TWI580570B - Laminated film - Google Patents

Description

Laminate film

The present invention relates to a laminated film comprising a polypropylene resin and/or a polyethylene resin as a main component on at least one side of an A layer containing a cyclic olefin resin as a main component. The layer is a laminated film excellent in moldability, mold release property, processability, water vapor barrier property, and heat sealability.

Recently, in order to impart scratch resistance, weather resistance, color, pattern, or imparting photosensitive resin or electromagnetic shielding to a circuit member, the method of transferring a functional resin to various members has been expanded to meet such requirements. The development of functional functional resin transfer films has continued to progress.

For example, in the use of building materials, automobile parts, mobile phones, and motor products, the demand for solvent-free coating and plating alternatives has increased due to the increase in environmental awareness, and the use of film decoration methods has been Proposals related to the use of a film of a cyclic olefin resin have been proposed (for example, Patent Documents 1 and 2).

In addition, a large number of electronic components such as mobile phones, video cameras, and notebook computers that are rapidly becoming smaller and higher in performance are widely used in circuit boards such as flexible printed wiring boards (hereinafter referred to as "FPC"). Used to load circuits in complex mechanisms. In such electronic machines, when When the FPC receives electromagnetic waves generated from other parts or machines, the circuit may be damaged or malfunctioned, and there may be a disorder or noise of the image. Therefore, the FPC needs to block electromagnetic waves originating from the outside, that is, The "electromagnetic wave shielding property" and the shielding flexible printed wiring board (hereinafter referred to as shielding FPC) having electromagnetic shielding properties are widely used.

As such a function for transferring a functional resin to a circuit member The film has been proposed to use a biaxially stretched polyester film (for example, refer to Patent Document 3) or a proposal to use a cyclic olefin-based film (see, for example, Patent Documents 4 and 5).

On the other hand, a film or food is placed outside the lithium ion battery. A film for packaging, such as a film for packaging and a packaging film for medical use, which is compatible with water vapor barrier properties, oxygen barrier properties, bending flexibility, heat sealability, solvent resistance, and electrolyte resistance. It is a film, a polypropylene film, a metal foil or a metal vapor-deposited layer, a nylon film, a polyester film, etc., and has various required characteristics. The water vapor barrier property and the like can be mainly imparted by a metal foil or a metal deposition layer. However, when the film is formed into a bag shape and heat-sealed, water vapor can be obtained by a metal foil or a metal deposition layer on the surface of the film. Barrier property, but the heat seal layer at the end of the bag body is not protected by the metal foil or the metal vapor deposition layer, so that there is a problem that water vapor permeates from the end portion. Therefore, the heat seal layer itself also requires water vapor barrier properties.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2012-206299

Patent Document 2 Japanese Patent Laid-Open Publication No. 2013-043396

Patent Document 3 Japanese Patent Laid-Open Publication No. 2002-252458

Patent Document 4 Japanese Patent Laid-Open Publication No. 2006-257399

Patent Document 5 Japanese Patent Laid-Open Publication No. 2009-040982

The film described in Patent Documents 1 and 2 does not have a layer containing a polypropylene resin and/or a polyethylene resin as a main component in the surface layer, and the mold release property may be insufficient depending on the composition of the functional resin layer.

Although the film described in Patent Document 3 has good processing suitability, the moldability is insufficient for a deep-drawn molded member (that is, a molded member having a large molding magnification) or a circuit member having a high step. In the film described in Patent Document 4, the layer constituting the surface of the film contains a cyclic olefin resin as a main component, and the mold release property is insufficient depending on the type of the functional resin layer. Further, in the case of using a resin having a high glass transition temperature, a transfer of a resin member having a low heat-resistant temperature and a sufficiently insufficient molding temperature, or a circuit member having a high step, the moldability may be insufficient. In the film described in Patent Document 5, the layer constituting the surface of the film also contains a cyclic olefin resin as a main component, and the mold release property is also insufficient depending on the type of the functional resin layer.

Therefore, an object of the present invention is to solve the above problems. In other words, when the film is used as a film for transferring a functional resin layer, it is a laminate film having good moldability, mold release property, and processability, and water vapor barrier properties and heat sealability when used as a film for various packagings. Good laminated film.

The present invention for solving the above problems has the following constitution:

(1) A laminated film having a B layer mainly composed of a polypropylene resin and/or a polyethylene resin as a main component of the A layer containing a cyclic olefin resin as a main component.

(2) The laminated film according to (1), which has a B layer on both sides of the layer A.

(3) The laminated film according to (1) or (2), wherein the glass transition temperature of the layer A is 130 ° C or more and 150 ° C or less.

(4) The laminated film according to any one of (1) to (3), wherein the A layer contains 15% by mass or more and 40% by mass or less of ethylene based on 100% by mass of the total of the total components of the A layer. Copolymerized resin.

(5) The laminated film according to any one of (1) to (4), wherein the storage elastic modulus at 120 ° C is 101 MPa or more and 3,000 MPa or less, and the storage elastic modulus at 170 ° C is 100 MPa or less.

(6) The laminated film according to any one of (1) to (5) wherein the surface layer free energy of the layer B is 25 mN/m or more and 35 mN/m or less.

(7) The laminated film according to any one of (1) to (6) wherein the B layer is mainly composed of a polypropylene resin and further contains a petroleum resin.

(8) The laminated film according to any one of (1) to (6) wherein the B layer is mainly composed of a polyethylene resin which is a linear low density polyethylene or a high density poly Ethylene.

(9) The laminated film according to any one of (1) to (8), wherein the surface roughness SRa of both surfaces is 50 nm or more and 3,000 nm or less.

(10) The laminated film according to any one of (1) to (9), which has a haze of 65% or more and 90% or less.

(11) The laminated film according to any one of (1) to (10), wherein the color tone L value is 75 or more and 100 or less.

(12) The laminated film according to any one of (1) to (11), wherein a laminate ratio (total thickness (μm) of layer B/thickness (μm) of layer A) is 0.1 or more and 0.15 or less, and total thickness of film It is 40 μm or more and 300 μm or less.

(13) The laminated film according to any one of (1) to (11), wherein a laminate ratio (total thickness (μm) of layer B/thickness (μm) of layer A) is 0.25 or more and 2 or less, total thickness of film It is 40 μm or more and 300 μm or less.

(14) A functional resin layer transfer film having the laminated film according to any one of (1) to (13) and a functional resin layer.

(15) A film for packaging having the laminated film according to any one of (1) to (13).

In the present invention, (particularly, a layer B having a polypropylene resin and/or a polyethylene resin as a main component in at least one side of the layer A having a cyclic olefin resin as a main component) is formed. It is excellent in mold release property, processing suitability, water vapor barrier property, and heat sealability, and can be applied to decorative films for building materials, automobile parts, or molded parts of mobile phones, motor products, game machine parts, etc., or electromagnetic waves like circuit components. Masking layer transfer film or various packaging films.

[Formation of the Invention]

In the present invention, the B layer having a polypropylene resin and/or a polyethylene resin as a main component is provided on at least one side of the A layer containing the cyclic olefin resin as a main component. Hereinafter, the laminated film of the present invention will be specifically described.

(A layer)

In the laminated film of the present invention, it is important to have the A layer from the viewpoint of workability and moldability. Here, the layer A refers to a layer mainly composed of a cyclic olefin resin. In addition, the term "main component" as used herein means a cyclic olefin-based resin containing more than 50% by mass and not more than 100% by mass when the total amount of the total components of the layer A is 100% by mass. When the total amount of the total components of the layer A is 100% by mass, the content of the cyclic olefin resin contained in the layer A is preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass. The form of % or less is more preferable, and it is especially preferable if it is 90% by mass or more and 100% by mass or less. Further, the layer A is mainly composed of a cyclic olefin resin, but the layer A may be composed of only a cyclic olefin resin, and may contain other olefin resins or a resin other than the olefin resin. In addition, when the total amount of the total components of the layer A is 100% by mass, the ethylene content is 15% by mass or more and 40% by mass or less, based on the viewpoint of maintaining the dimensional stability during the processing step and suppressing the fine cracks during the molding. The form of the copolymerized resin is preferably a form of a cyclic olefin-based resin contained in the A layer of more than 60% by mass and not more than 85% by mass based on the total of the total components of the layer A.

By making the main component of the layer A a cyclic olefin resin, the processability and moldability of the laminated film can be improved.

Here, the "cyclic olefin resin" means a resin having an alicyclic structure in a main chain of a polymer obtained by polymerizing a cyclic olefin as a monomer.

In addition, the cyclic olefin resin of the present invention is a resin obtained by polymerizing a cyclic olefin monomer or the like, and means that it is derived from a cyclic olefin monomer in 100% by mass of the polymer of the cyclic olefin resin. The polymer in a form in which the total amount of the components exceeds 50% by mass and is 100% by mass or less.

Examples of the cyclic olefin monomer include monocyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclopentadiene, and 1,3-cyclohexadiene; bicyclo [2, 2, 1]hept-2-ene, 5-methyl-bicyclo[2,2,1]hept-2-ene, 5,5-dimethyl-bicyclo[2,2,1]hept-2-ene, 5 -ethyl-bicyclo[2,2,1]hept-2-ene, 5-butyl-bicyclo[2,2,1]hept-2-ene, 5-ethylene-bicyclo[2,2,1 Hept-2-ene, 5-hexyl-bicyclo[2,2,1]hept-2-ene, 5-octyl-bicyclo[2,2,1]hept-2-ene, 5-octadecyl- Bicyclo[2,2,1]hept-2-ene, 5-methylene-bicyclo[2,2,1]hept-2-ene, 5-vinyl-bicyclo[2,2,1]hept-2 a dicyclic olefin such as a olefin, 5-propenyl-bicyclo[2,2,1]hept-2-ene; a tricyclo[4,3,0,1 ^2.5 ]indole-3,7-diene, tricyclic ring [4,3,0,1 ^2.5 ]癸-3-ene, tricyclo[4,3,0,1 ^2.5 ]undec-3,7-diene, tricyclo[4,3,0,1 ^2.5 11-carbon-3,8-diene, tricyclo[4,3,0,1 ^2.5 ]undec-3-ene, 5-cyclopentyl-bicyclo[2,2,1]heptan-2- Alkene, 5-cyclohexyl-bicyclo[2,2,1]hept-2-ene, 5-cyclohexenylbicyclo[2,2,1]hept-2-ene, 5-phenyl-bicyclo[2, 2,1] a tricyclic olefin such as hept-2-ene; tetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodeca-3-ene, 8-methyltetracyclo[4,4,0 ,1 ^2.5, 1 ^7.10] dodeca-3-ene, 8-ethyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodeca-3-ene, 8-Methylene-tetracyclo [4, 4,0,1 ^2.5 ,1 ^7.10 ]dodec-3-ene, 8-ethylenetetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodec-3-ene, 8-vinyl Tetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodec-3-ene, 8-propenyl-tetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodeca-3-ene a tetracyclic olefin; and 8-cyclopentyl-tetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodec-3-ene, 8-cyclohexyl-tetracyclo[4,4,0, 1 ^2.5 ,1 ^7.10 ]dodec-3-ene, 8-cyclohexenyl-tetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodec-3-ene, 8-phenyl-ring Amyl-tetracyclo[4,4,0,1 ^2.5 ,1 ^7.10 ]dodec-3-ene, tetracyclo[7,4,1 ^3.6 ,0 ^1.9 ,0 ^2.7 ]tetradec-4,9, 11,13-tetraene, tetracyclo[8,4,1 ^4.7 ,0 ^1.10 ,0 ^3.8 ] fifteen carbon-5,10,12,14-tetraene, pentacyclo[6,6,1 ^3.6 ,0 ^2.7 , 0 ^9.14 ]-4-hexadecene, pentacyclo[6,5,1,1 ^3.6 ,0 ^2.7 ,0 ^9.13 ]-4-pentadecene, pentacyclo[7,4,0,0 ^2.7 ,1 ^3.6 ,1 ^10.13 ]-4-pentadecenyl, hepta[8,7,0,1 ^2.9 ,1 ^4.7 ,1 ^11.17 ,0 ^3.8 ,0 ^12.16 ]-5-hexadecene, hepta[8,7,0 1 ^2.9 0 ^3.8 1 ^4.7 0 ^12.17, 1 ^13.16] -14- eicosene, cyclopentadiene Tetramer like polycyclic olefins. These cyclic olefin monomers may be used alone or in combination of two or more.

Among the above, among the above, from the viewpoint of productivity and surface properties, bicyclo[2,2,1]hept-2-ene (hereinafter referred to as norbornene) and tricyclo[4,3 are preferably used. , 0,12.5] anthracene-3-ene and other carbon tricyclic olefins (hereinafter referred to as tricyclodecene), tetracyclo[4,4,0,12.5,17.10]dodec-3-ene, etc. A tetracyclic olefin having a carbon number of 12 (hereinafter referred to as tetracyclododecene), cyclopentadiene or 1,3-cyclohexadiene.

In the polymer of the cyclic olefin resin of 100% by mass, the cyclic olefin resin is derived from the total of the components of the cyclic olefin monomer. When it exceeds 50% by mass and is 100% by mass or less, it may be a resin obtained by polymerizing only the above cyclic olefin monomer (hereinafter referred to as COP), or copolymerizing the above cyclic olefin monomer and a chain olefin monomer. Any of the resins (hereinafter referred to as COC).

As a manufacturing method of COP, a cyclic olefin single A known method such as addition polymerization or ring-opening polymerization of a body, for example, a method in which a norbornene, a tricyclodecene, a tetracyclic terpene, and a derivative thereof are subjected to ring-opening metathesis polymerization and hydrogenation, and a method of hydrogenating A method in which an alkene or a derivative thereof is subjected to addition polymerization, a method in which cyclopentadiene or cyclohexadiene is subjected to 1,2-, 1,4-addition polymerization, followed by hydrogenation. Among these, from the viewpoint of productivity and moldability, a resin obtained by subjecting norbornene, tricyclodecene, tetracyclononene, and a derivative thereof to ring-opening metathesis polymerization and hydrogenating is preferably used.

In the case of COC, as a preferred chain olefin monomer, Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene , 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-B 1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene , 1-hexene and the like. Among these, ethylene is particularly preferred from the viewpoint of productivity and cost. Further, as 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 a cyclic olefin monomer and a chain olefin monomer may be mentioned, and for example, A method of addition polymerization of norbornene and its derivatives with ethylene. Among them, from the viewpoint of productivity and moldability, a copolymer of norbornene and ethylene is preferred.

The layer A of the laminated film of the present invention can contain COC, When the total amount of the total components of the layer A is 100% by mass, the total amount of COC and COP may be more than 50% by mass and 100% by mass or less, and both COC and COP may be contained. However, based on the productivity of the raw material sheet, the A layer is preferably composed mainly of COC; and based on the film quality, the A layer is preferably composed mainly of COP. Further, based on the adhesion between the layers of the layer A and the layer B, when the layer B to be described later is mainly composed of a polyethylene resin, the layer A is preferably composed mainly of COC; and the layer of layer B is mainly composed of a polypropylene resin. The layer A is preferably composed mainly of COP.

As mentioned above, the layer A may also contain other olefin-based resins. As the olefin-based resin other than the cyclic olefin-based resin, for example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear medium-density polyethylene, linear low-density polyethylene, and metal aromatics can be used. Density polyethylene, metal aromatic linear low density polyethylene, metal aromatics. Various polypropylene resins such as high-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, propylene-butene copolymer, etc. (for ethylene-propylene copolymer, ethylene) A propylene-butene copolymer or a propylene-butene copolymer may be a polyolefin resin such as a random copolymer or a block copolymer, or a methylpentene polymer.

In addition, it can also be used to contain ethylene, propylene, 1-butene, a polymer of a chain olefin monomer such as 1-pentene, 4-methyl-1-pentene, 1-hexene or 1-octene; a random copolymer comprising the chain olefin monomer, comprising the chain A block copolymer of an olefin monomer or the like.

Among them, based on the compatibility with the cyclic olefin resin From the viewpoint of the adhesion between the layers and the layer B, it is preferable to use various polyethylene resins and various polypropylene resins as the olefin resin other than the cyclic olefin resin suitable for the A layer.

Here, the "linear" of the various polyethylene-based resins used in the present invention means that the main chain of the polymer produced by the main low-pressure method is linear, as long as it is a radical polymerization under high pressure. The long and short branching structure such as the high-pressure method low-density polyethylene produced may also be in the form of a branch. Further, "low density" means a resin having a density of 0.91 g/cm ³ or more and less than 0.93 g/cm ³ as determined according to JIS K6922-2-2010; "medium density" means according to JIS K6922-2-2010 the obtained density 0.93g / cm ³ or more is less than 0.942g / cm ³ of resin; "high density" refers to the sum determined in accordance with JIS K6922-2-2010 a density of 0.942g / cm ³ or more of the resin. In addition, "metal aromatic low-density polyethylene, metal aromatic linear low-density polyethylene, metal aromatic medium, high-density polyethylene" each refers to low-density polyethylene made of metal aromatic catalyst, linear Low density polyethylene, medium. High-density polyethylene.

Further, in the present invention, "polyethylene resin" means only a package. A homopolymer containing ethylene, or propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene , 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 a copolymer obtained by copolymerizing a chain olefin such as octadecene or 1-eicosene.

In the present invention, the main component is a cyclic olefin resin. The A layer contains a polyethylene resin or a polypropylene resin, which can reduce the shear stress in the extrusion step, can suppress the generation of impurities due to crosslinking, and can further improve the toughness and enhance the interlayer adhesion with the B layer. Sexually better. On the other hand, when the content of the polyethylene resin or the polypropylene resin is increased, the self-retaining property and the workability tend to be lowered.

Based on the viewpoint of quality, resilience and self-retention, The content of the olefin resin and/or the polypropylene resin is preferably from 1 to 40% by mass based on 100% by mass of the total of the total components of the A layer, and more preferably from 1 to 25% by mass. 1 to 10% by mass is particularly good.

Further, among polyethylene resins and polypropylene resins, From the viewpoint of compatibility with the cyclic olefin resin, a polyethylene resin is preferably used for the other olefin resin contained in the layer A, and a high density polymer is preferably used among the polyethylene resin from the viewpoint of compatibility and heat resistance. Ethylene, linear low-density polyethylene, metal aromatic linear low-density polyethylene, metal aromatics. High-density polyethylene, especially in the case of heat resistance, the best use of high-density polyethylene, metal aromatics. High-density polyethylene; especially in the case of emphasizing compatibility, linear low-density polyethylene and metal-aromatic linear polyethylene are preferably used.

Moreover, when the layer A contains a polypropylene resin, From the viewpoint of compatibility of the cyclic olefin resin, an ethylene-propylene copolymer or an ethylene-propylene-butene copolymer is preferably used.

In addition, when layer A contains both polyethylene resin and polypropylene In the case of the olefin resin, the total amount of the polyethylene resin and the polypropylene resin is preferably in the above range, that is, the total composition of the A layer with respect to 100% by mass. The total amount is preferably 1 to 40% by mass, more preferably 1 to 25% by mass, and particularly preferably 1 to 10% by mass.

Furthermore, the "polyethylene resin of the present invention" means In the polymer of the polyethylene resin of 100% by mass, the total amount of the components derived from ethylene is more than 50% by mass and is 100% by mass or less.

Moreover, "the polypropylene resin of the present invention" means 100 In the polymer of the polypropylene resin having a mass%, the total amount of the components derived from propylene is more than 50% by mass and is 100% by mass or less.

Further, in the present invention, it is a mixture of ethylene and propylene. In the copolymer, the copolymerization ratio (content ratio) of the component derived from ethylene in the polymer of 100% by mass is 50% by mass, and the copolymerization ratio (content ratio) of the component derived from propylene is 50% by mass. The system is attributed to a polyethylene resin.

For the layer A of the laminated film of the present invention, based on the improvement The glass transition temperature is preferably 130 ° C or higher, more preferably 130 ° C or more and 180 ° C or less, and more preferably 130, from the viewpoint of dimensional stability in the processing step and the viewpoint of excessive deformation in the press step in suppressing application to a circuit member or the like. Above °C below 150 °C. When the glass transition temperature of the layer A is less than 130° C., in the processing steps such as coating, lamination, printing, and vapor deposition, the dimensional change of the laminated film of the present invention is not sufficiently suppressed, and the planarity of the processed film is insufficient. . In addition, when the glass transition temperature of the layer A exceeds 150 ° C, the moldability of the laminated film of the present invention is insufficient, and the component derived from the chain olefin which constitutes the cyclic olefin resin is reduced, so that it is used as the layer B. The adhesion point between the polypropylene resin and/or the polyethylene resin of the main component is reduced, so that the phase-to-phase adhesion between the A layer and the B layer is insufficient.

In order to have higher dimensional stability and formability, layer A The glass transition temperature is particularly preferably from 130 ° C to 140 ° C. Further, when there is a glass transition temperature of a plurality of A layers, the glass transition temperature on the high temperature side is employed as the glass transition temperature of the A layer.

In order to make the glass transition temperature of layer A reach 130 ° C and above 150 ° C Hereinafter, for example, when a copolymer of norbornene and ethylene is used as the COC, the glass transition temperature can be shifted to a high temperature by continuously increasing the content of the norbornene in the layer A. Furthermore, the glass transition temperature of the layer A can also be adjusted by blending two kinds of COCs having different levels of decane. Further, for example, when a resin obtained by subjecting norbornene, tricyclodecene, tetracyclododecene, and the like to hydrogenation by ring-opening metathesis polymerization is used as the COP, the ring to be polymerized is increased. The molecular weight of the olefin (norbornene, tricyclodecene, tetracyclododecene, and the like) or the increase in the number of rings 俾 form a rigid structure, which allows the glass transition temperature to be transferred to a high temperature. Further, the glass transition temperature of the layer A can also be adjusted by blending two kinds of COPs having different glass transition temperatures.

The layer A of the laminated film of the present invention is based on a cyclic olefin From the viewpoint of the compatibility of the hydrocarbon-based resin, and the dimensional stability in the processing step of the laminated film, and the suppression of the fine crack at the time of molding, it is preferable to contain 15% by mass or more when the total content of the total components of the layer A is 100% by mass. 40% by mass or less of the ethylene-based copolymer resin. When the ethylene-based copolymer resin contained in the layer A is less than 15% by mass, in the deep drawing (that is, molding in which the molding magnification is increased), the laminated film cannot be formed, and micro cracks may occur. When a micro-crack is generated, when the laminated film of the present invention is used as a functional resin layer transfer film, the functional resin layer is also produced. The crack or flatness is deteriorated, and the appearance is poor, or the surface hardness and conductivity are poor. In addition, when the ethylene-based copolymer resin contained in the layer A exceeds 40% by mass, the glass transition temperature of the layer A is lowered, and the dimensional stability in the processing step of the laminated film is insufficient, or the plane after processing of the laminated film Insufficient circumstances.

Here, the "ethylene-based copolymer resin" means the aforementioned aggregation. Among the vinyl resins, various polyethylene resins containing only components derived from ethylene are included. Specifically, it means a resin containing a composition of a component derived from a monomer other than an ethylene monomer in a total amount of components derived from ethylene of 100% by mass or less based on 100% by mass of the polymer.

For the vinyl copolymer resin, based on processing and molding From the viewpoint of the crystallization inhibition under heating and the flexibility at high temperature, and the compatibility with the cyclic olefin resin, it is preferable to contain 10% by mass or more and less than 50% by mass of the polymer derived from 100% by mass of the polymer. The component of the monomer other than the monomer is more preferably contained in an amount of 20% by mass or more and less than 50% by mass. When the component derived from the monomer other than the ethylene monomer is less than 10% by mass, crystallization proceeds during heating at the time of processing or molding, and the moldability may be insufficient. When the content of the monomer other than the monomer of the ethylene monomer is 50% by mass or more, the production cost of the ethylene-based copolymer resin may be increased or the compatibility with the cyclic olefin resin may be insufficient. Further, from the same viewpoint, the ethylene-based copolymer resin preferably contains, in 100 mol% of the polymer, 5 mol% or more and less than 40 mol% of a component derived from a monomer other than the ethylene monomer. In the ethylene-based copolymer resin, a large amount of monomers other than the ethylene monomer are copolymerized, even during processing and molding. Heating and crystallization are not easy to carry out, and the flexibility is high even at a high temperature. Therefore, the twist generated when the cyclic olefin resin is subjected to deep drawing (that is, molding with an increased molding magnification) is partially buffered by the vinyl copolymer resin. It is possible to suppress minute cracks during molding.

Other than the ethylene monomer constituting the vinyl copolymer resin The monomer is preferably chain-like, such as propylene, 1-butene, 1-pentene, 1-hexene or 1-octene, from the viewpoint of compatibility with the cyclic olefin resin which is a main component of the A layer. Olefins.

Specifically, examples of the ethylene-based copolymer resin include An ethylene-propylene copolymer, an ethylene-propylene-butene copolymer, an ethylene-butene copolymer, an ethylene-hexene copolymer, an ethylene-octene copolymer, or the like.

Among these, based on the need to reduce the glass transition temperature of layer A Degree (the glass transition temperature of the layer A is maintained at 130 ° C or more and 150 ° C or less), and the compatibility with the cyclic olefin resin which is a main component of the layer A is good, and the processing suitability of the laminated film can be maintained. The ethylene-based copolymer resin is preferably a resin obtained by copolymerizing ethylene and a chain olefin, and is particularly preferably an ethylene-hexene copolymer or an ethylene-octene copolymer from the viewpoint of suppressing minute cracks during molding.

If the ethylene-based copolymerized resin is a copolymerized ethylene and a chain olefin In the case of the resin which is a hydrocarbon, the ethylene-based component of the 100% by mass of the ethylene-based copolymer resin is used in view of compatibility with the cyclic olefin resin which is a main component of the A layer and suppression of minute cracks. The content is preferably 60% by mass or more and 90% by mass or less, and particularly preferably 70% by mass or more and 80% by mass or less. When the ethylene-derived resin has an ethylene-derived component of less than 60% by mass, it has a cyclic olefin as a main component of the layer A. When the compatibility of the resin is insufficient, when the component derived from ethylene exceeds 90% by mass, the suppression of minute cracks during molding may be insufficient.

When the ethylene-based copolymer resin is a resin obtained by copolymerizing ethylene and a chain olefin, the density of the ethylene-based copolymer resin in the state of the raw material sheet before processing into a film is preferably 0.84 g/cm ³ or more and 0.89 g/ Below cm ³ . Here, the density refers to a value measured in accordance with JIS-K7112 (1999). When the raw material sheet of the ethylene-based copolymerized resin before being processed into a film is a copolymer of ethylene and an α-olefin, when the density is 0.89 g/cm ³ or less, the flexibility is particularly good, and when the laminated film is molded, It is preferred that the micro-crack suppression effect is improved and the stamping heat resistance is good. The density of the raw material sheet before processing into a film of the ethylene-based copolymer resin is more preferably 0.88 g/cm ³ or less, particularly preferably 0.86 g/cm ³ or less. In addition, when the ethylene-based copolymer resin is a copolymer of ethylene and an α-olefin, it is preferably 0.84 g/cm ³ or more from the viewpoint of productivity.

Further, in the layer A of the laminated film of the present invention, it is not damaged The styrene-ethylene-butylene-styrene copolymer and the styrene-ethylene-propylene-styrene copolymer which are not the ethylene-based copolymer resin may be contained within the range of processing suitability such as dimensional stability of the laminated film of the present invention. Or a styrene-based copolymer resin (styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer).

The A layer may be composed of 1 layer, or further by the a1 layer, a2 Any one of the layer and the plurality of layers may be used, but it is preferably one layer in terms of the quality of the productive or functional resin layer. When the layer A is composed of the a1 layer, the a2 layer, and the plurality of layers, the interface number is likely to be distorted during molding due to an increase in the number of interfaces of the layer, and distortion is transmitted to the functional resin layer to cause poor appearance or various functionalities. Case.

(B layer)

The laminated film of the present invention is important in view of the release property of the functional resin when used as a functional resin layer transfer film (for example, the release property of the conductive layer when used as an electromagnetic wave shielding layer transfer film). It is to have a B layer on at least one side of the A layer. As the resin constituting the layer B, it is important to use a polypropylene resin and/or a polyethylene resin as a main component from the viewpoint of mold release property and moldability. Here, "having a B layer on at least one side of the A layer" means that the layer B is provided on any one of the A layers without interposing another layer. Further, the laminated film of the present invention is preferably a structure having a B layer on both sides of the layer A from the viewpoint of handling property during processing and warpage resistance. That is, it is preferable that the B layer/A layer/B layer is directly laminated without interposing another layer.

In addition, the B layer means a layer mainly composed of a polypropylene resin and/or a polyethylene resin. In addition, the term "main component" as used herein means a polypropylene resin and/or a polyethylene resin containing more than 50% by mass and not more than 100% by mass when the total content of the total components of the layer B is 100% by mass.

In other words, when the total content of the total components of the B layer is 100% by mass, the total amount of the polypropylene resin and the polyethylene resin exceeds 50 mass. In the state of 100% by mass or less, the polypropylene resin or the polyethylene resin is often not prevented. Further, the ratio of the polypropylene resin to the polyethylene resin can be appropriately adjusted in view of the composition of the layer A or the adhesion to the functional resin layer.

Polypropylene resin and/or polyethylene contained in layer B When the total amount of the total components of the B layer is 100% by mass, the resin is preferably contained in an amount of 70% by mass or more and 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less. It is contained in the form of 90% by mass or more and 100% by mass or less. The above-mentioned ethylene-based copolymer resin or propylene-based copolymer resin is used for the layer B (the "propylene-based copolymer resin" means that the total amount of the component derived from propylene is less than 50% by mass in 100% by mass of the polymer. When 100% by mass and a resin containing a component derived from a monomer other than a propylene monomer), adhesiveness occurs in the layer B, and blocking occurs at the time of winding depending on production conditions. The polypropylene resin and/or the polyethylene resin contained in the layer B are preferably various homopolypropylene resins/various homopolymers containing 100% by mass of the component derived from propylene or 100% by mass of the component derived from ethylene. Vinyl resin.

In addition, the electromagnetic wave shielding layer is applied to the FPC In the processing of the printing film, it is generally carried out by applying a heat and pressure to the FPC with the electromagnetic wave shielding layer transfer film for about several minutes, and the functional resin layer in the electromagnetic wave shielding layer transfer film (conducting) The portion other than the layer is formed by laminating a hard layer and a soft layer, and the soft layer is compressed with respect to the convex portion of the FPC, and the concave portion is easily pressed toward the concave portion only by the one side of the initial self-contact. In. Further, by including a layer which is harder than the soft layer in the film, it is easier to transmit the force to the bottom side of the concave portion, and the moldability is good. It is important that the main component of the B layer is a polypropylene resin and that the moldability and the mold release property due to the flexibility are excellent, and the adhesion to the hard layer (layer A) having excellent workability is important. / or polyethylene resin.

The main component of layer B can be polypropylene resin and/or polyethylene Any one of the olefinic resins, which is used as an adhesive layer having a high softening temperature in the decorative film, or when applied as an electromagnetic wave shielding layer transfer film for a circuit member such as heat and pressure for a long period of time. The main component of the layer B is preferably a polypropylene resin based on the viewpoint of dimensional stability in the improved processing step and the viewpoint of excessive deformation in the press step at the time of application to a circuit member or the like.

(B layer polypropylene resin)

The polypropylene-based resin of the present invention is a polymer in which the total amount of the components derived from propylene exceeds 50% by mass and is 100% by mass or less based on 100% by mass of the polymer of the polypropylene resin. Examples of the polypropylene resin used in the layer B of the present invention include various polypropylene resins such as polypropylene, an ethylene-propylene copolymer, an ethylene-propylene-butene copolymer, and a propylene-butene copolymer. Among these, in particular, in applications requiring heat resistance such as an electromagnetic wave shielding layer transfer film for a circuit member, the polymer derived from the polypropylene resin is derived from propylene based on the dimensional stability in the processing step. The more the component system, the better, and it is preferably a polypropylene containing only a component derived from propylene. Further, the copolymer may be either a random copolymer or a block copolymer. Among these, in particular, in the use of adhesion to the interlayer of the layer A, an ethylene-propylene copolymer or an ethylene-propylene-butene copolymer is preferred. Further, the copolymerization ratio of ethylene and 1-butene in the ethylene-propylene copolymer and the ethylene-propylene-butene copolymer is preferably 2 to 6 by mass in terms of productivity and mechanical properties. % is preferably from 3 to 15% by mass in terms of 1-butene.

(B layer of polyethylene resin)

The polyethylene-based resin of the present invention is a polymer having a total content of components derived from ethylene of more than 50% by mass and 100% by mass or less in a polymer of a polyethylene resin of 100% by mass.

The polyethylene-based resin used in the layer B of the present invention may, for example, be high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear medium-density polyethylene, linear low-density polyethylene, or low in metal aromatics. Density polyethylene, metal aromatic linear low density polyethylene, metal aromatics. Various polyethylene resins such as high density polyethylene. In addition, in order to carry out the modification of strength, etc., it is preferable to use a chain-like olefin monomer to copolymerize a polyethylene-based resin. Examples of the chain-like olefin monomer include 1-butene and 1- Pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4- Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1 Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like. Among these, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like are more preferably used from the viewpoint of strength, productivity, and cost. From the viewpoint of compatibility and mechanical properties of the A layer with the cyclic olefin resin, 1-hexene is most preferable.

When the main component of the layer B of the present invention is a polyethylene-based resin, high-density polyethylene and linear low-density polyethylene are preferably used as the polyethylene-based resin from the viewpoint of interlayer adhesion to the layer A and heat resistance. Metal aromatic linear low density polyethylene, or metal aromatics. High-density polyethylene, especially in the case of heat resistance, better use of high density Polyethylene, or metal aromatics. High-density polyethylene; especially in the case of emphasizing compatibility, linear low-density polyethylene or metal-aromatic linear low-density polyethylene is more preferably used. Further, when heat resistance is emphasized, the polyethylene resin is preferably a composition derived only from a component derived from ethylene; and when compatibility is important, the polyethylene resin having a main component of the B layer is preferably a linear chain. A metal-aromatic linear polyethylene obtained by copolymerizing low-density polyethylene or 1-hexene or 1-octene.

In addition, the polyethylene resin contained in the B layer only needs to satisfy the source. A resin suitable as the above-mentioned ethylene-based copolymer resin can also be used as a component of the total of the components of the ethylene of more than 50% by mass and not more than 100% by mass.

(B layer of petroleum resin)

When a polypropylene-based resin is used as the main component of the layer B of the present invention, the heat resistance is better than that of the polyethylene-based resin, but the composition of the cyclic olefin-based resin which is a main component of the layer A is occasionally inter-layered. The adhesion is less than that of the polyethylene resin. Therefore, when a polypropylene resin is used as the main component of the B layer, it is preferable to make the layer B contain a petroleum resin to improve the interlayer adhesion between the layer A and the layer B.

Here, "petroleum resin" refers to a polymerization of a part of a by-product oil (c5 (carbon number 5) fraction or C9 (carbon number 9) fraction) which is passed through the light oil cracking used in the petrochemical industry. Examples of the resin include a C5-based petroleum resin obtained by cationically polymerizing a chain olefin mixture of C5, a dicyclopentadiene petroleum resin obtained by thermal polymerization of a dicyclopentadiene fraction, and a C9 aromatic olefin mixture. Cationic polymerization of C9 petroleum resin, C5C9 copolymerized petroleum resin, extraction of C9 fraction A petroleum resin called "pure elemental resin" produced by pure α-methylstyrene, and a resin obtained by hydrogenation, etc., which are contained in α-methylstyrene. Since the petroleum resin has a structure similar to the cyclic olefin resin which is a main component of the A layer, it has high compatibility with the cyclic olefin resin, and the inclusion of the petroleum layer in the B layer improves the adhesion between the A layer and the B layer. From the viewpoint of the adhesion improving effect, a C9-based petroleum resin and a C5C9 copolymerized petroleum resin are preferable.

Specific examples of the petroleum resin include "I-MARV (registered trademark)", "ESCOREZ (registered trademark)" by Tonen, "ALCON (registered trademark)" by Arakawa Chemical Co., Ltd., and "Petcoal (registered trademark) by TOSOH). ", "Petrotack (registered trademark)" and so on.

The petroleum resin contained in the layer B has a softening point of preferably from 80 to 150 ° C, more preferably from 90 to 125 ° C, from the viewpoint of moldability and processability of the improved laminated film. When the softening point of the petroleum resin is less than 80 ° C, the petroleum resin portion is deformed during heating such as a drying step, and the planarity is insufficient. When the softening point of the petroleum resin exceeds 150 ° C, there is a case where the portion of the petroleum resin is not subjected to the hot pressing and the laminated film is broken.

When the total amount of the total components of the layer B is 100% by mass, the layer B of the present invention preferably contains 0.1% by mass or more and 15% by mass or less of the petroleum resin, more preferably 1% by mass or more and 12% by mass or less. It is preferably 5 mass% or more and 10 mass% or less. When the petroleum resin contained in the layer B is less than 0.1% by mass, the phase-to-phase adhesion to the layer A may be insufficient. When the amount of the petroleum resin contained in the layer B exceeds 15% by mass, the laminated film may be embrittled or the mold release property may be insufficient.

When the polypropylene resin is used for the layer B of the present invention, the interlayer adhesion between the layer A and the layer A can be improved by including the petroleum resin in the layer B, but it is also possible to prevent the layer B from being damaged. The layer contains an adhesive resin other than petroleum resin to improve the adhesion between the A layer and the B layer. Examples of the adhesive resin other than the petroleum resin include rosin-based resins such as rosin, rosin ester, hydrogenated turpentine, and polymeric turpentine, or terpene such as α-pinene polymer, β-pinene polymer, and terpene-phenol polymer. A resin, a cyclic olefin resin containing a polar group, a polyolefin resin other than a cyclic olefin resin containing a polar group, or the like. Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, a decylamino group, an ester group, and a hydroxyl group.

However, the polyolefin resin other than the cyclic olefin resin containing a polar group or the cyclic olefin resin containing a polar group is in close contact with a pipe or a nozzle of a production facility because of high adhesion to a metal, and the film appearance is poor. In the case where the resin or the nozzle is cleaned, the productivity is lowered. Therefore, when the total amount of the total components of the layer B is 100% by mass, the resin is preferably 5% by mass or less, more preferably 2% by mass. It is more preferably 1% by mass or less, and it is particularly preferable to use only a petroleum resin, a rosin-based resin, or a terpene-based resin to exhibit interlayer adhesion between the A layer and the B layer.

(Characteristics of resin of layer B)

The polypropylene resin and the polyethylene resin used in the layer B of the present invention preferably have a melt flow rate (MFR) of 1 to 1 according to JIS-K7210 (1999) at 230 ° C and a load of 2.16 kg. 80g/10 minutes, more preferably 2~50g/10 minutes, and then better 3~30g/10 minutes; Good for 4~10g/10 minutes. When the MFR of the polyethylene resin or the polypropylene resin is less than 1 g/10 minutes, the melt viscosity is high, so that the extrusion property is lowered and the thickness unevenness is increased. When the MFR of the polyethylene resin or the polypropylene resin exceeds 80 g/10 minutes, the crystallinity is increased to cause a large decrease in film formability or a decrease in mechanical properties of the laminated film. In the case where the crystallization of the layer B is excessively performed, the surface is roughened and the printing accuracy is lowered.

Polyethylene resin used in the layer B of the present invention, poly The ultimate viscosity [η] of the propylene resin is preferably from 1.4 to 3.2 dl/g, more preferably from 1.6 to 2.4 dl/g, from the viewpoint of having appropriate crystallinity. When [η] is less than 1.4 dl/g, there is a possibility that the laminated film is embrittled due to excessive crystallinity; when it exceeds 3.2 dl/g, the crystallinity is remarkably lowered, and the heat resistance of the laminated film is lowered.

For the layer B of the present invention, drying based on the functional resin layer The melting point is preferably in the range of 100 to 170 ° C, more preferably 130 to 165 ° C, and more preferably 145 ° C to 160 ° C from the viewpoint of processing suitability or moldability at a temperature. When the melting point is lower than 100 ° C, the thermal deformation of the film may increase, resulting in insufficient processing suitability; when it exceeds 170 ° C, the moldability may be insufficient.

When a polypropylene resin is used as a main component of the layer B, In the layer B of the present invention, the heat of crystal melting determined by the differential scanning calorimeter according to JIS K7121-1987 and JIS K7122-1987 is preferably 20 mJ/mg or more and 25 mJ/mg or less. The heat of crystal melting indicates the degree of progress of crystallization. If the heat of crystal melting of the layer B is less than 20 mJ/mg, the progress of crystallization is insufficient, and there is a decorative film or structure which is an adhesive layer having a high softening temperature, or Applied as a When the electromagnetic wave shielding layer transfer film for a circuit member such as heat and pressure is added for a long period of time, dimensional stability during the processing step and excessive deformation in the press step when applied to a circuit member or the like occur. When the heat of crystal melting of the layer B exceeds 25 mJ/mg, the crystallization may be excessively performed, and the moldability may be insufficient. The heat of crystal melting of the layer B is preferably 21 mJ/mg or more and 23 mJ/mg or less, and particularly preferably 21.5 mJ/mg or more, based on the dimensional stability in the processing step or the suppression of excessive deformation in the press step and the moldability. 22.5mJ/mg or less.

As the crystal of the B layer is melted to a heat of 20 mJ/mg For the method of 25 mJ/mg or less, for example, a method of transferring an appropriate amount of heat to the film during the production of the laminated film of the present invention may be mentioned. As a method for obtaining the laminated film of the present invention, for example, a method in which a film-like molten polymer extruded from a nozzle is sandwiched between a rubber roll and a metal roll and cooled and solidified is used, and specifically, In the above-described manufacturing method, the casting temperature (metal roll temperature) is set to a high temperature of 40 ° C to 110 ° C, and a rubber roller or the like is used, and a nip pressure of 0.1 to 1 MPa is used for sandwiching.

(surface free energy of layer B)

In the layer B of the laminated film of the present invention, the surface free energy is preferably 25 based on the mold release property of the functional resin layer and the adhesion to the functional resin layer in the step (processing step or molding step). ~35mN/m, more preferably 27~33mN/m, especially preferably 28~32mN/m. In addition, the "processing step" as described above refers to a processing step in coating processing, printing processing, metal deposition processing, and the like performed on the laminated film of the present invention in the case of producing a functional resin layer transfer film to be described later. Again The molding step includes a step of disposing the functional resin layer transfer film on a molding machine or a press, or a step of heating the resin layer transfer film by a heater before molding.

When the surface free energy of the layer B of the laminated film of the present invention is less than 25 mN/m, the adhesion between the laminated film and the functional resin layer is weak, and therefore, the laminated film and the conductive layer (functional resin layer) of the present invention are provided. The electromagnetic wave shielding layer transfer film is disposed on the FPC and is subjected to hot pressing, and the laminated film and the conductive layer are peeled off. On the other hand, when the surface free energy of the layer B of the laminated film of the present invention exceeds 35 mN/m, the adhesion between the laminated film and the functional resin layer becomes strong, and the release of the functional resin layer after hot pressing is performed. Insufficient circumstances.

Here, "surface free energy" means a value obtained by the measurement method in the embodiment.

The method for making the surface free energy of the layer B in the range of 25 to 35 mN/m includes a method of using a polyethylene resin and/or a polypropylene resin as a main component of the layer B, and the layer B is slippery. The method for reducing the surface free energy of the agent, and the surface treatment by corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, laser treatment, flame treatment, high frequency treatment, glow discharge treatment, ozone oxidation treatment, etc. A method which can be added, and a method in which the layer B contains a resin having a low surface free energy such as a polymethylpentene-based resin or the like. These methods can be combined depending on the characteristics of the functional resin layer.

Further, examples of the lubricant which can be preferably used include higher fatty acid guanamines, higher fatty acid esters, waxes, and eucalyptus oils, and preferred higher fatty acid guanamines and higher fatty acid esters. Again, this can be separate Use, you can also use at least 2 kinds together. Examples of the higher fatty acid amides include saturated fatty acid decylamine, unsaturated fatty acid decylamine, and di-fatty acid decylamine. Examples of the saturated fatty acid guanamine include, for example, dodecylamine, tetradecylamine, octadecylamine, and behenylamine; and examples of the unsaturated fatty acid guanamine include guanyl erucamide and decyl oleate. Examples of the di-fatty acid decylamines include, for example, methylenebisoctadecylamine, methylene bismuth oleate, ethylene octadecylamine, and ethylene bismuth oleate. Examples of the higher fatty acid esters include acetylated glycerides, medium chain fatty acid triglycerides having a fluorenyl group having 8 to 12 carbon atoms, and polyglycerin fatty acid esters having at least one alcoholic hydroxyl group.

Further, the laminated film of the present invention is used, for example, in the following form.

(functional resin layer transfer film)

The laminated film of the present invention can be suitably used as a functional resin layer transfer film having the laminated film of the present invention and the functional resin layer by further laminating the functional resin layer because of its good moldability, mold release property, and processability.

Here, the "functional resin layer" means a layer for imparting scratch resistance, weather resistance, color, pattern, or the like to a molded member, or providing a circuit member with a photosensitive or electromagnetic wave shielding property for forming a circuit pattern. A transparent layer, a colored layer, a conductive layer of an adhesive layer or an electromagnetic wave shielding layer transfer film, for example, a decorative film to be described later.

Further, the functional resin layer transfer film of the present invention is a film having a functional resin layer on the outermost surface, which means that the functional resin layer of the outermost surface is bonded to the molded member or the circuit member by heat or pressure. The film obtained by removing and removing a portion other than the functional resin layer includes, for example, a molding transfer foil or an electromagnetic wave shielding layer transfer film which will be described later. By bonding the functional resin layer to the molded member or the circuit member and removing the portion other than the functional resin layer, that is, the so-called transfer structure, when the decorative film is used, the trimming after the transfer of the functional resin layer is not required. The step or the thinning of the functional resin layer can achieve high performance and low cost, which is preferable.

(decorative film)

The laminated film of the present invention is preferably used for molding purposes because of its moldability, mold release property, and processability, and particularly preferably used for molding transfer foil. The decorative layer is laminated on the laminated film of the present invention and transferred to the molded body (transferred body) at the same time as molding, whereby the laminated film and the decorative layer of the present invention can be easily peeled off, and the surface having excellent surface appearance can be obtained. member. The structure of the molded transfer foil is not particularly limited, and a structure in which a decorative layer is laminated on the laminated film of the present invention is preferred. Here, the decorative layer is a layer for adding a decoration such as coloring, pattern, wood grain, metallic color, pearl color, or the like. It is preferable to further laminate a transparent layer from the viewpoint of scratch resistance, weather resistance, and designability of the molded member after transfer. At this time, the transparent layer is preferably laminated on the side of the film for molding. Further, it is preferable to use a laminated adhesive layer from the viewpoint of the adhesion between the molded body (transferred body) after transfer and the decorative layer. At this time, the adhesive layer is preferably laminated on the side of the molded body (transferred body).

In other words, as a preferred embodiment of the molded transfer foil, a structure of the "multilayer film/transparent layer/decorative layer/adjacent layer of the present invention" can be mentioned. The term "transparent layer" as used herein refers to the layer located at the outermost layer of the molded member. It is a layer of high gloss and high transparency for enhancing the appearance of the molded member. Here, the term "decorative layer" as used herein refers to a layer for adding a decoration such as coloring, unevenness, pattern, wood grain, metallic color, pearl color, or the like.

Here, the resin used as the transparent layer is not particularly limited as long as it is a highly transparent resin, and a thermosetting resin, a light or an ultraviolet curable resin is preferably used from the viewpoint of scratch resistance. As the thermosetting resin, for example, a thermosetting acrylic resin, a phenoxy resin, an epoxy resin or the like is preferably used. As the light or ultraviolet curable resin, a urethane acrylate resin or a polyester acrylic acid is preferably used. An ester resin, an unsaturated polyester resin, a polyoxy acrylate resin, an epoxy acrylate resin, or the like. Among these resins, a photopolymerization initiator, a hardener, a hardening accelerator, a binder, a surface conditioner, a pigment, a plasticizer, an ultraviolet absorber, an ultraviolet reflector, a light stabilizer, and the like may be mixed as needed. Further, the resin used for the transparent layer may be a copolymer or a mixture of two or more kinds of resins. Further, when a light or ultraviolet curable resin is used, it is preferable to carry out a hardening treatment after molding, from the viewpoint of moldability of the modified transfer foil.

Examples of the method for forming the transparent layer include a direct formation method, a method of temporarily forming the carrier film, and transferring the film. If it is desired to bring the drying temperature after the formation of the transparent layer to a high temperature, it is preferred to use a method which is temporarily formed on the carrier film and then transferred. As a method of forming the transparent layer, in addition to the roll coating method, the brush coating method, the spray coating method, and the dip coating method, a gravure coater, a die coater, and a horn coater (comma coater) may be used. ), a bar coater, and a knife coater.

The method for forming the decorative layer is not particularly limited, and can be formed, for example, by coating, printing, metal deposition, or the like. When applying the coating, A coating method such as a gravure coating method, a roll coating method, a notch wheel coating method, or the like can be employed. Further, when printing is performed, a printing method such as a lithography method, a gravure printing method, or a screen printing method can be employed. As the resin used at this time, a polyester resin, a polyolefin resin, an acrylic resin, a urethane resin, a fluorine resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate is preferably used. A copolymer resin, an ethylene-vinyl acetate copolymer resin copolymer, or the like. The coloring agent to be used is not particularly limited, and is preferably selected from dyes, inorganic pigments, organic pigments, and the like in consideration of dispersibility and the like.

As a result of giving a molded body (adhered body, transfer target) The material of the adhesive layer provided for the purpose of the purpose may be a heat sensitive type or a pressure sensitive type. When a resin molded body formed by injection molding or the like is used as a molded body (adhered body or transfer target), when the laminated film of the present invention is transferred thereto, an adhesive layer can be designed according to the resin. In the case of an acrylic resin, an acrylic resin is preferably used; if it is a polyphenylene ether. When a polystyrene resin, a polycarbonate resin, a styrene copolymer resin, or a polystyrene resin is used, an acrylic resin, a polystyrene resin, and a polyamine which have affinity with these resins are preferably used. Resin or the like. When the resin molded body contains a polypropylene resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a cyclized rubber, or a benzofuran-ruthenium resin is preferably used.

The method of forming the layer can be carried out by various methods and can be used. For example, a coating method such as a roll coating method, a gravure coating method, or a notch wheel coating method may be employed, for example, a printing method such as a gravure printing method or a screen printing method.

Form transfer using a laminate film using the present invention The molded body (transferred body) which is decorated with a foil is not particularly limited, and for example, polypropylene, acrylic, polystyrene, or polyacrylonitrile can be used. Styrene, polyacrylonitrile. Butadiene. A resin such as styrene or a metal member.

When using a transfer foil using the laminated film of the present invention When the decorative layer is transferred to the molded body (transferred body), various molding methods such as vacuum forming, vacuum pressure forming, plug assist molding, and hot press forming may be employed.

As a specific method of molding, if, for example, vacuum is used In the vacuum forming process, the four corners of the forming transfer foil are fixed by the frame attached to the molding machine, and the forming transfer foil is heated to a softening temperature by a heater or the like, and then vacuum and atmospheric pressure are applied to the film. Or the pressure difference between vacuum and pressure is made to correspond to the molded body. After the molding is completed, only the laminated film portion is peeled off from the molded body to which the molded transfer foil is bonded, whereby a molded body to which the decorative layer is transferred can be obtained.

(electromagnetic wave shielding layer transfer film)

The laminated film of the present invention is excellent in moldability, mold release property, and processability, and can be suitably used as an electromagnetic wave shielding layer transfer film having the laminated film and the conductive layer of the present invention by further laminating a conductive layer.

Here, the conductive layer is preferably configured to contain a conductive filler in the adhesive. As the adhesive, a thermoplastic resin such as a polystyrene type, a vinyl acetate type, a polyester type, a polyethylene type, a polypropylene type, a polyamide type, a rubber type, or an acrylic type, or a phenol type or an epoxy type can be used. A thermosetting resin such as a urethane type, a melamine type or an alkyd type. Such as When heat resistance is not particularly required, it is preferably a polyester-based thermoplastic resin which is not limited to storage conditions and the like; and when heat resistance or more excellent flexibility is required, it is preferable to have high reliability after forming an electromagnetic wave shielding layer. An epoxy-based thermosetting resin. Further, in any of the resins, it is preferred that the bleeding (resin outflow) at the time of hot pressing is small.

As a conductive filler, carbon, silver, copper, nickel, Solder, aluminum, and copper powder are silver-plated silver-clad copper fillers, and a metal-plated filler such as resin beads or glass beads or a mixture of such fillers can be used. Due to the high price of silver, the lack of heat resistance reliability of copper, the lack of moisture resistance reliability of aluminum, and the fact that solder is not easy to obtain sufficient conductivity, silver-coated copper filler or nickel which is relatively inexpensive and has excellent electrical conductivity and even high reliability is used. Preferably.

The blending ratio of the conductive filler in the adhesive resin depends on the shape of the filler, etc., and in the case of the silver-coated copper filler, it is preferably 10 to 400 parts by mass based on 100 parts by mass of the adhesive resin. It is better to use 20 to 150 parts by mass. When the amount is more than 400 parts by mass, the adhesion to the ground circuit (copper foil) is lowered, and the flexibility of the printed wiring board or the like is deteriorated. When the amount is less than 10 parts by mass, the electrical conductivity is remarkably lowered. Further, in the case of the nickel filler, it is preferably 40 to 400 parts by mass, more preferably 100 to 350 parts by mass, per 100 parts by mass of the adhesive resin. When the amount is more than 400 parts by mass, the adhesion to the ground circuit (copper foil) is lowered, and the flexibility such as the shielding FPC is deteriorated. When the amount is less than 40 parts by mass, the electrical conductivity is remarkably lowered. The shape of the metal filler may be any of a spherical shape, a needle shape, a fiber shape, a sheet shape, and a resin shape. Further, the conductive filler is preferably a low melting point metal.

Electromagnetic wave shielding layer transfer using the laminated film of the present invention The thin film is provided with a thin metal layer formed by vapor deposition or the like between the laminated film and the conductive layer, thereby reducing the thickness plating of the conductive layer and improving the electromagnetic wave shielding property. The metal layer may, for example, be any one of nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium, zinc, and any one or more of alloys containing such materials, and the metal material and thickness may be as required. The electromagnetic wave shielding characteristics and the repeated bending-sliding resistance can be appropriately selected. Further, in terms of thickness, the thickness is preferably from 0.1 μm to 8 μm. Examples of the method for forming the metal layer include a plating method, an electroless plating method, a sputtering method, an electron beam evaporation method, a vacuum vapor deposition method, a CVD (Chemical Vapor Deposition) method, and printing and firing using a metal organic paste. Method, etc.

As a laminated film of the present invention, it acts as an electromagnetic shielding layer The method of transferring the film and transferring the electromagnetic wave shielding layer to the FPC may employ various molding methods such as vacuum forming, vacuum pressure forming, plug assist molding, and hot press forming.

As a specific method of molding, for example, by hot press forming When the concave-convex substrate side of the FPC is overlapped with the electromagnetic wave shielding layer side of the electromagnetic wave shielding layer transfer film, the electromagnetic wave shielding layer transfer film side is pressed by the heated metal plate, and the electromagnetic wave shielding layer transfer film corresponds to the FPC. Bump. After the molding is completed, the FPC (shielding FPC) to which the electromagnetic wave shielding layer is transferred is obtained by peeling only the laminated film portion from the FPC to which the electromagnetic wave shielding layer transfer film is bonded.

(film for packaging)

The laminated film of the present invention can be used as a film for packaging. When the laminated film of the present invention is used as a film for packaging, the layer A is It can improve the water vapor barrier property and the B layer can improve the heat sealability, and can be applied to various packaging films which are used as a film for lithium ion battery, a film for food packaging, and a film for medical use. As a general structure of the film for packaging, for example, a biaxially stretched polyethylene terephthalate film (hereinafter referred to as BO-PET), a biaxially stretched nylon film (hereinafter referred to as ONy), or a polypropylene system is used. Stretch film (hereinafter referred to as CPP) and aluminum foil (hereinafter referred to as Al foil) to form BO-PET/ONy/Al foil/CPP, BO-PET/Al foil/ONy/CPP or BO-PET/Al foil/CPP structure After the laminated body, the CPP layer side is used as a bag body; by using the laminated film of the present invention as the CPP layer, the water vapor barrier property of the end portion of the bag body can be made better than the conventional CPP layer. Packaging film.

Further, the laminated film of the present invention preferably satisfies the following characteristics (any one or more or all of them).

(Surface roughness)

The laminated film of the present invention has a surface roughness SRa of 50 nm or more and 3,000 nm or less on both sides, and is preferable from the viewpoints of winding properties, design properties, and productivity. When the laminated film of the present invention is heated in the processing step or the molding step, the layer having a larger surface roughness SRa (SRa is 50 nm or more) when the Sra of the surface is less than 50 nm and the surface of the other surface is 50 nm or more. The layer is accumulated in a large amount, and the surface unevenness of the layer on the larger side of the surface roughness SRa becomes smaller. As long as the surface roughness SRa of both sides is 50 nm or more, even if the roughness is different, the reduction of the unevenness is small; the laminated film of the present invention has a surface roughness SRa on both sides of the surface of the laminated film, particularly when the matte design is required. It is preferably 50 nm or more.

In addition, it is incident on either side of the film (referred to as "A" The light of the surface is refracted at the interface between the surface of the film A and the atmosphere. reflection. Thereafter, the light entering the inside of the film is refracted at the interface between the other side of the film (referred to as "B side" as convenient) and the atmosphere. Reflect and shoot toward the outside of the film. Therefore, by making the surface roughness SRa of both surfaces of the laminated film 50 nm or more, the light can be refracted at the interface (the interface between the A surface and the atmosphere and the interface between the B surface and the atmosphere) at two interfaces. reflection. That is, when the light is incident on the laminated film of the present invention, the amount of light that is directly penetrated can be reduced, and as a result, the whiteness of the film can be improved, and the visibility of the film is good (it can be easily combined with the molded body). It is preferable to print (visually discriminate).

When the SRa exceeds 3,000 nm, the surface is uneven. When the functional resin layer is laminated on the laminated film having the functional layer of the present invention, the bubbles are not detached, and the appearance is poor or the functional layer of the functional resin is degraded (electromagnetic wave shielding layer) The case where the electromagnetic wave shielding property is lowered). In addition, there is a case where the functional resin layer cannot be uniformly laminated on the concave portion of the surface of the laminated film. In this case, since the portion where the functional resin layer and the laminated film are in contact with each other forms only a convex portion, the adhesion between the laminated film and the functional resin layer may be insufficient.

Furthermore, the laminated film of the present invention is rolled into a roll shape for storage In the case where the surface on which the functional resin layer is laminated (hereinafter referred to as the first surface) is directly in contact with the surface on the opposite side of the first surface (hereinafter referred to as the second surface); in other words, The second surface is held in a state of being pressed against the first surface. Therefore, the surface shape (surface roughness) of the second surface is transferred The surface of the first surface is deformed so that the surface shape of the first surface is deformed. As described above, since the surface roughness of the first surface is preferably 3,000 nm or less, the surface roughness of the first surface may be changed by the influence of the surface shape of the second surface, and the surface roughness of the second surface may be It is preferably 3,000 nm or less.

Based on the above, the laminated film of the present invention preferably has a surface roughness SRa of 3,000 nm or less on both surfaces.

As a method of setting the surface roughness SRa to 50 nm or more and 3,000 nm, for example, a film-like molten polymer extruded from a nozzle is sandwiched between two rolls whose surface is adjusted to have appropriate roughness and cooled and solidified. A method of forming a film, transferring the roughness of the roll to both sides of the film, or the like. In addition, in the case of the two rolls, the ease of adjustment based on the thickness unevenness, the ease of transfer of the surface roughness of the roll, and the transfer of the uniform roughness pattern to the film viewpoint are as follows. Another one is preferably a metal roller.

(haze)

When the laminated film of the present invention is used as a transfer film of a functional resin, the haze is preferably 65% or more and 90% or less in order to prevent peeling residue or forgetting to peel off. When the haze of the laminated film is less than 65%, it is difficult to visually recognize the presence or absence of the film depending on the color of the molded body (transferred body). When the haze of the laminated film is more than 90%, it may be difficult to visually coat the surface from the opposite side of the coated surface when the functional resin layer is applied. For example, the decorative film used in the laminated film of the present invention is constructed by "layered film/transparent layer/decorative layer/adhesive layer", and "transparent layer/decorative layer/adhesive layer" is equivalent to functional resin. Floor. Thereafter, when the functional resin layer is transferred to the molded body using the decorative film, the layer located on the outermost layer of the molded member becomes a transparent layer. Therefore, if the position of the transparent layer can be specified in advance by, for example, confirming the application state of the functional resin layer before the transfer step, the transfer to the molded body can be avoided (the transparent layer is free from defects). As a result, the functional resin layer can obtain a molded member excellent in appearance in a high yield. In other words, when the haze of the laminated film is 90% or less, it is easy to visually coat the surface from the opposite side of the coated surface when the functional resin layer is applied, and as a result, it is possible to obtain an excellent appearance in a high yield. member. On the other hand, when the haze of the laminated film is more than 90%, it is difficult to visually coat the surface from the opposite side of the coated surface when the functional resin layer is applied, so that it is not possible to obtain an excellent appearance in a high yield. The condition of the component.

In order to make the haze of the laminated film 65% or more and 90% For example, a method in which the surface roughness SRa of both surfaces of the roll for cooling and solidifying the molten polymer in the production of the laminated film is 50 nm or more and 3,000 nm or less is used. The larger the surface roughness, the more diversified the direction of the light-refracting interface (the interface between the film surface and the atmosphere) when light is incident on the surface of the film, and the less the amount of light that moves straight in the film thickness direction. The higher the degree of fogging.

However, if the surface roughness is excessively increased until the haze value exceeds When 90% (e.g., the surface roughness exceeds 3,000 nm), the surface of the layer B has an excessively large unevenness, so that a portion where the thickness is thin in the layer B is locally generated. If there is a portion where the thickness is thin in the B layer, there is a case where the layer A is peeled off from the point where the layer is removed, and as a result, the adhesion between the layer A and the layer B is lowered.

Also used to make the haze of the laminated film 65% or more The other method of 90% or less may be a method of increasing the thickness of the laminated film of the present invention and increasing the refraction of light inside the film to increase the haze. Specifically, the thickness of the film is preferably from 100 to 300 μm. Moreover, it is also preferable to use a method of containing a known coloring pigment such as titanium oxide in an amount of 1 to 20% by mass based on the entire laminated film.

However, when the haze of the laminated film exceeds 90%, When the laminated film contains a large amount of a known colored pigment such as titanium oxide to increase the haze, if the content of the colored pigment is excessively increased to a haze value of more than 90% (for example, the content of the colored pigment exceeds 20% by mass), A large amount of coloring pigment is also present at the interface of the A layer/B layer. Therefore, at the interface between the layer A and the layer B, the portion of the resin constituting the layer A and the resin constituting the layer B are less likely to adhere, and as a result, the adhesion between the layer A and the layer B may be lowered.

(tone)

When the laminated film of the present invention is used as a transfer film of a functional resin, the color tone L value measured in the penetration mode based on JIS P8123-1961 is preferably 75 or more and 100 or less in order to prevent peeling residue or forgetting to peel off. . When the color tone L value is less than 75, it may be difficult to visually recognize the presence or absence of the film depending on the color of the molded body (transferred body). The color tone L value can be used as a standard value of whiteness, and particularly when the color tone of the molded film of the present invention is a dark color tone, if the color tone L value of the laminated film of the present invention is 75 or more, peeling residue can be effectively prevented. Or forget to strip.

When the color tone L value of the laminated film exceeds 100%, the surface of the opposite side of the coated surface is hard to be applied when the functional resin layer is applied. The condition of the coating state was visually observed. For example, the decorative film used in the laminated film of the present invention has a structure of "layered film/transparent layer/decorative layer/adhesive layer", and "transparent layer/decorative layer/adhesive layer" corresponds to a functional resin layer. Thereafter, when the functional resin layer is transferred to the molded body using the decorative film, the layer located on the outermost layer of the molded member becomes a transparent layer. Therefore, if the position of the transparent layer can be specified in advance by, for example, confirming the application state of the functional resin layer before the transfer step, the transfer to the molded body can be avoided (the transparent layer is free from defects). As a result, the functional resin layer can obtain a molded member excellent in appearance in a high yield. In other words, when the color tone L value of the laminated film is 100, when the functional resin layer is applied, it exhibits a white state which can be visually coated from the opposite side of the coated surface, and as a result, high yield can be obtained. A molded member having an excellent appearance is obtained. On the other hand, when the color tone L value of the laminated film is 100, the functional state of the functional resin layer may be difficult to produce in a white state due to the fact that it is not easily visually applied from the opposite side of the coated surface. The rate is obtained in the case of a molded member having an excellent appearance.

However, if the surface roughness is excessively increased to the color of the laminated film When the L value exceeds 100 (for example, the surface roughness exceeds 3,000 nm), the surface unevenness of the B layer is too large, so that a portion where the thickness is thin in the B layer is locally generated. If there is a portion where the thickness is thin in the B layer, there is a case where the layer A is peeled off from the point where the layer is removed, and as a result, the adhesion between the layer A and the layer B is lowered.

However, when the L-value of the laminated film exceeds 100, the laminated film is made to contain a large amount of a known coloring pigment such as titanium oxide to increase the color. When the L value is adjusted, if the content of the coloring pigment is excessively increased until the color tone L value exceeds 100 (for example, the content of the coloring pigment exceeds 20% by mass), there is also a large amount of coloring at the interface of the A layer/B layer. The case of pigments. Therefore, at the interface between the layer A and the layer B, the portion of the resin constituting the layer A and the resin constituting the layer B are less likely to adhere, and as a result, the adhesion between the layer A and the layer B may be lowered.

The color L value is set to be 75 or more and 100 or less. As another method, a method of increasing the thickness of the laminated film of the present invention and increasing the refraction of light inside the film to increase the haze may be mentioned.

In order to make the laminated film have a hue L value of 75 or more and 100 In the following, a method for preparing a known coloring pigment such as titanium oxide in an amount of 1 to 20% by mass based on the entire laminated film, and a surface roughness SRa of a roller for cooling and solidifying the molten polymer in the production of the laminated film is 50 nm. The above method of 3,000 nm or less. Further, the larger the surface roughness SRa, the whiter the appearance of the laminated film, and the larger the tone L value.

In addition, as another method, a laminate for the present invention can be cited. The thickness of the film is adjusted to a thickness of 100 to 300 μm to improve the whiteness of the laminated film of the present invention and to increase the color tone L value.

(layering ratio, thickness)

In the use of the laminated film of the present invention, for example, in the electromagnetic wave shielding layer transfer film which is required to have a fine shape, the laminate ratio (the total thickness (μm) of the layer B/the thickness (μm) of the layer A) is 0.1 or more and 0.15. Hereinafter, it is preferable based on the viewpoint of the moldability of a fine shape. Further, when the laminated film has two B layers, that is, when the B layer is formed on both sides of the A layer, the laminated ratio (the total thickness (μm) of the B layer / the thickness (μm) of the A layer) is [there are two layers The total thickness of the B layer] / [the thickness of the A layer]. On the other hand, when the build-up film has one B layer, that is, the B layer is formed only on one side of the A layer, the buildup ratio (the total thickness of the B layer (μm) / the thickness of the A layer (μm)) is [B layer Thickness] / [thickness of layer A].

If the laminate ratio is less than 0.1, the thickness of the B layer is uneven. Larger case where the thickness of the B layer is extremely thin. In this case, there is a case where the layer B having a good mold release property is not sufficiently laminated, and the layer A is exposed on the surface on the side of the layer B of the laminated film. Further, as a result, the mold release property is insufficient, and the adhesion between the layers of the layer A and the layer B is insufficient.

If the laminate ratio exceeds 0.15, the thickness of the B layer is thickened. There is a case where the moldability of the fine shape is insufficient. The laminate ratio can be measured by observing the cross section of the film at a magnification of 500 times or more and 10,000 times or less by using a scanning electron microscope, a transmission electron microscope, an optical microscope, or the like.

On the other hand, for example, the laminated film of the present invention is packaged When the decorative film is used, the laminated film of the present invention has a laminate ratio (the total thickness of the layer B (μm) / the thickness of the layer A based on the adhesion between the layers of the layer A and the layer B, the mold release property, and the processing suitability ( Μm)) is preferably 0.25 or more and 2 or less.

In particular, when the decorative decorative layer is molded by using the decorative film of the present invention and the molding magnification of the laminated film is increased, the decorative film is pushed deep into the depth direction along the shape of the molded body. Thereafter, when only the laminated film is peeled off from the decorative film, a large force (peeling force) is sometimes required. Therefore, in this case, the adhesion between the layers of the A layer and the B layer is sometimes higher.

If the laminate ratio (the total thickness of layer B (μm) / thickness of layer A When (μm) is less than 0.25, the adhesion between the layers of the A layer and the B layer may be insufficient, and the mold release property may be insufficient. When the thickness exceeds 2, the workability may be insufficient. Further, in terms of the buildup ratio (the total thickness of the B layer (μm) / the thickness (μm) of the A layer), when there are two B layers, that is, when there are B layers on both sides of the A layer, there are two layers. The total thickness of the B layer / the thickness of the A layer; when there is one B layer, that is, only the B layer on one side of the A layer, the thickness of the B layer / the thickness of the A layer. The laminate ratio (the total thickness (μm) of the layer B/the thickness (μm) of the layer A) is more preferably 0.25 or more and 1.2 or less, and particularly preferably 0.25 or more and 0.5 or less. The laminate ratio can be measured by observing the cross section of the film at a magnification of 500 times or more and 10,000 times or less by using a scanning electron microscope, a transmission electron microscope, an optical microscope, or the like.

For the laminated film of the present invention, based on the A layer and the B layer The total thickness of the film is preferably 40 μm or more and 300 μm or less from the viewpoint of interlayer adhesion, moldability, mold release property, and process suitability. More preferably, it is 60 μm or more and 200 μm or less, and more preferably 80 μm or more and 150 μm or less. When the total thickness of the film is less than 40 μm, the adhesion between the layers of the A layer and the B layer may be insufficient, and the processing suitability may be insufficient. When the total thickness of the film exceeds 300 μm, moldability may be insufficient.

The B layer of the present invention can be used to melt the B layer from the T-shaped mold. The molten resin is extruded into a film, and is extruded and laminated on a single layer film having an A-layer structure, and the resin of the A layer and the B layer is extruded by an individual extruder. The feedblock is laminated, and the resin discharged from the T-die is obtained by a known method such as a co-extrusion method in which a cooling roll is solidified.

(peel strength of layer A and layer B)

In the laminated film of the present invention, the peel strength under the 180° C peel test of the A layer and the B layer is preferably 0.5 N/10 mm or more and 5 N/10 mm or less from the viewpoint of interlayer adhesion. When the peeling strength is less than 0.5 N/10 mm, peeling occurs between the layer A and the layer B at the time of various processing or transfer of the functional resin, resulting in deterioration of workability or insufficient transfer of the functional resin. Happening. Further, the higher the peel strength, the better, but depending on the method of improving the peel strength, the appearance of the laminated film may be deteriorated, and it is preferably 5 N/10 mm or less.

When the peeling strength of the layer A and the layer B of the laminated film of the present invention is 0.5 N/10 mm or more and 5 N/10 mm or less, it is preferable to use "when the layer B is mainly composed of a polyethylene resin, the layer A is COC. When the B layer is composed of a polypropylene resin as a main component, the A layer is mainly composed of COP, and the A layer contains a vinyl copolymer resin; a casting drum is provided. That is, the temperature of the metal roll) is 40 ° C or more to activate the movement of the polymer chains of the respective layers and simultaneously cast, thereby increasing the entanglement of the interface between the A layer and the B layer; manufacturing by a nip roll method, and clamping The method of pressing 0.2 to 1.0 MPa and the combination thereof.

(storage elastic modulus)

The laminated film of the present invention preferably has a storage elastic modulus at 120 ° C of from 101 MPa to 3,000 MPa, from the viewpoints of workability and moldability. The storage elastic modulus at 120 ° C is 101 MPa or more, and after drying, for example, after applying the functional resin layer, or in the step of performing metal vapor deposition, deformation or the like of the film does not occur. Good processing suitability. In particular, by setting the drying temperature after coating to a high temperature, the linear velocity at the time of drying can be accelerated, and the processing cost can be reduced. The higher the storage elastic modulus at 120 ° C, the better the dimensional stability is better, and if it is desired to be higher than 3,000 MPa, the moldability is lowered. In order to achieve higher dimensional stability and moldability, the storage elastic modulus at 120 ° C is preferably 500 MPa or more and 3,000 MPa or less, and more preferably 1,000 MPa or more and 3,000 MPa or less.

In the laminated film of the present invention, as a method of setting the storage elastic modulus at 120 ° C to the range of 101 MPa or more and 3,000 MPa or less, a method of adjusting the glass transition temperature of the A layer or the like can be mentioned.

In the present invention, the method for controlling the glass transition temperature of the layer A is not particularly limited. For example, when a copolymer of norbornene and ethylene is used as the cyclic olefin resin, the glass can be transferred by continuously increasing the content of the decene. The temperature is transferred to a high temperature; for example, when a resin obtained by subjecting norbornene, tricyclodecene, tetracyclononene or a derivative thereof to ring-opening metathesis polymerization and hydrogenating is used as a cyclic olefin resin, The molecular weight of the cyclic olefin to be polymerized (norbornene, tricyclodecene, tetracyclononene, and derivatives thereof) or a ring number increase to form a rigid structure allows the glass transition temperature to be shifted to a high temperature. Further, the glass transition temperature of the layer A can be adjusted by blending two kinds of cyclic olefin-based resins having different glass transition temperatures. In the case where a resin other than the cyclic olefin resin is mixed in the layer A, if a plurality of glass transition temperatures are present, the glass transition temperature on the high temperature side is used as the glass transition temperature of the layer A.

The laminated film of the present invention preferably has a storage elastic modulus at 170 ° C of 100 MPa or less based on moldability. Storage at 170 ° C When the modulus of elasticity is 100 MPa or less, it is preferable to set the molding temperature to at least 170 ° C to obtain excellent moldability. If it is required to have higher moldability, the storage elastic modulus at 170 ° C is preferably 50 MPa or less, and preferably 20 MPa or less. Further, as the lower limit of the storage elastic modulus, it is preferably 0.5 MPa or more. By setting the storage elastic modulus to 0.5 MPa or more, the drawdown of the laminated film can be suppressed when the laminated film is placed in a vacuum forming machine or a vacuum pressure forming machine.

In addition, if the storage modulus of the laminated film is less than In the case of 0.5 MPa, in the case where the electromagnetic wave shielding layer transfer film is thermoformed by FPC, the thickness of the electromagnetic wave shielding layer transfer film existing in the portion sandwiched between the convex portion of the FPC and the heated metal plate is significantly changed. Thin case. As a result, in the step of peeling off the laminated film after hot press forming, the peeling stress concentrates on the thin portion of the thickness of the electromagnetic wave shielding layer transfer film, so that the laminated film is broken. On the other hand, when the storage elastic modulus of the laminated film is 0.5 MPa or more, the fracture of the laminated film can be suppressed.

In the laminated film of the present invention, as a storage at 170 ° C The method in which the elastic modulus is 100 MPa or less is a method of adjusting the glass transition temperature of the layer A, and the like.

Here, "the storage elastic modulus at 120 ° C is 101 MPa. The storage elastic modulus of 3,000 MPa or less and 170 ° C is 100 MPa or less, which means that the above numerical value is satisfied in any direction of the laminated film and in a direction orthogonal to the direction.

In the laminated film of the present invention, further attention is paid to processing In the case of sex, the storage elastic modulus at 130 ° C is preferably 101 MPa. Above 3,000 MPa. The storage elastic modulus at 130 ° C is more preferably 500 MPa or more and 3,000 MPa or less, and more preferably 1,000 MPa or more and 3,000 MPa or less.

In the laminated film of the present invention, in order to be buried deeper during molding, the storage elastic modulus at 160 ° C is preferably 100 MPa or less, and the storage elastic modulus at 150 ° C is more preferably 100 MPa or less.

(additive)

The laminated film of the present invention may contain a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a plasticizer, an adhesion imparting agent, a defoaming agent such as polysiloxane, a pigment or the like according to an appropriate amount. A coloring agent such as a dye. Further, it can contain talc, mica, cerium oxide, aluminum oxide, titanium oxide, zeolite, glass, montmorillonite, hectorite, AEROSIL, zinc oxide, iron oxide, carbon black, graphite, organic to the extent that the effects of the present invention are not impaired. A powdery or fibrous filler such as a metal salt or an oxidized metal. Can be blended for use.

The antioxidant is not particularly limited, and any of a well-known phosphite-based antioxidant, an organic sulfur-based antioxidant, and a hindered phenol-based antioxidant can be used.

[Examples]

The production and evaluation of the laminated film were carried out in the following manner.

(1) The total thickness of the laminated film and the thickness of each layer

When the overall thickness of the laminated film is to be measured, the thickness of any of the 5 mm long and 10 mm wide samples of the laminated film is measured by a gauge, and the average value is determined. In addition, when the layer thickness of each layer of the equivalent laminated film is used, a metal microscope is used. Leica DMLM (manufactured by Leica MICROSYSTEMS), a light-transmissive photograph was taken on a section of the film at a magnification of 100 times. Thereafter, from the photographs taken, the thickness of any five layers was measured for each layer of the laminated film, and the average value thereof was used as the layer thickness of each layer.

(2) Glass transfer temperature, melting point, and crystal melting heat

The measurement and analysis were carried out in accordance with JIS K7121-1987 and JIS K7122-1987 using a differential scanning calorimeter (RDC220 manufactured by SEIKO Electronics Co., Ltd.). Take 5 mg as a sample, and read the specific heat change caused by the transfer of the sample from the glass state to the rubber state when the sample was heated from 25 ° C to 20 ° C / min to 300 ° C. The intermediate point of the intersection of the straight line parallel to the straight line and the curve of the phase change portion of the glass transition at the equidistance (intermediate point) in the direction in which the straight line extending each line is extended is obtained. The glass transition temperature is set to the glass transition temperature. Further, when there are a plurality of glass transition temperatures, the glass transition temperature on the high temperature side is used as the glass transition temperature.

Further, the peak temperature of the endothermic melting curve when the sample was heated from 25 ° C to 20 ° C / min to 300 ° C was taken as the melting point.

Further, the area of the portion surrounded by the baseline and the endothermic melting curve was taken as the heat of melting crystallization.

Further, the film having the laminated structure was confirmed by the method of (1), and the surface layer and the inner layer were cut to measure the glass transition temperature and melting point of each layer.

Further, for example, the glass transition temperature of the cyclic olefin resin is close to the melting temperature of the polypropylene resin or the polyethylene resin, so that the curve of the stepwise change portion of the glass transition temperature overlaps with the melting point peak. In the case of the intermediate point glass transition temperature and melting point value read by the overlapping peaks.

(3) Surface free energy of layer B

Under the conditions of 23 ° C and 65% RH, the contact film was used for 24 hours of humidification using a contact angle meter (CA-D type of Kyowa Interface Chemical Co., Ltd.), and water, ethylene glycol, formamide and diiodine were used. For the four kinds of measuring liquids of methane, the contact angle meter CA-D type made by the Kyowa Interface Chemical Co., Ltd. was used to determine the static contact angle with the surface of the film. Each component of the contact angle with respect to each liquid and the surface tension of the measuring liquid was substituted into the following formula, and the quaternary equation including the formula of 4 was solved for γ ^L , γ ⁺ , and γ ⁻ .

(γ ^L γ _j ^L ) ^1/2 +2(γ ⁺ γ _j ^- ) ^1/2 +2(γ _j ⁺ γ ^- ) ^1/2 =(1+cosθ)[γ _j ^L +2(γ _j ⁺ γ _j ^- ) ^1/2 ]/2

However, γ = γ ^L + 2 (γ ⁺ γ _- ) ^1/2 γ _j = γ _j ^L + 2 (γ _j ⁺ γ _j ^- ) ^1/2 . Here, γ, γ ^L , γ ⁺ , γ ⁻ respectively represent the surface free energy of the surface of the film, the long-distance force term, the Lewis acid parameter, and the Lewis base parameter; and γ _j , γ _j ^L , γ _j ⁺ , γ _j ^- respectively indicates the surface free energy, the long distance force term, the Lewis acid parameter, and the Lewis base parameter of the measuring liquid used.

The surface tension of each of the liquids used herein is the value of Table 1 proposed by Oss ("Fundamentals of Adhesion", L.H. Lee (Ed.), p153, Plenum ess, New York (1991).

(4) Storage elastic modulus

A film was cut into a rectangular shape of 60 mm × 5 mm in width in any direction and in a direction orthogonal to the direction to prepare a sample. The storage elastic modulus (E') at 120 ° C and 170 ° C was measured by a dynamic viscoelasticity measuring device (DVE-V4 FT Rheospectra, manufactured by Rheology) under the following conditions.

Frequency: 10 Hz, sample length (distance between chucks): 20 mm, displacement amplitude: 10 μm; measurement temperature range: 25 ° C to 200 ° C, temperature increase rate: 5 ° C / min.

(5) Peel strength between layer A and layer B

Nippon Electric Co., Ltd. OPP tape (Dunplon Ace No. 375) was adhered to one side of the laminated film, and cut into a rectangle having a width of 10 mm and a length of 150 mm to prepare a sample. The sample was forcibly peeled off at the laminate interface, and a 180° peel test was performed by using a tensile tester (TENSILON UCT-100 manufactured by Orientec) and setting a distance between the initial stretching chucks of 100 mm and a stretching speed of 20 mm/min. The measurement was carried out until the peeling length was 130 mm (the distance between the chucks was 230 mm), and the average value of the load of the peeling length of 25 mm to 125 mm was taken as the peeling strength. In addition, the measurement system was carried out 5 times, and the average value was used. In the case of a three-layer structure such as a B layer/A layer/B layer, a peeling test was performed on both surfaces, and an average value of five times on each side and a total of ten times on both sides was used.

In addition, the peel strength was measured in a room where the temperature was adjusted to 25 °C.

(6) Surface roughness

Both sides were measured using a surface roughness meter (SE4000 manufactured by Otaru Research Institute). Radius at the front end of the stylus is 0.5μm, measuring force The measurement was performed under conditions of 100 μN, a measurement length of 1 mm, a low-range intercept value of 0.200 mm, and a high-range interception value of 0.000 mm, and an arithmetic mean roughness SRa was obtained in accordance with JIS B0601-2001.

(7) Haze

It was measured by a haze meter (NDH7000 manufactured by Nippon Electric Industrial Co., Ltd.) in accordance with JIS K7136-2000. When any surface of the laminated film is the A surface and the other surface is the B surface, the haze value is measured 5 times with the incident surface of the light as the A surface. Thereafter, the incident surface of the light was changed to the B surface, and the haze value was measured 5 times. The average of the measured values of 10 times in total was obtained as the haze value of the laminated film.

(8) tone L value

The measured value in the breakthrough mode according to the Hunter method was measured by a colorimeter (Suga test mechanism SM-T) in accordance with JIS P8123-1961. When any one surface of the laminated film is the A surface and the other surface is the B surface, the color tone L value is measured five times with the light incident surface as the A surface. Thereafter, the incident surface of the light was changed to the B surface, and the tone L value was measured 5 times. The average of the measured values for the total of 10 times was obtained as the hue L value of the laminated film.

(9) Formability

A 10 cm square brass plate having a comb pattern of L/S=100 μm/100 μm and a depth of 300 μm was formed on the surface of the FPC, and the laminated film was placed on both sides of the brass plate and the laminated film at 150 ° C. 4 MPa was hot pressed by a press for 30 minutes to prepare a sample for evaluation. Here, L means the length of the width of the mountain portion in the comb pattern (i.e., the line width (L width) in the FPC); and S refers to the length of the width of the valley portion (i.e., the space width (S width) of the FPC). In other words, the comb patterns are equally spaced One of the convex portions has a width L and the convex portion has an S width. The cross section of the sample for evaluation after punching was observed using a Microscope VHX-2000 manufactured by KEYENCE, and it was judged that it was judged by a close contact with no more than 9 of the comb patterns at 10 places.

Then, in addition to the depths of 500 μm, 800 μm, and 1,000 μm, samples for evaluation of the same brass plate as described above were prepared and evaluated according to the following criteria.

S: It is a pattern of depth of 1,000 μm and is qualified.

A: It is a pattern with a depth of 1,000 μm, which is unqualified, but is a pattern with a depth of 800 μm.

B: It is a pattern with a depth of 800 μm, which is unqualified, but is a pattern having a depth of 500 μm, which is acceptable.

C: It is a pattern of 500 μm in depth, which is unqualified, but is a pattern with a depth of 300 μm.

D: It is a pattern with a depth of 300 μm, which is unqualified.

(10) Demoulding

100 parts by mass of an epoxy-based adhesive ("AS-60" manufactured by Toagosei Co., Ltd.) was mixed with 150 parts by mass of silver-coated copper powder having a 50% particle diameter (median diameter) of 5.9 μm (Futian metal foil) A conductive paste of "Cu-HWQ5 μm" manufactured by Powder Industries was applied to the side of the B layer of the laminated film to form a functional resin layer (conductive layer), thereby forming an electromagnetic wave shielding layer transfer film. Further, the applicator was used for the coating system, and the coating thickness before drying was 100 μm, and the drying conditions were 100 ° C for 10 minutes. After drying, it was cut into a rectangle having a width of 10 mm and a length of 150 mm to prepare a sample. The sample was forcibly peeled off at the laminate interface and evaluated according to the following criteria.

A: It can be peeled off without resistance.

B: Although resistance was felt at the time of peeling, the functional resin layer (conductive layer) was not transferred to the side of the laminated film.

C: A part of the functional resin layer (conductive layer) was peeled off and transferred to the side of the laminated film.

D: The laminated film and the functional resin layer (conductive layer) have strong adhesion and cannot be forcibly peeled off.

(11) Processing suitability

A film was cut into a rectangular shape of 50 mm × 4 mm in width in any direction and in a direction orthogonal to the direction to prepare a sample. A thermomechanical analyzer (TMA EXSTAR6000 manufactured by Seiko Instruments) was used for the sample, and the temperature was raised under the following conditions. During the heating process, the temperature was changed to 1.0% according to the dimensional change rate, and the evaluation was performed based on the following criteria. Moreover, the dimensional change rate is measured to one decimal place.

Sample length: 15mm, load: 19.6mN, heating rate: 5°C/min, measuring temperature range: 25~220°C

Dimensional change rate (%) = {|sample length (mm) - film length after holding (mm) | / sample length (mm)} × 100

S: 130 ° C or more

A: 125 ° C or more and less than 130 ° C

B: 120 ° C or more and less than 125 ° C

C: 100 ° C or more and less than 120 ° C

D: less than 100 ° C.

(12) Adhesion to functional resin layer

The functional resin layer (conductive layer) described in (10) was applied onto the film by a die coater to prepare an electromagnetic wave shielding layer transfer film. Further, the drying conditions were 100 ° C for 10 minutes, and the thickness of the functional resin layer (conductive layer) after drying was adjusted to 50 μm. A transfer film of 500 mm wide and 200 m long electromagnetic wave shielding layer wound around a core having a diameter of 6 吋 and a width of 550 mm was prepared, and a winding core having a diameter of 3 inches and a width of 550 mm was bundled according to the following conditions, according to the following criteria. Conduct an assessment.

Winding tension: 100N/m

Speed: 5m/min

A: No peeling occurred between the film layer/functional resin layer (conductive layer).

B: Peeling was observed between the film layer/functional resin layer (conductive layer), but no air entrapment occurred at the peeling point.

C: Peeling was observed between the film layer/functional resin layer (conductive layer), and air entrapment occurred at the peeling place.

(13) Warpage resistance

The electromagnetic wave shielding layer transfer film obtained in the same manner as in (12) was evaluated for the ease of handling of the press machine installed in the A4 size according to the following criteria.

A: There is no warpage, and the film can be set without any problem.

B: Warpage can be seen, and it is necessary to fix the electromagnetic wave shielding layer transfer film with a tape beforehand in the press machine.

(14) Adhesion between layer A and layer B

10 pieces of the film were cut into a size of 15 mm × 110 mm, and the MIT folding test machine (MID-D manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used at a rotation speed of 175 cpm, and the load was measured: 25 N (250 gf), and the bending angle was: A sample for evaluation of bending of the film for 10 times under conditions of 135 ° was visually evaluated according to the following criteria.

A: No peeling occurred between the layers at the bend.

B: It was found that more than one sample which was peeled off at the end portion of the bending portion was observed, but no sample in which the peeling portions at both ends of the one bent portion were connected to each other was observed.

C: A sample in which the peeling portions at both ends of one or more of the bending portions of less than five were connected to each other was observed.

D: A sample in which the peeling portions at both ends of the five or more bending portions are connected to each other can be seen.

(15) Stamping heat resistance

The film was cut into strips (rectangular) having a width of 10 mm and a length of 100 mm to obtain a sample. Thereafter, marks (straight lines) are drawn with black oily ink in the width direction every 10 mm in length. In other words, a straight line (mark) is drawn in a direction parallel to the width direction of the sample at a position 10 mm from one end in the longitudinal direction of the sample. Further, at this position from the position, a straight line (mark) is drawn in a direction parallel to the width direction of the sample at a position spaced apart by 10 mm in the longitudinal direction of the film. The same operation was repeated, and a total of nine straight lines (marks) were drawn on the sample.

A rectangular film (sample) was sandwiched between 120 mm of each polyimide film ("Kapton (registered trademark)" manufactured by Du Pont-Toray Co., Ltd.) 100H. Both sides were hot pressed by a press at 150 ° C and 4 MPa from both sides through an iron plate for 30 minutes. After the hot pressing was completed, the rectangular film was peeled off from the polyimide film, and the average value of the lengths of the eight black oily inks was determined and evaluated according to the following criteria. That is, the distance between all adjacent straight lines (marks) (the distance in the longitudinal direction of the film) is obtained. The obtained eight values were averaged to obtain an average value, and the evaluation was performed based on the following criteria.

A: The average width of the rectangle (the distance between the straight lines (marks)) is 10 mm or more and less than 10.5 mm.

B: The average width of the rectangle (the distance between the straight lines (marks)) is 10.5 mm or more and less than 11 mm.

C: The average width of the rectangle (the distance between the straight lines (marks)) is 11 mm or more and less than 12 mm.

D: The average value of the width of the rectangle (the distance between the straight lines (marks)) is 12 mm or more.

(16) Visual identity

After the film was cut into a shape of 1 mm × 5 mm, it was placed at any position of the B4 size black cardboard, so that the observer located at a position away from 2 m sought the position of the film. The observers are exchanged and evaluated according to the following criteria.

A: Of the 5 observers, 5 found the film within 10 seconds.

B: Among the five observers, one or more of the four or less were found to have a film within 10 seconds.

C: None of the five observers found the film within 10 seconds.

(17) Resin used in the production of the laminated film of the present invention (Cyclic olefin copolymer resin A (COC-A))

"TOPAS (registered trademark)" 6013F-04 (a resin obtained by copolymerizing ethylene and norbornene) having a glass transition temperature of 138 ° C and having a total composition of the resin of 100% by mass, derived from norbornene The mass ratio of the portion of the (cyclic olefin) was estimated to be 76% by mass, and the mass ratio of the portion derived from ethylene (chain olefin) was estimated to be 24% by mass.

(Cyclic olefin copolymer resin B (COC-B))

"TOPAS (registered trademark)" 8007F-04 (a resin obtained by copolymerizing ethylene and norbornene) having a glass transition temperature of 78 ° C and having a total composition of the resin of 100% by mass, derived from norbornene The mass ratio of the portion of the (cyclic olefin) is estimated to be 64% by mass, and the mass ratio of the portion derived from ethylene (chain olefin) is estimated to be 36% by mass.

(Cyclic olefin resin C (COP-C))

"ZEONOR (registered trademark)" 1420R (a cyclic olefin resin having a glass transition temperature of 135 ° C) manufactured by ZEON, Japan was used.

(cyclic olefin resin D (COC-D))

"TOPAS (registered trademark)" 6017S-04 (a resin obtained by copolymerization of ethylene and norbornene), a glass transition temperature of 178 ° C, and a total component of the resin of 100% by mass, derived from hail The mass ratio of the portion of the olefin (cyclic olefin) is estimated to be 82% by mass, and the mass ratio of the portion derived from ethylene (chain olefin) is estimated to be 18% by mass.

(Calcium Olefin Copolymerized Resin A (COC-A) Titanium Oxide Mixture) (COC-T)

100 parts by mass of "TOPAS (registered trademark)" 6013F-04 (a resin obtained by copolymerization of ethylene and norbornene) having a glass transition temperature of 138 ° C and a total composition of the resin of 100% by mass. The mass ratio of the portion of the self-decreasing terpene (cyclic olefin) is estimated to be 76% by mass, the mass ratio of the portion derived from ethylene (chain olefin) is estimated to be 24% by mass), and 100 parts by mass of the titanium oxide particles ( Titan industrial "KA-10") was kneaded and extruded at 280 ° C using a twin-screw extruder to obtain a fine gut. The obtained fine lines are cooled by water and cut into pieces.

(Metal aromatic linear low density polyethylene resin (m-LLDPE))

"Evolue (registered trademark)" SP2540 manufactured by Prime Polymer (MFR of 3.8 g/10 min according to JIS K7210-1999, melting point of 123 ° C, density determined according to JIS K6922-2-2010, 0.924 g/cm ³ , It is a resin obtained by copolymerizing ethylene and 1-hexene (the content ratio of 1-hexene is 5 mol% or less), and a metal aromatic linear low-density polyethylene resin).

(Linear Medium Density Polyethylene Resin (LMDPE))

"ULTZEX (registered trademark)" 4050 manufactured by Prime Polymer (MFR of 6 g/10 min according to JIS K7210-1999, melting point of 125 ° C, density determined according to JIS K6922-2-2010, 0.937 g/cm ³ , genus A resin obtained by copolymerizing ethylene and 1-hexene (content ratio of 1-hexene is 5 mol% or less), and linear low-density polymerization by polymerization of a catalyst different from a metal aromatic catalyst Vinyl resin).

(Low Density Polyethylene Resin (LDPE))

"Sumikathene (registered trademark)" F412-1 manufactured by Sumitomo Chemical Co., Ltd. (MFR according to JIS K7210-1999 is 5 g/10 min, melting point is 110 ° C, and density determined according to JIS K6922-2-2010 is 0.921 g/cm ³ Low density polyethylene resin).

(High Density Polyethylene Resin (HDPE))

"HI-ZEX (registered trademark)" 2200J manufactured by Prime Polymer (MFR according to JIS K7210-1999 is 5.2 g/10 min, melting point is 135 ° C, and density determined according to JIS K6922-2-2010 is 0.921 g/cm. ³ high density polyethylene resin).

(polypropylene resin E (PP-E))

"Nobrene (registered trademark)" R101 (manufactured by Sumitomo Chemical Co., Ltd.) R101 (having a MFR of 19 g/10 min according to JIS K7210-1999, a melting point of 160 ° C, and a homopolypropylene resin containing only a component derived from propylene).

(Polypropylene resin F (PP-F))

"Prime Polypro (registered trademark)" E111G (a MFR of 0.5 g/10 min according to JIS K7210-1999, a melting point of 164 ° C, and a homopolypropylene resin containing only a component derived from propylene) was used.

(Polypropylene resin (ethylene-propylene random copolymer resin) (EPC))

"Prime Polypro (registered trademark)" Y-2045GP manufactured by Prime Polymer Co., Ltd. (density according to JIS K6922-2-2010 is 0.91 g/cm ³ , MFR according to JIS K7210-1999 is 24 g/10 min, melting point is A resin of 145 ° C, an ethylene-propylene random copolymer resin (polypropylene resin) obtained by polymerizing a ratio of 4% by mass of ethylene to 96% by mass of propylene.

(ethylene-based copolymer resin G (E-co-G))

"Affinity (registered trademark)" manufactured by Dow Chemical Co., Ltd. is used according to EG8200 (JIS-K7112 (1999) has a density of 0.86 g/cm ³ and an ethylene-derived component of 76% by mass (ethylene content is 92.7 mol). %), an ethylene-octene copolymer resin derived from an octene component of 24% by mass (octene content: 7.3 mol%).

(styrene-ethylene-butylene-styrene copolymer resin H (SEBS-H))

"Tuftec (registered trademark)" H1051 (a density of 0.93 g/cm ³ according to JIS-K7112 (1999) and 42% by mass of styrene-ethylene-butene derived from styrene) - styrene copolymer resin).

(petroleum resin)

"ALKON (registered trademark)" P100 (a completely hydrogenated petroleum resin containing a C9 fraction as a main component at a softening point of 100 ° C according to JIS K2207-1996) was used.

(polymethylpentene resin (PMP))

"TPX (registered trademark)" MX002 (polymethylpentene resin having a melting point of 224 ° C) manufactured by Mitsui Chemicals Co., Ltd. was used.

(slip agent)

"NEUTRON-S (registered trademark)" (erucic acid decylamine) manufactured by Nippon Seika Co., Ltd., "NEUTRON (registered trademark)" (oleic acid amide) manufactured by Nippon Seika Co., Ltd., and "ALFLOW AD281F (registered trademark)" manufactured by Nippon Oil Co., Ltd. (Ethylene bismuth oleate) These three kinds are mixed in 100 parts by mass each.

(Example 1)

It is made into a three-layer structure. The composition of each layer was supplied to a uniaxial extruder (L/D=28) as shown in the table, and melted at a supply unit temperature of 240 ° C and a subsequent temperature of 260 ° C, and passed through a filtration precision of 20 μm. After the leaf disk filter, it is layered in the layerer of the upper part of the mold by layer B/A layer/B layer (the thickness of each layer is referred to the attached table), and then controlled from the T-shaped mold. The metal roll (SRa = 0.03 μm) at a temperature of 85 ° C was discharged into a film form. At this time, it was clamped with a rubber roller (SRa = 0.6 μm) (nip pressure: 0.2 MPa) to obtain a laminated film having a thickness of 100 μm. The obtained film was evaluated according to the methods described in (1) to (16). In addition, as for the surface roughness SRa of the metal roll and the rubber roll, a cellulose triacetate film (manufactured by BIODEN RFA Co., Ltd., which is dissolved in a cellulose triacetate solvent (methyl acetate)) is used to make cellulose triacetate. The film was applied with a line pressure of 9.8 N/cm on the roll surface by a pressure roller and the surface shape of the transfer roll was dried, and the solvent was dried at room temperature, and the replicated sample was used as a quantity test sample for measurement. The moldability, the adhesion to the functional resin, the warpage resistance, and the adhesion to the A layer/B layer were all good. In addition, in the thickness ratio of each layer, the 1/2/1 system shown in the table indicates the layer structure (B/A/B in the case of Example 1) described in the table with respect to the total thickness of the film of 100 μm. Each layer is composed of a thickness ratio of 1/2/1, that is, a form of B layer/A layer/B layer=1/2/1 (=25 μm/50 μm/25 μm). Still, the same applies to other embodiments or comparative examples.

(Example 2)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer B was changed to LMDPE. According to the obtained film The results of the methods described in (1) to (16) were evaluated, and approximately the same results as in Example 1 were obtained.

(Example 3)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer B was changed to LDPE. As a result of evaluating the obtained film according to the methods described in (1) to (16), the heat resistance of the press was inferior to that of Example 1.

(Example 4)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer B was changed to HDPE. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was inferior to that of Example 1.

(Example 5)

A laminated film was obtained in the same manner as in Example 1 except that the laminated structure was changed to the two-layer structure of the A layer/B layer. As a result of evaluating the obtained film according to the methods described in (1) to (16), the warp resistance was inferior to that of Example 1.

(Example 6)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer B was changed to PP-E. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was inferior to that in Example 1, but the mold release property and the press heat resistance were good.

(Example 7)

A laminate film was obtained in the same manner as in Example 6 except that the composition of the layer B was changed to PP-F. The results obtained by evaluating the obtained film according to the methods described in (1) to (16) gave approximately the same results as in Example 6.

(Example 8)

A laminate film was obtained in the same manner as in Example 7 except that the layer B was a petroleum resin. As a result of evaluating the obtained film according to the methods described in (1) to (16), the release property was inferior to that of Example 7, but the adhesion between the A layer and the B layer was good.

(Example 9)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer A was changed and the Tg of the layer A was changed to 97 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the workability and the heat resistance of the press were inferior compared to Example 1.

(Embodiment 10)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer A was changed, the Tg of the layer A was 172 ° C, and the temperature of the supply portion of the extruder was 265 ° C and the subsequent temperature was 275 ° C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability was good, but the moldability and the adhesion between the A layer and the B layer were inferior.

(Example 11)

A laminate film was obtained in the same manner as in Example 1 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A/B layers was inferior to that in Example 1, but the processing suitability was good.

(Embodiment 12)

A laminate film was obtained in the same manner as in Example 1 except that the laminate ratio was changed and the thickness of the layer B was decreased. The results obtained by evaluating the obtained film according to the methods described in (1) to (16) gave approximately the same results as in Example 1.

(Example 13)

A laminate film was obtained in the same manner as in Example 1 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the workability was better than that of Example 1.

(Example 14)

A laminate film was obtained in the same manner as in Example 1 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability was inferior compared to Example 1.

(Example 15)

A laminate film was obtained in the same manner as in Example 1 except that the total thickness was reduced. As a result of evaluating the obtained film according to the methods described in (1) to (16), the moldability and the adhesion between the A layer and the B layer were inferior to those in Example 1.

(Embodiment 16)

A laminate film was obtained in the same manner as in Example 1 except that the total thickness was reduced. As a result of evaluating the obtained film according to the methods described in (1) to (16), the moldability was inferior to that of Example 1.

(Example 17)

A laminate film was obtained in the same manner as in Example 15 except that the total thickness was reduced. As a result of evaluating the obtained film according to the methods described in (1) to (16), the moldability, the workability, and the adhesion between the A layer and the B layer were inferior to those of Example 15.

(Embodiment 18)

A laminate film was obtained in the same manner as in Example 16 except that the layer thickness was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the heat resistance of the press was inferior to that of Example 16.

(Embodiment 19)

A laminate film was obtained in the same manner as in Example 1 except that the layer B was a lubricant. As a result of evaluating the obtained film according to the methods described in (1) to (16), the mold release property was good as compared with Example 1, but the adhesion between the A layer and the B layer was poor.

(Embodiment 20)

A laminate film was obtained in the same manner as in Example 1 except that the layer B contained COC-B. The obtained laminated film was subjected to surface treatment by a corona treatment machine at an E value of 3 on both sides. As a result of evaluating the obtained film according to the methods described in (1) to (16), the mold release property and the adhesion between the A layer and the B layer were inferior to those of Example 1.

(Example 21)

A laminate film was obtained in the same manner as in Example 1 except that the layer B contained a lubricant and a PMP. As a result of evaluating the obtained film according to the methods described in (1) to (16), the mold release property was good as compared with Example 1, but the adhesion to the functional resin layer and the adhesion between the A layer and the B layer were good. Poor connection. Further, two points were detected in terms of the melting point, and the heat of crystal melting was determined separately, and the respective values are shown in the table.

(Example 22)

A laminate film was obtained in the same manner as in Example 20 except that the COC-B concentration in the layer B was increased and the E value of the corona treatment machine was set to 10. As a result of evaluating the obtained film according to the methods described in (1) to (16), the mold release property was inferior to that of Example 20.

(Example 23)

A laminate film was obtained in the same manner as in Example 6 except that the composition of the layer A was changed and the Tg of the layer A was 126 °C. The results obtained by evaluating the obtained film according to the methods described in (1) to (16) gave approximately the same results as in Example 6.

(Example 24)

A laminate film was obtained in the same manner as in Example 23 except that the composition of the layer A was changed and the Tg of the layer A was changed to 130 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability was better than that of Example 23.

(Embodiment 25)

A laminate film was obtained in the same manner as in Example 24 except that the composition of the layer A was changed and the Tg of the layer A was 138 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability was better than that in Example 24.

(Example 26)

A laminate film was obtained in the same manner as in Example 6 except that the composition of the layer A was changed and the Tg of the layer A was changed to 145 °C. Right place The film was evaluated according to the methods described in (1) to (16), and about the same results as in Example 25 were obtained.

(Example 27)

A laminate film was obtained in the same manner as in Example 6 except that the composition of the layer A was changed and the Tg of the layer A was 155 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the moldability and the adhesion between the layer A and the layer B were inferior to those in the example 26.

(Embodiment 28)

A laminate film was obtained in the same manner as in Example 25 except that the m-LLDE of the layer A was changed to the ethylene-based copolymer resin (E-co-G) and the concentration in the table was adjusted. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was better than that in Example 25.

(Example 29)

A laminate film was obtained in the same manner as in Example 28 except that the concentration of the ethylene-based copolymer resin was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was better than that in Example 28.

(Embodiment 30)

A laminate film was obtained in the same manner as in Example 29 except that the concentration of the ethylene-based copolymer resin was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability was inferior to that of Example 29.

(Example 31)

A laminate film was obtained in the same manner as in Example 30 except that the concentration of the ethylene-based copolymer resin was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability and the stamping heat resistance were inferior to those in Example 30.

(Example 32)

A laminate film was obtained in the same manner as in Example 29 except that the ethylene copolymer resin was changed to a styrene-ethylene-butylene-styrene copolymer resin. As a result of evaluation of the obtained film according to the methods described in (1) to (16), the processing suitability and the phase-to-phase adhesion between the A layer and the B layer were inferior compared to Example 29.

(Example 33)

A laminated film was obtained in the same manner as in Example 29 except that the temperature of the metal roll was 40 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the phase-to-phase adhesion between the A layer and the B layer was inferior to that in Example 29.

(Example 34)

A laminated film was obtained in the same manner as in Example 33 except that the temperature of the metal roll was 25 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the phase-to-phase adhesion between the A layer and the B layer was inferior compared to Example 33.

(Example 35)

A laminated film was obtained in the same manner as in Example 29 except that the temperature of the metal roll was 120 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the formability was inferior to that of Example 29.

(Example 36)

A laminate film was obtained in the same manner as in Example 1 except that the composition of the layer B was changed to EPC. As a result of evaluating the obtained film according to the methods described in (1) to (16), the heat resistance of the press was better than that of Example 1.

(Example 37)

A laminate film was obtained in the same manner as in Example 29 except that the laminate ratio was changed and the thickness of the layer B was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the workability and the heat resistance of the press were inferior to those of Example 29.

(Example 38)

A laminate film was obtained in the same manner as in Example 29 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was inferior to that in Example 29.

(Example 39)

A laminate film was obtained in the same manner as in Example 29 except that the type of the ethylene copolymer resin was changed. As a result of evaluating the obtained film according to the methods described in (1) to (16), moldability and press heat resistance were inferior compared to Example 29.

(Embodiment 40)

A laminate film was obtained in the same manner as in Example 29 except that the layer A contained COC-T. As a result of evaluating the obtained film according to the methods described in (1) to (16), the visual recognition property was better than that of Example 29 and Example 31.

In addition, although the COC-T contains titanium oxide, the column "the ratio (% by mass) of the cyclic olefin resin of the A layer" in the table describes the content of the titanium oxide-free resin, that is, only the cyclic olefin resin. The content. In other words, in the column of "the ratio (% by mass) of the cyclic olefin resin of the A layer" in the example 40 in the table, the total amount of COC-A and COC-T constituting the layer A is subtracted from the titanium oxide. The value of the content of a substance other than the cyclic olefin system. Still, the same applies to other embodiments or comparative examples.

(Example 41)

A laminate film was obtained in the same manner as in Example 40 except that the content of COC-T in the layer A was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the visibility was better than that of Example 40.

(Example 42)

A laminate film was obtained in the same manner as in Example 40 except that the content of COC-T in the layer A was increased. The results of the evaluation of the obtained film according to the methods described in (1) to (16) gave the same results as in Example 40.

(Example 43)

A laminate film was obtained in the same manner as in Example 42 except that the content of COC-T in the layer A was increased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was inferior to that in Example 42.

(Example 44)

A laminate film was obtained in the same manner as in Example 43 except that the content of COC-T in the layer A was increased. According to the obtained film As a result of the evaluation by the methods described in (1) to (16), the adhesion to the functional resin layer was inferior to that of Example 43.

(Example 45)

A laminated film was obtained in the same manner as in Example 29 except that the surface roughness SRa of the metal roll was 0.05 μm and the temperature of the metal roll was 30 °C. The results obtained by evaluating the obtained film according to the methods described in (1) to (16) gave approximately the same results as in Example 29.

(Example 46)

A laminated film was obtained in the same manner as in Example 29 except that the surface roughness SRa of the metal roll was 0.05 μm. As a result of evaluating the obtained film according to the methods described in (1) to (16), the visual recognition property was better than that of Examples 29 and 45.

(Example 47)

A laminated film was obtained in the same manner as in Example 46 except that the surface roughness SRa of the metal roll was 0.63 μm. As a result of evaluating the obtained film according to the methods described in (1) to (16), the visual recognition property was better than that of Example 46.

(Example 48)

A laminated film was obtained in the same manner as in Example 47 except that the surface roughness SRa of the metal roll was 3.0 μm and the temperature of the metal roll was 30 °C. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion to the functional resin layer was inferior to that of Example 47.

(Example 49)

A laminated film was obtained in the same manner as in Example 29 except that the surface roughness SRa of the metal roll was 3.0 μm. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion to the functional resin layer was inferior to that of Example 48.

(Example 50)

A laminate film was obtained in the same manner as in Example 29 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the adhesion between the A layer and the B layer was inferior to that in Example 29.

(Example 51)

A laminate film was obtained in the same manner as in Example 50 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the moldability was better than that of Example 50.

(Example 52)

A laminate film was obtained in the same manner as in Example 51 except that the laminate ratio was changed and the thickness of the layer B was decreased. The obtained film was evaluated according to the method described in (1) to (16), and the same results as in Example 51 were obtained.

(Example 53)

A laminate film was obtained in the same manner as in Example 52 except that the laminate ratio was changed and the thickness of the layer B was decreased. As a result of evaluating the obtained film according to the methods described in (1) to (16), the mold release property was inferior to that of Example 51.

(Example 54)

A laminate film was obtained in the same manner as in Example 29 except that the ratio of the cyclic olefin resin of the A layer was lowered. The results obtained by evaluating the obtained film according to the methods described in (1) to (16) gave approximately the same results as in Example 29.

(Example 55)

A laminate film was obtained in the same manner as in Example 54 except that the ratio of the cyclic olefin resin of the A layer was lowered. As a result of evaluating the obtained film according to the methods described in (1) to (16), the processing suitability was inferior to that of Example 54.

(Example 56)

A laminated film was obtained in the same manner as in Example 29 except that the laminated structure was changed to the two-layer structure of the A layer/B layer. As a result of evaluating the obtained film according to the methods described in (1) to (16), the warpage resistance was inferior to that of Example 29.

(Comparative Example 1)

It is made into a single layer structure. The mixed resin was composed as shown in the table, and supplied to a uniaxial extruder (L/D = 28). The mixture was melted at a supply temperature of 240 ° C and a subsequent temperature of 260 ° C, and filtered through a filtration precision of 20 μm. Disc. Thereafter, it was discharged into a sheet shape from a T-die (lip gap: 0.4 mm) on a metal roll controlled to 85 °C. At this time, it was clamped with a rubber roller (clamping pressure: 0.2 MPa) to obtain a single-layer film having a thickness of 100 μm. The obtained film was evaluated according to the methods described in (1) to (16).

(Comparative Example 2)

A single-layer film was obtained in the same manner as in Comparative Example 1, except that the composition was as shown in the table, and the temperature of the supply portion of the extruder was 190 ° C and the subsequent temperature was 220 ° C. The obtained film was evaluated according to the methods described in (1) to (16).

(Comparative Examples 3 and 4)

A laminate sample was obtained in the same manner as in Example 1 except that the composition was as shown in the table. The obtained film was evaluated according to the methods described in (1) to (16).

The details of the respective examples and comparative examples are shown in the table.

In addition, in the application of the electromagnetic wave shielding layer transfer film which is required to have a correspondence with a fine shape, it is preferable that the moldability is S, and the adhesion between the A layer and the B layer is C. When peeling and transferring from a deep-drawn molded body (that is, a molded body having an increased molding magnification) as a decorative use, since the film corresponding to the depth is to be peeled off, the moldability is evaluated by A or more, and between A and B layers. The adhesion is particularly good for B.

In the table, "PE resin" means "polyethylene resin", and "PP resin" means "polypropylene resin".

Claims (14)

A laminated film having a B layer mainly composed of a polypropylene resin and/or a polyethylene resin as a main component of the A layer containing a cyclic olefin resin as a main component, and only the B layer and the A layer. The three layers of the B layer are composed, and the storage elastic modulus at 120 ° C is 101 MPa or more and 3,000 MPa or less, and the storage elastic modulus at 170 ° C is 100 MPa or less. The laminated film according to claim 1, wherein the glass transition temperature of the layer A is 130 ° C or more and 150 ° C or less. The laminated film according to claim 1 or 2, wherein the A layer contains 15% by mass or more and 40% by mass or less of the ethylene-based copolymer resin when the total of the total components of the layer A is 100% by mass. The laminate film of claim 1 or 2, wherein the surface layer free energy of the layer B is 25 mN/m or more and 35 mN/m or less. The laminated film according to claim 1 or 2, wherein the B layer is mainly composed of a polypropylene resin and further contains a petroleum resin. The laminated film according to claim 1 or 2, wherein the B layer is mainly composed of a polyethylene resin which is a linear low density polyethylene or a high density polyethylene. The laminated film of claim 1 or 2 has a surface roughness SRa of 50 nm or more and 3,000 nm or less on both surfaces. The laminate film of claim 1 or 2 has a haze of 65% or more and 90% or less. The laminated film of claim 1 or 2 has a hue L value of 75 or more and 100 or less. The laminated film of the claim 1 or 2 has a laminate ratio (the total thickness (μm) of the layer B/the thickness (μm) of the layer A) of 0.1 or more and 0.15 or less, and the total thickness of the film is 40 μm or more and 300 μm or less. In the laminated film of the claim 1 or 2, the laminate ratio (the total thickness (μm) of the layer B/the thickness (μm) of the layer A) is 0.25 or more and 2 or less, and the total thickness of the film is 40 μm or more and 300 μm or less. The laminated film according to claim 3, wherein the ethylene-based copolymer resin has a density of 0.84 g/cm ³ or more and 0.86 g/cm ³ or less. A functional resin layer transfer film having the laminated film and the functional resin layer according to any one of claims 1 to 12. A film for packaging having the laminated film according to any one of claims 1 to 12.