arbitrarily selected, the Young's modulus of the laminated film is measured by the method described later. Next, the measurement direction was rotated 5° to the right, the same measurement was performed, and this was repeated until the angle formed by the measurement direction and the initial measurement direction reached 175°. Then, the maximum value of the obtained measured value is defined, the direction in which the maximum value can be obtained is regarded as the X2 direction, and the direction orthogonal to the X2 direction in the film plane is regarded as the Y2 direction. In addition, the above-mentioned X1, Y1, X2, Y2 are as described above, and they may not be the same due to different determination methods.

The Young's modulus system can be determined by the following procedure. First, prepare a rectangular sample of 100 mm (measurement direction) × 10 mm, and mark the center with a 50-mm mark parallel to the measurement direction as a measurement sample. For the obtained measurement sample, the Young's modulus (MPa) was measured by a tensile testing machine at a tensile speed of 200 mm/min under an environment of a room temperature of 23° C. and a relative humidity of 65%. In addition, the tensile tester can be appropriately selected as long as it can measure. For example, "TENSILON" (registered trademark) UCT-100 (manufactured by Rientec) can be suitably used.

(Surface free energy) The laminated film of the present invention, from the viewpoint of both the adhesion between the laminated film and the design layer in the processing step of the molded transfer foil, and the release property of the laminated film and the design layer after the molding step, at least one of them The surface free energy of the outermost 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 still more preferably 35 mN/m or more and 38 mN/m or less. Since the surface free energy of at least one of the outermost surfaces is 35 mN/m or more, the release property of the laminated film and the design layer after the forming step can be improved. On the other hand, since 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 forming the transfer foil can be improved. Regarding the surface free energy when the film is used for molding purposes, it is preferable that the side on which the design layer or the like is laminated falls within the above range; the opposite side may have any value regardless of whether it is within or outside the above range.

In the laminated film of the present invention, the method for making the surface free energy 35 mN/m or more and 45 mN/m or less is not particularly limited. For example, it can be increased by increasing the content of the cyclic olefin resin in the layer B. Surface free energy.

The surface free energy can be measured by the following procedure. First of all, for the laminated film after 24 hours of temperature and humidity adjustment at a room temperature of 23°C and a relative humidity of 65%, four types of measurement solutions of water, ethylene glycol, formazan and diiodomethane are used to The contact angle meter obtains the static contact angle to the surface. Next, the static contact angles obtained in the respective liquids and the dispersion terms, polar terms, and hydrogen bonding terms of the surface free energy of each liquid described in Panzer: J. Colloid Interface Sci., 44,142 (1973). Akio and Hata Toshio: The "Hat and Kitazaki Expansion Fowkes Formula" described in 8, (3) 131 (1972). of the Japan Adhesion Association paper, find the surface free energy.

In addition, the contact angle meter can be selected from well-known ones, and for example, the contact angle meter CA-D manufactured by Kyowa Interface Chemistry (Stock) can be suitably used.

(Orientation) The laminated film of the present invention is preferably a non-aligned film from the viewpoint of improving moldability. The so-called non-aligned film refers to a film with a surface alignment coefficient (fn) of 0.00 or more and 0.05 or less; the so-called surface alignment coefficient (fn) refers to the refractive index in the direction of the largest refractive index in the film plane as (Nx), The refractive index in the direction orthogonal to the direction of the maximum refractive index in the film plane is regarded as (Ny), and the refractive index in the thickness direction of the film is regarded as (Nz), and the value is calculated by the following formula. At this time, the refractive index (Nx, Ny, Nz) in each direction can be measured with an Abbe refractometer using the sodium D line (wavelength 589nm) as the light source. In addition, the surface alignment coefficient (fn) is measured on both sides, and as long as the value of at least one meets the above requirements, it can be regarded as a non-aligned film. Furthermore, based on the above viewpoint, the plane alignment coefficient (fn) of the laminated film is more preferably 0.00 or more and 0.03 or less, and still more preferably 0.00 or more and 0.02 or less. In addition, as the Abbe refractometer system, for example, NAR-4T (manufactured by ATAGO Co., Ltd.) can be used.

Surface alignment coefficient (fn)={(Nx+Ny)/2}-Nz.

The method of making the surface orientation coefficient of the laminated film of the present invention 0.00 or more and 0.05 or less is not particularly limited. For example, it may be formed by a well-known method such as an inflation method, a tubular method, and a T-die casting method. And there is no extension method in either direction. Among them, in order to easily make the thickness of the laminated film 50 μm or more and 200 μm or less, a T-die casting method is preferably used.

(Uses and forming transfer foil) The use of the laminated film of the present invention is not particularly limited, but for toughness, grade, adhesion to the design layer or dimensional stability in the processing step of the molded transfer foil, and release of the design layer after the molding step Since it is excellent in properties and moldability, it is preferably a film for molding, and more preferably a film for molding transfer foil. Here, the so-called molding film refers to the support film used to transfer the design layer formed on the surface to the molding member (attached body); the so-called molding transfer foil refers to the surface of the molding film A laminate having a layer transferred to a molding member.

In the molding transfer foil of the present invention, it is important to arrange the film, the design layer, and the adhesive layer of the present invention in order from the viewpoint of easily adding decoration to the molding member. Here, the so-called design layer refers to the layer used to attach decorations such as coloring, pattern, wood grain style, metal style, and pearl style to the molded member; the so-called bonding layer refers to the bonding between the molded member and the design layer的层。 The layer. In addition, to arrange the laminated film, the design layer, and the adhesive layer of the present invention in order, that is, regardless of whether there are other layers between the laminated film and the design layer, the design layer and the adhesive layer of the present invention, as long as the laminate film of the present invention is arranged in order The film, the design layer and the adhesive layer are all the same. By using the molding transfer foil in this aspect, it is possible to transfer the design layer to the molding member, peel off the laminated film of the present invention, and obtain a product member (molded member after molding and decoration) excellent in design.

Furthermore, in the forming transfer foil of the present invention, from the viewpoint of protecting the surface of the product member, it is preferable that the protective layer is located between the laminated film of the present invention and the design layer. The protective layer here refers to a layer that plays a role of protecting the design layer transferred from the work-in-process component. By being in such a situation, the damage resistance, weather resistance, and design properties of the surface of the product member after the molded transfer foil is attached to the molded member and only the laminated film is peeled off will be improved.

The resin used in the protective layer of the molded transfer foil of the present invention is not particularly limited as long as it does not impair the effects of the present invention. However, from the viewpoint of not impairing the appearance of the product member, a resin with high transparency is preferred. For example, polyester resins, polyolefin resins, acrylic resins, urethane resins, fluorine resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and ethylene-based resins can be preferably used. Vinyl acetate copolymer, etc. Also, from the viewpoint of improving the damage resistance of the product components, it is preferable to use thermosetting resin, ultraviolet curing resin, electronic wire curing resin, and heat curing resin, and more preferably to use ultraviolet curing resin, electronic wire curing resin, etc. It is more preferable to use ultraviolet curable acrylic resin or electron beam curable acrylic resin. As long as these resins do not impair the effect of the present invention, they may be used alone or in combination of plural numbers. In addition, the protective layer can be formed by coating or lamination of a laminated film.

The method of forming the design layer is not particularly limited as long as it does not impair the effects of the present invention. For example, coating, printing, metal vapor deposition, etc. can be used. Examples of resins used in the design layer include polyester resins, polyolefin resins, acrylic resins, urethane resins, fluorine resins, polyvinyl acetate resins, and vinyl chloride-vinyl acetate. Copolymers and ethylene-vinyl acetate copolymers, etc. In addition, as long as these resins do not impair the effects of the present invention, they may be used alone or in combination of plural.

The coloring agent in the design layer is not particularly limited as long as it does not impair the effects of the present invention. It can be appropriately selected from well-known dyes, inorganic pigments, and organic pigments in consideration of dispersibility in the resin used in the design layer. When the design layer is formed by coating or printing, from the viewpoint of color retention or designability of the product member, the thickness is preferably 1 μm or more and 100 μm or less, more preferably 2 μm or more and 50 μm or less, and still more preferably 5 μm or more and 40 μm or less .

In addition, 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, etc. 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 the formability of the design layer, indium or tin is preferred, and indium is more preferred.

When the design layer is formed by metal vapor deposition, from the viewpoint of both the formability and designability of the design layer, the thickness is preferably 0.001 μm or more and 100 μm or less, more preferably 0.01 μm or more and 50 μm or less, and still more preferably 0.02 μm or more and 30 μm or less.

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, and heat-sensitive resins or pressure-sensitive resins can be used. As heat-sensitive resins, for example, polyester resins, polyolefin resins, acrylic resins, polyamide resins, and polyurethane resins are preferably used. As pressure-sensitive resins, for example, acrylic resins, polyphenylene ether-polystyrene resins, polycarbonate resins, styrene copolymer resins, polystyrene resins, polyamide resins, Chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin, polyurethane resin, polyvinyl ether resin and polyvinyl acetate resin Wait. In addition, as long as the effects of the present invention are not impaired, these systems may be used alone or in combination with plurals.

The formation method of the subsequent layer is not particularly limited as long as it does not impair the effect of the present invention. For example, coating methods such as roll coating, gravure coating, and cut-off wheel coating; and gravure printing and screen printing methods can be used. And other printing methods.

The molding member decorated with 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. Examples include polypropylene, acrylic, polystyrene, and polyacrylonitrile. -Styrene and polyacrylonitrile-butadiene-styrene and other resins as main components; or aluminum, magnesium, iron, titanium, copper, zinc and other metals as the main components.

(Manufacturing method of laminated film and molded transfer foil) Next, regarding the manufacturing method of the laminated film of the present invention, two three-layer constitutions of B layer/A layer/B layer are given as an example, and the composition of the B layers on both sides is the same as an example. However, the present invention The manufacturing method of the laminated film is not limited by this.

When the molten resin composition used to obtain the layer A of the laminated film, that is, when the total components are regarded as 100% by mass, when the molten resin composition contains more than 50% by mass of polypropylene and polyethylene resins in total, when obtaining a molten resin composition, It is preferable to use a melt-kneading method in which each component is melt-kneaded. The system of the melt-kneading method is not particularly limited, and well-known mixers such as a kneader, a roll mill, a Banbury mixer, and a single-shaft or twin-shaft extruder can be used. Among them, from the viewpoint of productivity, it is preferable to use a single-screw extruder. In addition, the method for obtaining the molten resin composition for obtaining the layer B of the laminated film, that is, the molten resin composition whose main component is a cyclic olefin resin and contains a thermoplastic elastomer, is also the same. At this time, the temperature of the raw material supply part or later can be appropriately set in consideration of the melting point of the resin and the like. For example, in any extruder, it is preferable to set the temperature to 200°C or more and 300°C or less.

Next, use a filtering device equipped with a disc filter etc. to remove foreign matter etc. from each molten resin composition obtained by melting and kneading, and use a feed head to layer-melt so as to become B-layer/A-layer/B-layer The resin composition is ejected from the T-shaped mold in the form of a sheet. At this time, by adjusting the size of the T-shaped lip gap, the thickness of the laminated film can be adjusted. Furthermore, by cooling and solidifying the thus obtained molten sheet on a casting roll whose temperature is controlled to be above 0°C and below 100°C, the laminated film of the present invention can be obtained, and it can also be wound into a roll. , Become a film roll.

In addition, from the viewpoint of easy adjustment of the surface roughness (SRa) of the laminated film, the surface roughness of the casting roll can be adjusted appropriately. In the stage of cooling and solidifying the molten sheet on the casting roll, it is also preferably Clamping is carried out with a rubber forming roller. At this time, by increasing the SRa of the casting roll or the rubber forming roll, the SRa of the laminated film to be transferred can also be increased.

The laminated film obtained in this way is excellent in grade or productivity, dimensional stability in processing steps, and moldability. Therefore, it is suitable for molding, and is preferably suitable as a film for molding transfer foil. Hereinafter, the manufacturing method of the molded transfer foil and an example in which the design layer is an acrylic/urethane-based black ink layer will be specifically described, but the molded transfer foil of the present invention is not limited thereto.

First, the film is rolled out from the film roll of the laminated film obtained by the previous method, and an acrylic/urethane-based black ink is coated on the surface of one side using an applicator to form a design layer. Furthermore, on the surface of the design layer, an adhesive is applied using an applicator and dried to form an adhesive layer. Moreover, as long as the effect of the present invention is not impaired, the adhesive system can be suitably selected from well-known ones, and specific examples include 892L manufactured by Nippon Chemical Industry Co., Ltd. In addition to excellent moldability, the molded transfer foil obtained in this manner also has excellent mold release properties from the design layer after the molding step. [Example]

Examples are shown below to explain the present invention more specifically, but the present invention is not limited by them at all.

[Measurement and evaluation method] The measurement or evaluation of each item is performed under the conditions shown below.

(1) Film thickness and layer thickness of each layer The thickness of the film (μm) is determined by measuring the thickness of any place (5 places) of the film sample using a dial gauge, and calculating the average value of the obtained values. The thickness (μm) of each layer of the laminated film was taken using a metal microscope Leica DMLM manufactured by Leica Microsystems Co., Ltd., and a cross-sectional photograph of the laminated film was taken at a magnification of 100 times, and the thickness of each layer was measured at any 5 points in the obtained photograph, and the result was calculated The average value of the value is calculated.

(2) Storage elastic modulus A sample of 60 mm (length direction)×5 mm (width direction) was arbitrarily cut out from the laminated film to obtain a measurement sample. Next, the obtained measurement sample was measured with a dynamic viscoelasticity measuring device (DVE-V4 FT Rheospectra manufactured by RHEOLOGY) under the following measurement conditions to obtain the storage elasticity in the longitudinal direction at 75°C and 120°C Modulus (MPa) (JIS K 7244-4: 2007). The storage elastic modulus (MPa) in the width direction at 75°C and 120°C was also measured and calculated in the same manner.

<Measurement conditions> Frequency: 10Hz Test length: 20mm Displacement amplitude: 10μm Measuring temperature range: 25℃～160℃ Heating rate: 5°C/min.

(3) Surface free energy For the laminated film after 24 hours of temperature and humidity adjustment at a room temperature of 23°C and a relative humidity of 65%, use the Kyowa interface with 4 types of measurement liquids of water, ethylene glycol, formazan and diiodomethane Chemical (strand) contact angle meter CA-D type, calculate the static contact angle to the surface. In addition, since the outermost layer of the laminated film in each of the examples and comparative examples is a layer of the same composition, the surface free energy system is expected to have almost the same value on both sides, so the measurement is only on the side where the laminated film is formed with the design layer, etc. The face is carried out. Next, J. Panzer: J. Colloid Interface Sci., 44, 142 (1973). The dispersion terms, polarity terms, and hydrogen bonding terms of the surface free energy of each liquid described in J. Panzer: J. Colloid Interface Sci., 44, 142 (1973). were introduced to Kitazaki Ningaki and Hata Toshio: Japan Then, the "Hat and Kitazaki's Expansion Fox Formula" described in 8, (3) 131 (1972). of the Association Paper, was obtained by solving the simultaneous equations.

(4) Thermal shrinkage rate at 80℃ (%) A rectangular sample of 250 mm (measurement direction)×10 mm was randomly cut out from the laminated film, and a 200 mm length parallel to the measurement direction was marked at the center as a measurement sample. A weight of 3 g was applied to this measurement sample, and it was heat-treated in a hot-air circulating oven at 80°C for 5 minutes, and the shrinkage rate in the measurement direction was calculated according to the following formula. Next, the measurement direction is rotated 5° to the right, the same measurement is performed, and the same measurement is repeated until the measurement direction is rotated from the initial measurement direction to the direction of 175° to the right. The direction in which the obtained measured value becomes the largest is set as the X1 direction, the direction orthogonal to the X1 direction in the film plane is set as the Y1 direction, and the measured values in the X1 and Y1 directions are regarded as the heat at 80°C in each direction. Shrinkage. Thermal shrinkage (%)={1-(length of marking line after heat treatment)/(length of marking line before heat treatment)}×100.

(5) Young's modulus A rectangular sample of 100mm (measurement direction)×10mm was randomly cut out of the laminated film, and a 50mm length parallel to the measurement direction was marked at the center as a measurement sample. Use a tensile tester ("TENSILON" (registered trademark) UCT-100 manufactured by RIENTEC) on the obtained measurement sample at a temperature of 23°C and a relative humidity of 65% to measure Young’s at a tensile speed of 200mm/min. Modulus (MPa) (JIS K 7161-1: 2014). Next, the measurement direction is rotated 5° to the right, the same measurement is performed, and the same measurement is repeated until the measurement direction is rotated from the initial measurement direction to the direction of 175° to the right. The direction in which the obtained measured value becomes the largest is defined as the X2 direction, the direction orthogonal to the X2 direction in the film plane is defined as the Y2 direction, and the measured values in the X2 direction and the Y2 direction are regarded as the Young's modulus in each direction.

(6) Cutability of laminated film The so-called cutability of the laminated film is the degree of occurrence of defects at the end of the film or defects such as bending or fracture during the processing step. In other words, it is an index for evaluating toughness. The method of measuring the cutability of the laminated film will be described with reference to Fig. 1. Using a twin-shaft cutting machine with a single blade (FAS-10) made of FEATHER safety razor (strand), the length of the length direction 1 is 200m as a laminated film, under the conditions of a tension of 15kg/m and a speed of 30m/min, It is cut parallel to the length direction 1 and perpendicular to the width direction 2 by aerial cutting. From the direction perpendicular to the film surface, visually observe the cut end 3 in the width direction to confirm whether there are irregularities. If there are irregularities, measure the period 4 and width in the longitudinal direction with a metal ruler (JIS1 ruler) The amplitude of the direction is 5. The cutability of the film was evaluated based on the following criteria, and B or higher was regarded as a pass.

A: No bumps or bumps with a period of less than 0.5mm and amplitude of less than 5mm are seen B: The irregularities with a period of 0.5mm or more and an amplitude of less than 5mm are seen C: The film was broken during cutting, or irregularities with an amplitude of 5 mm or more were seen.

(7) Adhesion between layer A and layer B A rectangular sample of 15 mm×110 mm was randomly cut out from the laminated film and used as a test piece. Next, with the MIT bending tester (MID-D manufactured by Toyo Seiki Seisakusho Co., Ltd.), the rotation speed is 175 cpm, the measured load: 25 N (2.6 kgf), and the bending angle: 135°, which is in line with the short side direction. The test pieces that were repeatedly bent 10 times in parallel were made into 10 evaluation samples, and the evaluation was performed using the following criteria. In addition, the adhesion between the A layer and the B layer is considered to be B or higher as a pass.

A: There is no interlayer peeling even at the bend B: At the end of the bend, more than one sample is seen to be peeled off, but there is no sample where the peeling at both ends of the bend is connected to each other. C: One or more samples in which the peeling points at both ends of the bend are connected to each other are seen.

(8) Surface orientation coefficient Randomly cut out a 50mm (length direction) x 50mm (width direction) rectangular sample from the laminated film and use it as a test piece, using the sodium D line (wavelength 589nm) as the light source, and using the Abbe refractometer NAR-4T ( (Made by ATAGO Co., Ltd.) to measure the refractive index in the longitudinal direction (nMD) and the refractive index in the width direction (nTD) in the B layer of any one of the laminated films. Next, the layer B was cut using a microtome (manufactured by LEICA), and the refractive index in the longitudinal direction (nMD) and the refractive index in the width direction (nTD) of the layer A in the layer A were measured by the same method as that of the layer B. Furthermore, a microtome was used to cut the test piece in the thickness direction, the thickness direction refractive index (nZD) of each layer of the laminated film was measured, and the surface alignment coefficient (fn) was calculated from the following formula.

fn=(nMD+nTD)/2-nZD.

(9) Processability when the design layer is formed Cut out a 100mm (length direction) x 100mm (width direction) square laminated film from any position of the film roll. Use an applicator to apply carbon dispersion in acrylic resin (6500B manufactured by Toyo Chemical Co., Ltd.) The black ink obtained from black was dried at 80°C for 5 minutes to form a design layer with a coating film thickness of 30 μm, which was used as a measurement sample. For the obtained measurement samples, the dimensional changes in the width direction and the length direction of the film were observed, and the workability was evaluated using the following criteria. At this time, the design layer was formed on the side of the mirror-like rubber shaping roller during film formation, and the dimensional change was calculated by measuring the change in the width and length of the film before and after drying using a vernier caliper. In addition, the workability at the time of forming the design layer is regarded as passing C or higher.

A: The size change in both the width direction and the length direction is less than 1mm B: There is a dimensional change of 1mm or more and less than 5mm in at least one of the width direction and the length direction, and there is no dimensional change of 5mm or more in any of the width direction and the length direction C: There is a dimensional change of 5 mm or more and less than 10 mm in at least one of the width direction and the length direction, and there is no dimensional change of 10 mm or more in any of the width direction and the length direction D: There is a dimensional change of 10 mm or more in at least one of the width direction and the length direction.

(10) Moldability of the molded transfer foil On one side of the laminated film rolled out from the film roll, the design layer was formed by the method described in (9), and a 200mm×200mm square shape was cut out as a sample. On the surface of the design layer of the obtained sample, an adhesive (892L manufactured by Nippon Chemical Co., Ltd.) was applied using an applicator, and then dried at 80°C for 10 minutes to form an adhesive layer with a coating film thickness of 20 μm, and a molded transfer foil sample was obtained. The molded transfer foil sample thus obtained was heated to a temperature of 120°C using a three-dimensional vacuum heating molding machine (TOM molding machine/NGF-0406-T) manufactured by Fushi Vacuum Co., Ltd., and then heated to a temperature of 50°C. ℃ polypropylene resin mold (column with bottom diameter 150mm), vacuum and air pressure molding (compressed air: 0.2MPa), to obtain a molded body with laminated film/design layer/adhesive layer/polypropylene resin mold in order . For the obtained molded body, from the state (deep drawing ratio: molding height/bottom diameter) after being molded along the polypropylene resin mold, the moldability of the molded transfer foil was evaluated using the following criteria. In addition, the moldability of the molded transfer foil is considered to be C or higher as a pass.

A: It can be finished with a deep drawing ratio of 1.0 or more B: Deep drawing ratio of 0.8 or more and less than 1.0 can be completed, but it cannot be completed with a deep drawing ratio of 1.0 or more C: Molding can be completed with a deep draw ratio of 0.7 or more and less than 0.8, but cannot be completed with a deep draw ratio of 0.8 or more D: Molding cannot be completed with a deep draw ratio of 0.7 or more.

(11) Releasability of film From the molded body obtained by the method (10), only the laminated film was forcibly peeled off, and the mold release properties of the film were evaluated using the following criteria. In addition, the releasability of the film is regarded as passing B or higher.

A: It can be peeled off without resistance B: Resistance is felt during peeling, but the design layer does not transfer to the laminated film side C: The design layer is peeled off and transferred to the laminated film side.

(12) Glass transition temperature of layer B From the laminated film rolled out of the film roll, only 5 mg of layer B was cut out as a sample. A differential scanning calorimeter (RDC220 manufactured by SEIKO Electronics Co., Ltd., in accordance with JIS K7121-1987, JIS K7122-1987) was used. When the temperature is increased from 25°C to 300°C under the condition of a temperature increase rate of 20°C/min, the specific heat change based on the transition from the glass state to the rubber state is measured. Regarding the obtained specific heat change, the midpoint of the point where a straight line extending from each baseline at an intermediate distance in the direction of the vertical axis (axis showing heat flow) intersects with the curve of the stepped portion of the glass transition is determined as the glass transition temperature . In addition, when there are multiple glass transition temperatures, the glass transition temperature on the high-temperature side is regarded as the glass transition temperature of the B layer.

(13) The surface appearance of the product component The surface appearance of the product component refers to the surface appearance of the product component after the laminate film is only peeled off by transferring the design layer and the subsequent layer to the product component by forming the transfer foil. Because the surface appearance of the product component is affected by the grade of the laminated film, it becomes the index of the evaluation grade. On the surface of the laminated film rolled from the film roll, use a die coater to coat acrylic/urethane-based black ink, and dry it at 80°C for 10 minutes to form a design layer with a coating thickness of 30μm. Furthermore, on the design layer, 892L manufactured by Nippon Chemical Industry Co., Ltd. was coated with a coater, dried at 80°C for 10 minutes to form an adhesive layer with a coating film thickness of 20 μm, and rewinded to produce a molded transfer foil roll. From the obtained forming transfer foil roll, the forming transfer foil is cut out at an arbitrary position with a size of 200mm (length direction)×300mm (width direction). Then, in the order of build-up film/design layer/adhesive layer/molding member (flat-shaped polypropylene resin mold), the transfer foil and the molding member are overlap-molded, and vacuum/air pressure molding is performed. The resulting molded body is irradiated Ultraviolet rays are irradiated so that the intensity becomes 2,000mJ/cm ^{2 to harden the adhesive layer.} Then, only the laminated film was peeled off from the molded body, and the surface of the obtained product member was observed at a magnification of 5 times using a scanning white interference microscope (VS-1000 manufactured by Hitachi High-Technologies Co., Ltd.), and the surface appearance was evaluated using the following criteria Fluctuation: the maximum point height of the product component-the minimum point height). In addition, the surface appearance of the product component is considered to be B or higher as acceptable.

A: The fluctuation is less than 0.01mm B: The fluctuation is 0.01mm or more and less than 0.1mm C: The undulation is 0.1 mm or more.

[Resin used in the manufacture of laminated film] As a resin for obtaining the laminated film of each Example and each comparative example, the following were used.

(Polypropylene resin) Random polypropylene resin ("Prime Polypro" (registered trademark) Y-2045GP made by PRIME POLYMER) (Polyethylene resin) Linear low-density polyethylene ("Evolue" (registered trademark) SP2540 made by PRIME POLYMER) (Cyclic olefin resin A) Copolymer of norbornene and ethylene ("TOPAS" (registered trademark) 8007F-04 made by POLYPLASTICS) (Cyclic olefin resin B) Copolymer of norbornene and ethylene ("TOPAS" (registered trademark) 6013F-04 made by POLYPLASTICS) (Thermoplastic elastomer) Ethylene-α olefin-based elastomer ("Esprene" (registered trademark) SPO manufactured by Sumitomo Chemical Co., Ltd.).

(Example 1) Make the raw materials for layer A and layer B have the composition shown in Table 1, and each are supplied to a separate uniaxial extruder (L/D=30), the temperature of the supply part is 230°C, and the temperature thereafter is 240°C, Perform melt kneading. Next, the foreign matter is removed from each molten thermoplastic resin composition by passing through a filtering device equipped with a disc filter with a filtering precision of 30 μm, and the thickness ratio becomes 15:70 in the feed head provided on the upper part of the mold. : After layering B-layer raw materials/A-layer raw materials/B-layer raw materials in the way of 15, from the T-die (lip gap: 0.4mm), the temperature is controlled at 40 ℃ matte metal forming roll (surface roughness Ra: 0.9μm) spit out flakes. At that time, a mirror-like rubber shaped roller whose temperature was controlled at 30°C was clamped (surface roughness Ra: 0.05μm, clamping pressure: 0.2MPa) to obtain a 100μm-thick laminated film, which was wound into a roll shape. Then, the molded transfer foil was manufactured in accordance with the method described in "(9) Processability at the time of design layer formation" and "(10) Moldability of molded transfer foil". Evaluation of each evaluation item was performed for the obtained laminated film and molded transfer foil. Table 1 shows the evaluation results.

(Examples 2-7, Comparative Examples 1-3) Except that the composition and lamination ratio of each layer were as described in Table 1, a lamination film and a molded transfer foil were produced in the same manner as in Example 1, and evaluated in the same manner. Table 1 shows the evaluation results.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Composition of layer A Polypropylene resin (mass%) 50 100 - 70 100 100 100 20 100 100 Polyethylene resin (mass%) 50 - 100 - - - - - - - Cyclic olefin resin (mass%) A - - - 25 - - - 70 - - B - - - 5 - - - 10 - - Composition of layer B Polypropylene resin (mass%) - - - - - 20 - - - 80 Polyethylene resin (mass%) 3 3 3 3 3 3 twenty one 3 20 - Cyclic olefin resin (mass%) A 70 70 70 70 70 50 70 70 70 - B 7 7 7 7 7 7 7 7 10 - Thermoplastic elastomer (mass%) 20 20 20 20 20 20 2 20 - 20 Amount of cyclic olefin resin in laminated film (mass%) 23.1 23.1 23.1 44.1 15.4 17.1 23.1 72.1 twenty four 0 Laminated structure (thickness: μm) B/A/B (15/70/15) B/A/B (15/70/15) B/A/B (15/70/15) B/A/B (15/70/15) B/A/B (10/80/10) B/A/B (15/70/15) B/A/B (15/70/15) B/A/B (15/70/15) B/A/B (15/70/15) B/A/B (15/70/15) Glass transition temperature of layer B (℃) 85 85 85 85 85 70 85 85 90 10 Storage elastic modulus at 75℃ (MPa) 270 500 150 950 400 350 500 2000 500 300 Storage elastic modulus at 120℃ (MPa) 15 20 10 5 45 50 twenty three 3 25 120 Surface free energy (mN/m) 36 36 36 36 36 30 36 36 42 20 Thermal shrinkage rate at 80℃ (%) X1 0.3 0.25 0.38 0.2 0.45 0.5 0.25 0.2 0.25 0.8 Y1 0.1 -0.05 0.2 -0.05 0.3 0.4 -0.05 -0.05 -0.05 0.6 Young's modulus (MPa) X2 250 400 150 500 300 270 400 700 400 250 Y2 150 350 75 450 250 250 350 650 350 200 Surface alignment coefficient of A layer 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Surface orientation coefficient of layer B 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Film thickness (μm) 100 100 100 100 100 100 100 100 100 100 Design layer thickness (μm) 30 30 30 30 30 30 30 30 30 30 Thickness of the next layer (μm) 20 20 20 20 20 20 20 20 20 20 Cutability of film A A A B A A A C A A Adhesion between layer A and layer B A A A A A A B A C A Processability when the design layer is formed B A B A B B A A A C Composition of transfer foil for molding Film/design layer/adhesive layer Moldability of transfer foil for molding A A A A C C A A B D Releasability of transfer foil for molding A A A A A B A A A C Surface appearance of product components A A A A A B A A A C

The component amount (mass%) of each layer is calculated by taking all the components constituting each layer as 100% by mass, and the amount of cyclic olefin resin in the laminated film (mass%) is calculated by taking all the components constituting the laminated film as 100% by mass And figure it out. Comparative Examples 1 to 3 do not have the requirements of the A layer or the B layer. Regarding these comparative examples, the two outer layers are described as the B layer, and the intermediate layer is described as the A layer. [Possibility of Industrial Utilization]

According to the present invention, it is possible to provide: a laminated film excellent in grade or productivity, dimensional stability in processing steps, and moldability; and a molded transfer foil using the laminated film. By using the laminated film and the molded transfer foil of the present invention, high design can be imparted to the product member (molded member after molding and decoration) in various molding methods such as vacuum molding, air pressure molding, and pressure molding. Therefore, the laminated film and the molded transfer foil of the present invention can be applied to, for example, decoration of molded parts such as building materials, automobile parts or mobile phones, electrical products, and game machine parts.

1: length direction 2: width direction 3: Width end 4: Period in the length direction 5: Amplitude in the width direction

Fig. 1 is a diagram showing the period in the length direction and the amplitude in the width direction in the evaluation of the cutability of a laminated film (a top view when viewed from a direction perpendicular to the film surface).

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Claims (13)

A laminated film characterized in that a layer containing a total of more than 50% by mass and 100% by mass or less of polypropylene and polyethylene resins is regarded as layer A, and the main component is cyclic olefin resin and contains thermoplastic When the elastomer layer is regarded as the B layer, it has the A layer and the B layer, and the B layer is located on the outermost surface on both sides. Such as the laminated film of claim 1, in which all components constituting the laminated film are regarded as 100% by mass, the cyclic olefin resin is contained in an amount of 5% by mass or more and 40% by mass or less. For example, the laminated film of claim 1 or 2 has a storage elastic modulus at 75°C of 101 MPa or more and less than 1,000 MPa, and a storage elastic modulus at 120°C of 100 MPa or less. According to any one of claims 1 to 3, the surface free energy of the outermost surface of at least one of them is 35 mN/m or more and 45 mN/m or less. The laminated film according to any one of claims 1 to 4, wherein at least one of the B layers contains 1% by mass or more and 40% by mass or less of thermoplastic elastomer. The laminated film according to any one of claims 1 to 5, wherein the thermoplastic elastomer system is an olefin-based elastomer. Such as the laminated film of any one of claims 1 to 6, in which the direction with the largest heat shrinkage rate at 80°C is regarded as the X1 direction, and the direction orthogonal to the X1 direction in the film plane is regarded as the Y1 direction , The thermal shrinkage rate of X1 direction and Y1 direction at 80℃ are both -0.50% or more and 0.50% or less. The laminated film of any one of claims 1 to 7, wherein the direction in which the Young's modulus at 25°C is the largest is regarded as the X2 direction, and the direction orthogonal to the X2 direction in the film plane is regarded as the Y2 direction When, the Young's modulus in the X2 direction and the Y2 direction at 25°C are both 50 MPa or more and 500 MPa or less. The laminated film according to any one of claims 1 to 8, wherein the laminated film is a non-aligned film. The laminated film according to any one of claims 1 to 9, wherein the laminated film is a film for molding. The laminated film according to claim 10, wherein the forming film is a film for forming transfer foil. A shaped transfer foil, characterized in that the laminated film, design layer and adhesive layer of any one of claims 1 to 11 are arranged in order. The forming transfer foil of claim 12, wherein the protective layer is located between the laminated film and the design layer.

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