JP2011152733A - Laminate film and molding sheet using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate film which has excellent mold releasability and printabiity and is manufactured without including steps for coating and extrusion laminating or the like. <P>SOLUTION: In the laminate film, a polyolefin layer (layer B) containing a polyolefin resin as the major component is laminated on at least one surface side of a polyester layer (layer A) containing an aromatic polyester resin as the major component. The lamination ratio of the layer B in a whole film, the layer B/the whole film=0.05-0.5, and the interlaminar adhesive force between the layer A and the layer B is 1 N/25 mm to 30 N/25 mm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a laminated film obtained by laminating a polyolefin layer mainly composed of a polyolefin resin on at least one surface of a polyester layer mainly composed of an aromatic polyester resin, and more specifically, release properties, molding The present invention relates to a laminated film having excellent properties and printability.

  Films having releasability are widely used in various surface protective films, transfer foils, and the like. The surface protective film is mainly used by being attached to adherends such as resin parts, metal products, glass products and the like, and plays a role of preventing scratches or foreign matter contamination during transportation, storage or processing. These surface protective films are required to have an appropriate adhesion to the adherend while being used as a protective film, and an appropriate releasability so that the protective film can be easily removed when the product is used. In the case of protecting a molded body having a three-dimensional shape, the surface protection film is required to have moldability in addition to adhesion and releasability.

  The transfer foil is formed by laminating a layer to be transferred (for example, a clear layer / decorative layer / adhesive layer) on one side of the film, in order to improve the transferability of the layer to be transferred. The film must have releasability. As a transfer method of the transfer foil, a transfer device is used to transfer to a transfer object with a heating roll, a so-called hot stamping method, or after setting the transfer foil in an injection molding machine mold, a resin is injection molded and molded In-mold transfer in which transfer is simultaneously performed and a molded product is taken out from a mold after cooling, and a method of molding and transferring to an adherend such as a resin molded product, a metal product, and a glass product are generally known. These transfer methods can be molded and transferred at the same time, so they are very useful for the application of complex patterns. Plastic molded products used in automobile interior and exterior parts, home appliances, electronic equipment, building materials, packaging containers, etc. Widely used in.

  Thus, as a film used for various surface protective films and transfer foils, a polyester film is preferably used from the viewpoint of handleability and shape retention, but the polyester film is poor in releasability and has releasability. It is necessary to grant. Examples of a method for imparting releasability include a method in which a resin having good releasability (such as a polyolefin resin) is combined with a polyester resin by alloying or lamination.

  As a method of laminating a resin having good releasability to a polyester resin, a method of coating a polyolefin resin on a polyester film (Patent Document 1), and laminating a polyolefin resin on a base film such as a polyester film by extrusion lamination Methods (Patent Documents 2 and 3), a method of blending a polyester resin and a polyolefin resin and coextrusion (Patent Document 4), and the like have been disclosed, and an improvement in releasability of various films has been proposed.

JP 05-138668 A Japanese Patent Laid-Open No. 12-037827 Japanese Patent Laid-Open No. 07-148899 JP 2009-132806 A

  In Patent Document 1, it is necessary to dry the coating solvent by applying heat after coating the polyolefin resin on the base film. Therefore, when a low heat resistant film is used as the base film, preheating during drying is required. Since it cannot withstand and is thermally deformed, it is difficult to apply to a film having low heat resistance.

  Also, in Patent Documents 2 and 3, if the heat resistance of the base film is low, the film is low in heat resistance because it cannot withstand the temperature of the polyolefin resin melt-extruded at the time of extrusion lamination and is thermally deformed. Application to was difficult.

  On the other hand, for Patent Document 4, since a sheet is produced by extrusion molding after dry blending a polyester resin and a polyolefin resin, it can be applied to a film having low heat resistance, but the polyolefin resin content in the surface layer Therefore, the releasability was insufficient.

  In view of these problems, the present invention is intended to provide a laminated film that is excellent in releasability and printability and can be produced without including steps such as coating and extrusion lamination.

The present invention employs the following means in order to solve such problems.
(1) A laminated film obtained by laminating a polyolefin layer (B layer) mainly comprising a polyolefin resin on at least one surface of a polyester layer (A layer) mainly comprising an aromatic polyester resin,
The lamination ratio of the B layer in the whole film is B layer / whole film = 0.05 to 0.5,
A laminated film having an interlayer adhesion between the A layer and the B layer of 1 N / 25 mm or more and 30 N / 25 mm or less.
(2) A modified polyolefin resin is included as the polyolefin resin of the B layer,
The laminated film according to (1), comprising 5% by mass to 95% by mass of the modified polyolefin resin with respect to 100% by mass of the entire polyolefin layer (B layer).
(3) The laminated film according to (2), wherein the modified polyolefin resin is a modified polyolefin resin with an unsaturated dicarboxylic acid.
(4) When performing thermal mass measurement (TG) of the B layer under the conditions of a measurement start temperature of 25 ° C., a heating rate of 10 ° C./min, and an ultimate temperature of 300 ° C. in a nitrogen atmosphere, the heat of the B layer at 275 ° C. The laminated polyester film according to (1), wherein the mass reduction rate is 3% by mass or less.
(5) The laminated film according to any one of (1) to (4), wherein the elongation at break at 100 ° C is 300% or more.
(6) A molding sheet comprising the laminated film according to any one of (1) to (5).

  According to the present invention, a laminated film excellent in releasability and printability can be obtained without including steps such as coating and extrusion lamination. More specifically, as for releasability, since it is excellent in releasability from the transfer target, peeling marks are hardly generated in the releasable process. Further, as for printability, various printing inks can be used because of excellent solvent resistance against solvents contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone and the like. The laminated film of the present invention is suitably used as a transfer foil in a decoration method such as in-mold transfer, and is suitably used in applications such as automotive interior / exterior parts, home appliance members, electronic equipment, building materials, and packaging containers.

In the present invention, as a result of intensive studies on a laminated film that is excellent in releasability and printability, and can be produced without including steps such as coating and extrusion lamination, a polyester layer containing an aromatic polyester resin as a main component ( A layer) is a laminated film obtained by laminating a polyolefin layer (B layer) containing a polyolefin resin as a main component on at least one surface of the A layer, and the lamination ratio of the B layer in the whole film is B layer / whole film = 0. It is 05-0.5, and it was investigated that this problem can be solved at once by using a laminated film having an interlayer adhesion between the A layer and the B layer of 1 N / 25 mm or more and 30 N / 25 mm or less.
Hereinafter, the laminated film of the present invention will be specifically described.

(Aromatic polyester resin)
The laminated film of the present invention needs to have a polyester layer (A layer) containing an aromatic polyester resin as a main component from the viewpoints of heat resistance and handleability. Here, the aromatic polyester as the main component of the polyester layer (A layer) is a polyester basically composed of a dicarboxylic acid component and a glycol component, and is an aromatic dicarboxylic acid component and / or an aromatic glycol component. It is polyester containing.

  Examples of the dicarboxylic acid component include aromatic compounds such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfonedicarboxylic acid, and phthalic acid. Aliphatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, paraoxybenzoic acid, etc. The oxycarboxylic acid of these can be mentioned. The dicarboxylic acid ester derivatives include esterified products of the above dicarboxylic acid compounds, such as dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, and dimethyl adipate. In addition, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are preferably used in terms of handleability.

  Examples of the glycol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Aliphatic dihydroxy compounds such as hexanediol and neopentyl glycol, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, alicyclic dihydroxy compounds such as 1,4-cyclohexanedimethanol and spiroglycol, bisphenol A, aromatic dihydroxy compounds such as bisphenol S and the like, but in terms of handling, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol It is preferably used.

  As described above, among these polyesters, the polyester layer (A layer) in the laminated film of the present invention needs to have an aromatic polyester resin as a main component. Here, the aromatic polyester resin is a main component. And means that 50% by mass or more and 100% by mass or less of the polyester layer (A layer) is 100% by mass of the aromatic polyester resin.

  Specifically, the aromatic polyester used as the main component of the A layer of the laminated film of the present invention is polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate ( PHT), polyethylene naphthalate (PEN), polypropylene naphthalate (PPN), polybutylene naphthalate (PBN), polycyclohexanedimethylene terephthalate (PCT), and the like. These copolymer resins are also preferably used. In particular, 1,4-cyclohexanedimethanol copolymerized PET, spiroglycol copolymerized PET, neopentyl glycol copolymerized PET, isophthalic acid copolymerized PET, 2,6-naphthalene dicarboxylic acid. Acid copolymerized PET is preferably used from the viewpoint of handleability. These aromatic polyesters may be used alone or as a mixture of two or more aromatic polyesters.

  As a method of mixing and using two or more kinds of aromatic polyesters, for example, polymer pellets of two or more kinds of aromatic polyesters are blended and supplied to an extruder, and kneaded in the extruder to have an arbitrary component configuration. Method for obtaining aromatic polyester (dry blending method) Method for obtaining aromatic polyester of any component by polymerization using two or more monomers (copolymerization method), combining dry blending method and copolymerization method It can be obtained by a known method such as a method. From the viewpoint of polymer production cost, productivity, and heat resistance, it is preferable to use a dry blend method.

(Reaction catalyst and anti-coloring agent for aromatic polyester production)
When manufacturing the aromatic polyester used as the raw material of the laminated film of the present invention, conventionally used reaction catalysts and anti-coloring agents can be used. As the reaction catalyst, for example, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and the like can be used. As a coloring inhibitor, for example, a phosphorus compound or the like can be used. Preferably, an antimony compound, a germanium compound, or a titanium compound is added as a reaction catalyst at any stage before the production of the aromatic polyester is completed. As a method of adding the reaction catalyst, for example, a method of adding the powder of the reaction catalyst as it is, a method of dissolving the reaction catalyst in the glycol component which is a starting material of polyester, and the like can be used. .

  The antimony compound is not particularly limited, and for example, antimony oxide such as antimony trioxide, antimony acetate, or the like can be used.

  Further, the titanium compound is not particularly limited, but alkyl titanate compounds such as tetraethyl titanate and tetrabutyl titanate, and composite oxides of titanium and an element selected from silicon, zirconium and aluminum can be preferably used.

(Viscosity of aromatic polyester)
The intrinsic viscosity of the aromatic polyester used in the polyester layer (A layer) containing the aromatic polyester as a main component of the laminated film of the present invention may be one having a range of 0.5 to 1.3 dl / g. preferable. More preferably, it is 0.55-1.2 dl / g, Most preferably, it is the range of 0.6-1.1 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the moldability of the laminated film may be lowered. In addition, when the intrinsic viscosity exceeds 1.3 dl / g, the productivity is lowered, or the thickness unevenness of the polyester layer (A layer) in the laminated film becomes remarkable, and as a result, the thickness unevenness also occurs in the laminated film. is there. In addition, when the polyester layer (A layer) in the laminated film of the present invention has a laminated configuration (for example, a configuration in which layers having a different main component aromatic polyester are laminated), the layer in the A layer It is preferable that each polyester used in each layer satisfies the viscosity condition of 0.5 to 1.3 dl / g (that is, if each layer in the A layer is an A1 layer, an A2 layer,. These layers each satisfy the requirements as the A layer, and it is preferable that all the layers A1, A2,... Satisfy the viscosity condition of 0.5 to 1.3 dl / g. .

(Thermal mass reduction rate of polyolefin (B layer))
The polyolefin layer (B layer) of the laminated film of the present invention was subjected to thermal mass measurement (TG) under the conditions of a measurement start temperature of 25 ° C., a heating rate of 10 ° C./min, and an ultimate temperature of 300 ° C. in a nitrogen atmosphere. The thermal mass reduction rate of the B layer at 275 ° C. is preferably 3% by mass or less. When the thermal mass reduction rate at 275 ° C. of the B layer is larger than 3% by mass, the heat resistance is inferior, gas and gel defects are generated during extrusion, and the quality may be lowered. More preferably, the thermal mass reduction rate of the B layer at 275 ° C. is 2% by mass or less, and most preferably 1% by mass or less. The method of setting the thermal mass reduction rate of the B layer at 275 ° C. to 3% by mass or less is not particularly limited, but the preferred range described below for the content of the modified polyolefin resin in the B layer, the acid value of the modified polyolefin resin, etc. The method of controlling can be mentioned. Further, it is preferable to select a modified polyolefin resin to be used that has a thermal mass reduction rate at 275 ° C. of 3% by mass or less, preferably 2% by mass or less, and most preferably 1% by mass or less under the above conditions.

  In addition, the thermal mass reduction rate at 275 ° C. of the polyolefin layer (B layer) is preferably as small as possible, and there is no particular lower limit, but in reality, about 0.01% by mass is considered the lower limit.

(Polyolefin resin)
The polyolefin layer (B layer) in the laminated film of the present invention must contain a polyolefin resin as a main component. Here, the main component of polyolefin resin means that 50% by mass or more and 100% by mass or less of the polyolefin layer (B layer) is 100% by mass.

  The polyolefin layer (B layer) in the laminated film of the present invention preferably contains a modified polyolefin resin for the purpose of improving adhesion with a polyester layer (A layer) containing an aromatic polyester resin as a main component.

  Specifically, the polyolefin resin constituting the polyolefin resin of the B layer of the laminated film of the present invention was polymerized using low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, metallocene catalyst. Polyolefin resins such as ethylene-α / olefin copolymers, polypropylene, ethylene-propylene copolymers, ethylene-propylene-butene copolymers, and methylpentene polymers can be used.

  Further, a polymer composed of an α-olefin monomer such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and a random copolymer composed of the α-olefin monomer. Also, a block copolymer comprising the α-olefin monomer can be used.

  As a random copolymer composed of such an α-olefin monomer, for example, in a propylene copolymer, a random copolymer of propylene and one or more α-olefin monomers excluding propylene from the α-olefin monomer is used. It is a polymerized polymer, and is a polypropylene obtained by copolymerizing one or more α-olefin monomers excluding propylene in a range of 2 to 15% by mass by a known method.

Moreover, as a block copolymer consisting of the above-mentioned α-olefin monomer, for example, in the case of propylene / ethylene block copolymer, 99 to 70% by mass of propylene and 1 to 30% by mass of ethylene and / or Alternatively, a copolymer part composed of an α-olefin and a copolymer part composed of propylene in the range of 1 to 30% by mass and ethylene in the range of 99 to 70% by mass is used in a block-like manner. be able to. The composition of each copolymer component and the molecular weight of each block can be controlled at the polymerization stage. Generally, it can be obtained by a polymerization method having two or more stages as disclosed in JP-A-59-115312. For example, the melting point of the propylene block copolymer is in the range of 145 to 165 ° C. Melting | fusing point can be changed with the amount of propylene components of the copolymer part which consists of the propylene of the range of 99-70 mass%, and the ethylene and / or alpha olefin of the range of 1-30 mass%. Further, the amount of ethylene and / or α-olefin component in the propylene / ethylene block copolymer is preferably 5 to 20% by mass, more preferably 5 to 15% by mass in terms of impact resistance of the film. is there.
In the present invention, the method for producing a polyolefin resin is not particularly limited, and a known method can be used. For example, in polypropylene resin, radical polymerization, coordination polymerization using Ziegler-Natta catalyst, anionic polymerization Any method such as coordination polymerization using a metallocene catalyst can be used.

(MFR and viscosity of polyolefin resin)
The polyolefin resin that is the main component of the polyolefin layer (B layer) of the laminated film of the present invention has a melt flow rate (MFR) measured under conditions of 230 ° C. and a load of 2.16 kg in accordance with JIS-K7210 (1999). 1-100 g / 10 minutes, preferably 2-80 g / 10 minutes, more preferably 4-60 g / 10 minutes. When the MFR of the polyolefin resin is in the range of 1 to 100 g / 10 min, the crystallinity is suitable and the dimensional stability, moisture resistance and surface smoothness of the laminated film of the present invention are good. Moreover, it is especially preferable that MFR is 10-40 g / 10min from a viewpoint of uniform lamination property with the polyester layer (A layer) which has an aromatic polyester resin as a main component, and interlayer adhesiveness. If the MFR of the polyolefin resin is smaller than 1 g / 10 min, the melt viscosity is too high and the extrudability tends to be lowered. In addition, when the MFR of the polyolefin resin exceeds 100 g / 10 minutes, the crystallinity is too high, so that the film forming property may be significantly lowered, or the mechanical properties of the laminated film may be greatly lowered. In addition, the crystallization of the B layer proceeds too much, and there is a risk that the printing accuracy will be lowered by roughening the surface.

  In addition, the intrinsic viscosity [η] of the polyolefin resin is preferably 1.4 to 3.2 dl / g, more preferably 1.6 to 2.4 dl / g, from the viewpoint of appropriate crystallinity. When [η] is smaller than 1.4 dl / g, the crystallinity is too high, and there is a concern that the laminated film may be embrittled. When it exceeds 3.2 dl / g, the crystallinity is remarkably lowered, and the heat resistance of the laminated film is reduced. May decrease.

(Melting point of polyolefin resin)
The polyolefin resin that is the main component of the polyolefin layer (B layer) of the laminated film of the present invention preferably has a melting point of 100 to 170 ° C., more preferably 120 to 120 ° C. from the viewpoint of heat resistance at the ink drying temperature and moldability. It is 165 degreeC, More preferably, it is 130 to 160 degreeC. When the melting point of the polyolefin is lower than 100 ° C., the heat resistance of the laminated film may be insufficient, and when the melting point of the polyolefin exceeds 170 ° C., the extrudability of the laminated film may be lowered.

(Content of modified polyolefin resin)
The laminated film of the present invention contains a modified polyolefin resin as a polyolefin resin of the B layer from the viewpoint of adhesion and heat resistance, and the modified polyolefin resin is modified with respect to 100% by mass of the entire polyolefin layer (B layer). It is preferable that 5 mass% or more and 95 mass% or less of polyolefin resin is included. It is preferable that the modified polyolefin resin is 5 mass% or more in the total 100 mass% of the B layer because the effect of improving interlayer adhesion is increased. In addition, the modified polyolefin resin can prevent heat resistance from being lowered by 95% by mass or less in 100% by mass of the entire B layer, and the thermal mass reduction rate at 275 ° C. of the B layer can be 3% by mass or less. It is preferable because generation of gas and gel is suppressed during extrusion.

  In order to set the thermal mass reduction rate at 275 ° C. of the B layer to 3% by mass or less, the modified polyolefin resin is more preferably 80% by mass or less with respect to 100% by mass of the entire polyolefin layer (B layer). The mass% or less is most preferable. Further, from the viewpoint of interlayer adhesion, the modified polyolefin resin is preferably contained in an amount of 10% by mass or more with respect to 100% by mass of the entire polyolefin layer (B layer), and most preferably 20% by mass or more. In addition, as polyolefin resin which is a main component of B layer, it is also possible to use together modified polyolefin resin and other polyolefin resin.

(Modified polyolefin resin)
The modified polyolefin resin in the present invention refers to a polyolefin resin containing one or more polar groups at least one of one end, both ends, and the inside of the polyolefin resin. Here, the polar group is a functional group containing an atom having a large electronegativity such as an oxygen atom or a nitrogen atom. Specifically, a functional group such as an amide group, a carboxyl group, or a hydroxyl group, and these functional groups It is a substituent containing.

  Examples of such modified polyolefin resins include ethylene-vinyl acetate copolymers, ionomer resins, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid. Ethylene-α-olefin polymerized using polyolefin copolymer resin containing polar group such as copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, metallocene catalyst Polyolefin resins such as copolymers, polypropylene, ethylene-propylene copolymers, methylpentene polymers, other random copolymers composed of α-olefin monomers, block copolymers, acrylic acid, methacrylic acid, maleic anhydride, Fumaric acid and other unsaturation A modified polyolefin resin modified by carboxylic acid or modified by oxidative decomposition of the resin can be used.

  Examples of the α-olefin monomer include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like, and are randomly composed of such α-olefin monomers. As the copolymer, for example, a propylene copolymer is a polymer obtained by random copolymerization of propylene and one or more α-olefin monomers excluding propylene from the α-olefin monomer. Polypropylene obtained by copolymerizing one or more α-olefin monomers excluding propylene in a range of 2 to 15% by mass by a method.

  These modified polyolefin resins are preferably polyolefin resins modified by unsaturated dicarboxylic acid or modified by oxidative decomposition of the resin, and more preferably modified polyolefin resins modified by unsaturated dicarboxylic acid. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-propylene copolymer, methylpentene A modified polyolefin resin obtained by modifying a polyolefin resin such as a random copolymer or block copolymer composed of a polymer or other α-olefin monomer with an unsaturated dicarboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, or fumaric acid. It is preferable in terms of interlayer adhesion with the polyester layer (A layer). As the unsaturated dicarboxylic acid, maleic anhydride is particularly preferable, that is, a modified polyolefin resin obtained by modifying a polyolefin resin with maleic anhydride is particularly preferable.

  Examples of such modified polyolefin resin with unsaturated dicarboxylic acid include “Yumex” manufactured by Sanyo Kasei, “Admer” manufactured by Mitsui Chemicals, “Modic” manufactured by Mitsubishi Chemical, “Orebak” manufactured by Arkema, “Rotada, manufactured by Toyo Kasei Examples of the modified polyolefin resin modified by oxidative decomposition of the resin include “Viscol” and “Sunwax” manufactured by Sanyo Chemical.

(Acid value of modified polyolefin resin)
The acid value of the modified polyolefin resin contained as the polyolefin resin that is the main component of the polyolefin layer (B layer) in the laminated film of the present invention is preferably 0.5 to 20. From the viewpoint of heat resistance and adhesion to the polyester layer (A layer), it is preferably 0.5 to 15, and most preferably 1 to 10. It is preferable that the acid value of the modified polyolefin resin is 0.5 or more because an effect of improving the interlayer adhesion between the polyester layer (A layer) and the polyolefin layer (B layer) is exhibited. Moreover, by making the acid value of the modified polyolefin resin 20 or less, the heat resistance of the modified polyolefin resin can be prevented from being lowered, and the thermal mass reduction rate at 275 ° C. of the B layer can be 3 mass% or less. It is preferable because decomposition of the modified polyolefin resin can be suppressed and generation of gel-like substances can be suppressed. The acid value here is a value according to JIS K0070 (1992 formula).

(Additive)
In each layer of the laminated film of the present invention, additives such as flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, plasticizers, tackifiers, polysiloxanes, etc., are added as necessary. An appropriate amount of a colorant such as an antifoaming agent, pigment or dye can be contained.

  Although it does not specifically limit as an antistatic agent used for the laminated | multilayer film of this invention, It is possible to use various well-known antistatic agents, such as anionic type, a cationic type, a nonionic type, and amphoteric. Among these, it is particularly preferable to use sodium alkylsulfonate or sodium alkylbenzenesulfonate which is an anionic antistatic agent from the viewpoint of heat resistance.

  In addition, as the antioxidant used in the laminated film of the present invention, various known ones such as a phenol-based antioxidant, a phosphite-based antioxidant, a thioether-based antioxidant can be used. These compounds may be used by mixing a plurality of compounds.

(Thickness of laminated film, lamination ratio)
The thickness of the laminated film of the present invention is preferably 10 to 600 μm from the viewpoint of production stability, moldability, and dimensional stability. More preferably, it is 50-400 micrometers, Most preferably, it is 100-300 micrometers. If the thickness of the laminated film is less than 10 μm, production stability and dimensional stability may be deteriorated. Moreover, when the thickness of a laminated film exceeds 600 micrometers, a handleability and a moldability may be aggravated.

  In addition, the layer (thickness) ratio of the B layer in the entire film is required to be B layer / entire film = 0.05 to 0.5 from the viewpoint of improving printability, shape retention, and moldability. is there. More preferably, B layer / entire film = 0.08 to 0.4 is preferable, and B layer / entire film = 0.1 to 0.3 is more preferable. In addition, B layer / whole film = 0.05-0.5 is the ratio of the thickness per B layer and the thickness of the whole film. That is, when there are B layers on both sides of the A layer, it is important that the B layers existing in the two layers look at the B layer / the whole film = 0.05 to 0.5, and 0.08 to 0 .4 is preferable, and 0.1 to 0.3 is more preferable. If the B layer / film as a whole is smaller than 0.05, the thickness of the B layer is too thin, resulting in insufficient chemical resistance, and printability and transferability may be deteriorated. On the other hand, if the B layer / film as a whole is larger than 0.5, the thickness of the B layer is too thick, and the shape retainability may be insufficient.

(Interlayer adhesion of laminated film)
In the laminated film of the present invention, in order to suppress delamination after molding, the interlayer adhesion between the polyester layer (A layer) and the polyolefin layer (B layer) needs to be 1 N / 25 mm or more and 30 N / 25 mm or less. It is. If the interlayer adhesion between the A layer and the B layer is less than 1 (N / 25 mm), peeling may occur at the interface between the A layer and the B layer after molding the laminated film of the present invention. Further, if the interlayer adhesion is substantially 30 N / 25 mm, there is no practical problem, and if it is attempted to increase it, the economy may be lowered. The interlayer adhesion is more preferably 2 (N / 25 mm) to 25 (N / 25 mm), and most preferably 3 (N / 25 mm) to 20 (N / 25 mm). In particular, when it is used for strict applications, it is more preferably 4 (N / 25 mm) or more.

  The interlaminar adhesion force here refers to the value (peeling strength) at that time when peeling is forcibly generated at the interface of the A layer / B layer, and then the load applied during peeling is measured by a tensile test or the like. Point to. Specifically, a film for bonding which becomes a support is bonded to the B layer side. The film for bonding used here is not particularly limited, and examples thereof include a polyester film, a polypropylene film, and a polyethylene film.

  The bonded sample is cut out to a width of 25 mm, and the peel strength when the 180 ° peel test is performed at a speed of 300 mm / min is defined as the interlayer adhesion (N / 25 mm) between the A layer and the B layer.

  The method for adjusting the interlayer adhesion between the polyester layer (A layer) and the polyolefin layer (B layer) of the laminated film of the present invention to 1 N / 25 mm or more and 30 N / 25 mm or less is the above-described melt flow rate of polyolefin resin, modified polyolefin resin The concentration and the acid value of the modified polyolefin resin can be controlled.

  As a polyolefin resin which is a main component of the polyolefin layer (B layer) and is preferably used for controlling the interlayer adhesion between the A layer and the B layer to 1 N / 25 mm or more and 30 N / 25 mm or less, JIS-K7210 (1999). ) And a melt flow rate (MFR) measured under conditions of 230 ° C. and a load of 2.16 kg is preferably a polyolefin resin at 10 to 40 g / 10 minutes. Moreover, when the modified polyolefin resin is included as the main component polyolefin resin of the B layer and the entire polyolefin layer (B layer) is 100% by mass, the modified polyolefin resin may be included in an amount of 5% by mass to 95% by mass. Although it is preferable for controlling the above-mentioned interlayer adhesion, it is particularly preferable that the modified polyolefin resin is contained in an amount of 20% by mass to 60% by mass in 100% by mass of the entire B layer from the viewpoint of adhesion. Further, these modified polyolefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene, ethylene-propylene. Polyolefin resins such as copolymers, methylpentene polymers, other random copolymers consisting of α-olefin monomers, block copolymers, etc., with unsaturated dicarboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. A modified polyolefin resin is preferable, and maleic anhydride is particularly preferable as the unsaturated dicarboxylic acid. The acid value of the modified polyolefin resin is most preferably 1-20.

  In order to control the interlayer adhesion between the A layer and the B layer to 1 N / 25 mm or more and 30 N / 25 mm or less, a method of increasing the film thickness of the laminated film is also effective. In order to improve interlayer adhesion, the film thickness is preferably 50 μm or more, more preferably 100 μm or more. In order to cope with deep drawing, it is more preferable if it is 200 μm or more.

  In addition, the aromatic polyester resin, which is the main component of the polyester layer (A layer), contains a polyester having metal ions, so that the interlayer adhesion is improved by the interaction with the modified polyolefin in the polyolefin layer (B layer). The interlayer adhesion can be controlled to 1 N / 25 mm or more and 30 N / 25 mm or less. For example, from the viewpoint of extrusion stability and moldability, as an aromatic polyester resin that is a main component of the polyester layer (A layer), a polyester containing 0.1 to 20 mol% of a residue having an alkali metal sulfonate is contained. It is a preferred embodiment. From the viewpoint of productivity, economy, and film handling, the residue having an alkali metal sulfonate is preferably contained in an amount of 0.1 to 15 mol%, and from the viewpoint of adhesion, 1 to 15 mol%. It is preferable to contain. Here, as the residue having an alkali metal sulfonate, an ester-forming alkali metal salt compound such as 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 2-sulfoisophthalic acid, sulfoterephthalic acid, etc. Examples thereof include alkali metal salts such as dicarboxylic acids and monocarboxylic acids such as 2-sulfobenzoic acid, and ester-forming derivatives thereof. Among these, it is preferable to use sodium salt, potassium salt, or lithium salt of 5-sulfoisophthalic acid or sulfoterephthalic acid from the viewpoint of handleability.

(Surface free energy)
The surface free energy of the polyolefin layer (B layer) of the laminated film of the present invention is preferably 25 to 40 mN / m from the viewpoint of releasability and handling properties. Preferably it is 27-38 mN / m, More preferably, it is 29-36 mN / m. When the surface free energy of the polyolefin layer (B layer) is lower than 25 mN / m, the clear layer or the like is laminated on the polyolefin layer (B layer) when the laminated film of the present invention is used for a transfer foil or the like. May be difficult. Moreover, when the surface free energy of a polyolefin layer (B layer) exceeds 40 mN / m, the mold release property of a polyolefin layer (B layer) and a clear layer may be inadequate.

  As a method for setting the surface free energy of the polyolefin layer (B layer) of the laminated film of the present invention in the range of 25 to 40 mN / m, it is modified as one of the polyolefin resins that are the main components of the polyolefin layer (B layer). Examples thereof include a method of using a polyolefin resin, further changing the kind and content of the modified polyolefin resin, and a method of adding a resin (for example, a polyester resin) having high surface free energy to the polyolefin layer (B layer).

(Elongation at break, stress)
The laminated film of the present invention preferably has a breaking elongation at 100 ° C. of 300% or more. The laminated film of the present invention is used for a surface protective film, a transfer foil, etc., but the laminated film of the present invention can be molded in a configuration laminated on a base film (attached film), or the laminated film can be formed simultaneously with injection molding. A method of molding and transferring, a method of transferring simultaneously with film molding to an adherend such as a resin molded product, a metal product, and a glass product are preferably used. The laminated film of the present invention is preferably molded at around 100 ° C. because it can be applied to transfer layers and adherends with low heat resistance, and at that time, the elongation at break is 300% for complicated follow-up. The above is preferable. More preferably, the elongation at break at 100 ° C. is 400% or more, and most preferably 500% or more. Furthermore, it is very preferable that the elongation at break is 1000% or more because it can be applied to ultra deep drawing. From the viewpoint of dimensional stability, the breaking elongation is preferably 1500% or less.

  When the elongation at break at 100 ° C. is less than 300%, the molding followability is inferior and it may not be possible to cope with a complicated shape member.

  Although it does not specifically limit as a method of making the breaking elongation in 100 degreeC of the laminated | multilayer film of this invention 300% or more, It is very preferable to make a laminated | multilayer film into an unstretched film. Moreover, when extending | stretching more than one axis | shaft, it is preferable as a draw ratio that it is 4 times or less, More preferably, it is 3 times or less, Most preferably, it is 2 times or less.

  In addition, as a method for setting the elongation at break of the laminated film at 100 ° C. to 300% or more, at least two kinds of dicarboxylic acid components and / or 2 are used as the aromatic polyester as the main component of the polyester layer (A layer). It is also a preferred embodiment to include more than one type of glycol component. Here, the dicarboxylic acid component and the glycol component that are preferably used are as described in the section of (Aromatic polyester resin), but as the dicarboxylic acid component, extrusion stability, heat resistance, economy, moldability In view of the above, it is preferable to include at least two kinds of terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid. Also, as a glycol component, excluding diethylene glycol by-produced during polymerization, ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl from the viewpoints of extrusion stability, heat resistance, economy, and moldability Glycopolyethylene glycol, spiroglycol and 1,4-cyclohexanedimethanol are preferably used.

  From the viewpoint of moldability, the laminated film of the present invention preferably has an F100 value at 100 ° C. of 0.5 to 10 MPa. When the F100 value at 100 ° C. is less than 0.5 MPa, the dimensional stability may decrease, which is not preferable. Further, if the F100 value at 100 ° C. is larger than 10 MPa, the stress during molding is high, and a deep shape may not be reproduced, which is not preferable. As a method of lowering the F100 value at 100 ° C., in addition to the above-described method of setting the elongation at break to 300% or more, a method of reducing the thickness of the polyolefin layer (B layer), and a polyolefin used for the B layer are copolymerized polyolefin and And a method of increasing the MFR are preferably used.

  Here, the elongation at break at 100 ° C. and the F100 value are a film sample cut into a rectangular shape with a test length of 20 mm, preheated for 60 seconds in a constant temperature layer set at 100 ° C., and then pulled at a strain rate of 200 mm / min. When the test was performed, the elongation when the film broke was the breaking elongation, and the stress at 100% elongation was the F100 value.

(Configuration of laminated film)
The laminated film of the present invention is not particularly limited as long as the polyolefin layer (B layer) is laminated on at least one side of the polyester layer (A layer), and the polyolefin layer (A layer) on one side of the polyester layer (A layer). B layer) or a polyolefin layer (B layer) on both sides of the polyester layer (A layer). In addition, the laminated film of the present invention is formed by laminating a B layer on at least one side of the A layer. However, the A layer and the B layer do not include layers other than the A layer and the B layer, that is, the A layer. It is preferable in terms of productivity and cost that the layer B and the layer B are directly laminated.

(Laminated film manufacturing method)
The laminated film of the present invention can be produced by a known method, but the coextrusion method is preferably used in terms of the handleability, productivity and production cost of the film. In addition, by manufacturing by a co-extrusion method, it becomes possible easily to set it as the aspect by which the A layer and the B layer were directly laminated | stacked about the laminated | multilayer film of this invention.

  The coextrusion method is a method in which each resin constituting the polyester layer (A layer) and the polyolefin layer (B layer) is supplied from a plurality of extruders to one die and simultaneously extruded to produce a laminated film. There is a law and inflation method. The laminated film of the present invention can be produced by either the T-die method or the inflation method, but the T-die method is preferably used from the viewpoint of productivity.

  Typical examples of the T-die method include a laminar flow method using a single manifold die, an intra-die lamination method using a multi-manifold die, and an outer die lamination method using a dual slot die. The laminated film of the present invention can be produced by any method, but the laminar flow method and the in-die lamination method can be preferably used from the viewpoint that the unevenness of the laminated thickness in the width direction is small and the productivity is good. In addition, when the polyester layer (A layer) and the polyolefin layer (B layer) are laminated, when the viscosity difference between the layers is large, the in-die lamination method can be particularly preferably used.

  When manufacturing by the T-die method, the laminated film of the present invention can be manufactured by drawing a multilayer sheet coextruded from a die onto a cast drum.

(Molding sheet)
The laminated film of the present invention is suitably used as a molding sheet. The laminated film of the present invention is a laminated film that satisfies both moldability and printability required for a deep-drawn transfer foil film, and further, for example, compared with a conventional laminated film such as JP-A-2004-188708. It is a laminated film with excellent cost. For these reasons, the laminated film of the present invention is a sheet for molding, and among them, the surface of a component having a complicated shape, for example, automotive interior / exterior parts, home appliance members, electronic equipment, building materials field, packaging containers, etc. It can be preferably used as a foil sheet.

  Although it does not specifically limit as a structure of a shaping | molding transfer foil sheet, It is preferable that it is the structure which laminated | stacked the decoration layer on the laminated | multilayer film of this invention. Here, the decoration layer is a layer for adding decoration such as coloring, pattern, wood grain, metal tone, pearl tone and the like. From the viewpoint of scratch resistance, weather resistance, and designability of the molded member (adhered body) after transfer, it is preferable to further laminate a clear layer. In this case, the clear layer is preferably laminated on the laminated film side. Moreover, it is preferable to laminate | stack an adhesive layer from a viewpoint of the adhesiveness of the molding member (adhered body) after a transcription | transfer, and a decoration layer. In this case, the adhesive layer is preferably laminated on the adherend side. That is, as a preferred embodiment, there is a configuration of the laminated film / clear layer / decorative layer / adhesive layer of the present invention. In addition, when the laminated | multilayer film of this invention are the aspects which have B layer only on one side, it is preferable that a clear layer is formed on B layer.

  Here, the resin used as the clear layer is not particularly limited as long as it is a highly transparent resin. However, polyester resin, polyolefin resin, acrylic resin, urethane resin, fluorine resin, polyvinyl acetate resin, chloride resin Vinyl-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin copolymer and the like are preferably used. From the viewpoint of scratch resistance, a thermosetting resin, an ultraviolet curable resin, or a heat ray curable resin is preferably used. Further, in order to improve the weather resistance, an ultraviolet absorber or an ultraviolet reflector may be added to the clear layer.

The clear layer preferably has a thickness of 10 to 100 μm, more preferably 15 to 80 μm, and most preferably 20 to 60 μm from the viewpoint of scratch resistance and design.
Examples of the method for forming the clear layer include a method for direct formation and a method for once forming and transferring to a carrier film. When the drying temperature after forming the clear layer needs to be high, a method of once forming on the carrier film and then transferring it is preferably used. Examples of the method for forming the clear layer include a roller coating method, a brush coating method, a spray coating method, a dip coating method, and a method using a gravure coater, a die coater, a comma coater, a bar coater, and a knife coater.

  Although it does not specifically limit as a formation method of a decoration layer, For example, it can form by a coating, printing, metal vapor deposition, etc. In the case of coating, a coating method such as a gravure coating method, a roll coating method, or a comma coating method can be used. In the case of printing, a printing method such as an offset printing method, a gravure printing method, or a screen printing method can be used. The resins used at this time include polyester resins, polyolefin resins, acrylic resins, urethane resins, fluorine resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, ethylene-vinyl acetate copolymers. Polymer based resin copolymers and the like are preferably used. Although it does not specifically limit as a coloring agent to be used, Considering dispersibility etc., it selects suitably from dye, an inorganic pigment, an organic pigment, etc.

  The thickness of the decorative layer formed by coating or printing is preferably 10 to 100 μm, more preferably 15 to 80 μm from the viewpoint of color tone retention after molding and design, and more preferably 20 to 80 μm. The thickness is most preferably 60 μm.

  Moreover, when the formation method of a decoration layer is metal vapor deposition, it does not specifically limit as a preparation method of a vapor deposition book film, However, A vacuum evaporation method, EB vapor deposition method, sputtering method, an ion plating method etc. can be used. In order to improve the adhesion between the polyester film and the vapor deposition layer, the vapor deposition surface is preferably pretreated by a method such as a corona discharge treatment or an anchor coating agent. As the metal used, it is preferable to deposit a metal compound having a melting point of 150 to 400 ° C. from the viewpoint of molding followability. The use of a metal in the melting point range is preferred because the polyester film can be molded in a temperature range and the deposited metal layer can be molded, and it is easy to suppress the occurrence of a deposited layer defect due to molding. The melting point of a more preferable metal compound is 150 to 300 ° C. Although it does not specifically limit as a metal compound whose melting | fusing point is 150-400 degreeC, Indium (157 degreeC) and tin (232 degreeC) are preferable, and indium can be used especially preferable. The lamination thickness of the decorative layer is preferably 0.001 to 100 μm, more preferably 0.01 to 80 μm, and most preferably 0.02 to 60 μm.

  As the material of the adhesive layer provided for the purpose of imparting adhesiveness to the molding resin, a heat sensitive type or a pressure sensitive type can be used. In the case of transferring to an injection molded resin or a resin molded body, an adhesive layer can be designed according to the resin. In the case of acrylic resin, acrylic resin, polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, in the case of polystyrene resin, acrylic resin having affinity with these resins, polystyrene resin, It is preferable to use a polyamide-based resin or the like. When the molding resin is a polypropylene resin, it is preferable to use a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone indene resin.

  Various methods are used as the method for forming the adhesive layer. For example, a coating method such as a roll coating method, a gravure coating method or a comma coating method, or a printing method such as a gravure printing method or screen printing is used.

  The adherend to be decorated using the molding sheet using the laminated film of the present invention is not particularly limited, and examples thereof include polypropylene, acrylic, polystyrene, polyacrylonitrile / styrene, polyacrylonitrile / butadiene / styrene, and the like. Resin, a metal member, etc. are used.

EXAMPLES Hereinafter, although this invention is demonstrated along an Example, this invention is not restrict | limited by these Examples. Various characteristics were measured by the following methods.

(1) Film thickness and layer thickness When measuring the total thickness of a laminated film, the thickness of five arbitrary places of the sample cut out from the film was measured using the dial gauge, and the average value was calculated | required.

  In addition, when measuring the layer thickness of each layer of the laminated film, using a metal microscope Leica DMLM manufactured by Leica Microsystems Co., Ltd., the transmitted light was photographed under the condition of a magnification of 100 times, and each layer of the laminated film was photographed. As for the layer thickness, arbitrary 5 points were measured for each layer, and the average value was defined as the layer thickness of each layer.

(2) Adhesive tape “Damplon Ace No. 3200” made by Nitto Denko CS System Co., Ltd. on the surface of the interlayer adhesion film (B layer side) between the polyester layer (A layer) and the polyolefin layer (B layer) using a laminator Bonding was performed (nip condition: 0.3 MPa, 10 m / min). The laminated film was sampled to a size of 150 mm × 25 mm, and forced peeling was performed between the A layer and the B layer from the end of the sample. Then, using a tensile tester (Orientec Tensilon UCT-100), an initial tensile chuck distance of 100 mm and a tensile speed of 300 mm / min were subjected to a 180 ° peel test, and an average load of 50% to 100% elongation was calculated. Interlayer adhesion was used.

(3) The stress at 100% elongation at 100 ° C. and the fracture elongation laminated film at 100 ° C. were cut into rectangles of length 100 mm × width 10 mm in the longitudinal direction and width direction, and used as samples. Using a tensile tester (Orientec Tensilon UCT-100), the tensile test was performed in the longitudinal direction and the width direction of the film at an initial tensile chuck distance of 20 mm and a tensile speed of 200 mm / min. For the measurement, a film sample was set in a constant temperature layer set in advance at 100 ° C., and a tensile test was performed after preheating for 60 seconds. When the sample is 100% elongated (when the distance between chucks is 40 mm), the load applied to the film is read, and the value divided by the cross-sectional area (film thickness × 10 mm) of the sample before the test is obtained. Stress (F100 value).

In addition, tensile tests were performed in the longitudinal direction and the width direction under the same measurement conditions, and the average value in the longitudinal direction and the width direction when the sample broke was defined as the breaking elongation at 100 ° C.
The measurement was performed five times for each sample and each direction for both stress and breaking elongation, and the average value was evaluated.

(4) Thermal mass reduction rate of polyolefin layer (B layer) at 275 ° C. The polyolefin layer (B layer) of the laminated film of the present invention is scraped, a sample is weighed, and a thermogravimetric analyzer (TGA-50 manufactured by Shimadzu Corporation). ) Was performed under a nitrogen atmosphere under the conditions of a measurement start temperature of 25 ° C., a heating rate of 10 ° C./min, and an ultimate temperature of 300 ° C. The mass at the measurement start temperature (25 ° C.) was defined as 100, and the thermal mass reduction rate at 275 ° C. was determined.

(5) As the surface free energy measurement liquid, water, ethylene glycol, formamide, and methylene iodide were used, and each of them was measured using a contact angle meter CA-D type manufactured by Kyowa Interface Chemical Co., Ltd. The static contact angle for the liquid film surface was determined. The components of the contact angle and the surface tension of the measurement liquid obtained for each liquid were substituted into the following equations, and the simultaneous equations consisting of four equations were solved for γSd, γSp, and γSh.

(ΓSdγLd) 1/2 + (γSpγLp) 1/2 + (γShγLh)
1/2 = γL (1 + COS θ) / 2
However, γS = γSd + γSp + γSh
γL = γLd + γLp + γLh
γS, γSd, γSp and γSh are the surface free energy, dispersion force component, polar force component and hydrogen bond component of the film surface, respectively, and γL, γLd, γLp and γLh are the surface free energy and dispersion force of the measurement solution used, respectively. It represents components, polar force components, and hydrogen bond components. Here, as the surface tension of each liquid used, the value proposed by Panzer (J. Panzer, J. Colloid Interface Sci., 44, 142 (1973)) was used.

(6) Grade A4 size sampled film is visually observed by transmission under a three-wavelength fluorescent lamp, the number of foreign matters having a major axis of 50 μm or more is counted, and the number of foreign matters per A4 size is as follows: Was evaluated.
A: No foreign matter was counted.
B: The number of foreign matters was 1 or more and less than 5.
C: The number of foreign matters was 5 or more and less than 10.
D: The number of foreign matters was 10 or more.

(7) 3 ml each of ethyl acetate, methyl ethyl ketone, toluene, and ethanol was dropped on the surface of the solvent resistant polyolefin layer (B layer) and left for 6 hours. Then, the solvent was wiped clean, and the surface condition was visually observed according to the following evaluation criteria. Was observed and judged. A and B are acceptable levels.
A: For all solvents, no whitening, shrinkage, deformation, or trace of solvent is observed.
B: A relatively light whitening, shrinkage, or deformation is recognized with respect to any solvent.
C: Whitening, shrinkage, or deformation is observed with any solvent.

(8) Moldability Using a far-infrared heater having a mold temperature of 400 ° C., the surface temperature was heated to 100 ° C., and vacuum molding was performed along a mold (bottom diameter 50 mm) heated to 50 ° C. The state of being molded along the mold was evaluated according to the following criteria using the molding degree (drawing ratio: molding height / bottom diameter). If it is AC, it is a pass level.
A: Molding was possible with a drawing ratio of 1.0 or more.
B: Molding was possible at a drawing ratio of 0.9 to less than 1.0.
C: Molding was possible at a drawing ratio of 0.8 or more and less than 0.9.
D: The followability was low and could not be formed into a shape with a drawing ratio of 0.8.

(9) The shape retention when the molded body molded by shape retention (8) was removed from the mold was evaluated according to the following criteria. A or B is a pass level.
A: The shape of the mold could be maintained.
B: Although the shape was slightly collapsed, it was at a level with no problem.
C: The shape of the mold could not be maintained.

(10) Releasability After forming a transfer foil sheet for molding under the conditions described in each example described later, a sample was cut into a rectangle of length 100 mm × width 25 mm in the longitudinal direction and the width direction. Part of the sample polyolefin layer (B layer) and the topcoat layer were peeled off, and then the laminated film side and the topcoat layer side were sandwiched between chucks using a tensile tester (Orientec Tensilon UCT-100). After that, a peeling test was conducted to determine the average value of the load at the time of peeling, and the determination was made according to the following criteria.

The initial chuck distance was 100 mm, the tensile speed was 300 mm / min, and the temperature was room temperature, and the test was performed in the longitudinal direction and the width direction of the film. In addition, the measurement was performed 5 times for each sample and each direction, and the average value was evaluated. S to B are acceptable.
S: 0 N / 25 mm or more and less than 0.2 N / 25 mm A: 0.2 N / 25 mm or more and less than 0.5 N / 25 mm B: 0.5 N / 25 mm or more and less than 1.0 N / 25 mm C: 1.0 N / 25 mm or more D: Delamination occurs between the polyester layer (A layer) and the polyolefin layer (B layer). (11) After removing the molded body molded with delamination (8) after molding from the mold, the molded part is removed with a cutter. The film was cut, and the adhesive tape “Dumplon Ace No. 3200” manufactured by Nitto Denko CS System Co., Ltd. was bonded to both sides of the film at the cut end, forcibly peeled, and evaluated as follows. If it is SC, it is a pass level.
S: No peeling occurred.
A: When forced peeling was repeated 5 times or more, partial peeling occurred at the end portion, but film breakage occurred and no further peeling occurred.
B: The forced peeling was less than 5 times, and the edge part was peeled off partially, but the film was cut and no further peeling occurred.
C: The forced peeling was less than 5 times, and the edge part was partially peeled off, but the peeling resistance was very strong.
D: Peeling occurred without resistance.

(12) Intrinsic viscosity The intrinsic viscosity can be calculated from the solution viscosity measured at 25 ° C. in orthochlorophenol according to [Formula].
Intrinsic viscosity: [eta] sp / C = [[eta]] + K [[eta]] 2 * C [Formula]
Here, ηsp = (solution viscosity / solvent viscosity) −1, C is the dissolved polymer mass per 100 ml of solvent (1.2 g / 100 ml), and K is the Huggins constant (0.343). The solution viscosity and the solvent viscosity can be measured using an Ostwald viscometer.

(13) Acid value According to JIS K0070 (1992 formula), the resin can be heated and dissolved in xylene and then titrated with a KOH solution using phenolphthalein as an indicator.

The following polyesters, polyolefins, and acid-modified polyolefins were used in Examples and Comparative Examples.

(Polyester A)
Polyethylene terephthalate resin (inherent viscosity 0.65) in which the terephthalic acid component is 100 mol% as the dicarboxylic acid component, the ethylene glycol component is 99 mol% and the diethylene glycol component is 1 mol% as the glycol component.

(Polyester B)
Copolyester (GN001 manufactured by Eastman Chemical Co., Ltd.) obtained by copolymerizing 33 mol% of 1,4-cyclohexanedimethanol with respect to the glycol component was used as cyclohexanedimethanol copolymerized polyethylene terephthalate (inherent viscosity 0.75).

(Polyester C)
Isophthalic acid copolymerized polyethylene terephthalate resin having 82.5 mol% terephthalic acid component as dicarboxylic acid component, 17.5 mol% isophthalic component, 99 mol% ethylene glycol component and 1 mol% diethylene glycol component as glycol components ( Intrinsic viscosity 0.7).

(Polyester D)
5-sodium isophthalic acid copolymer polyethylene terephthalate containing 95 mol% terephthalic acid as dicarboxylic acid component, 5 mol% 5-sodium isophthalic acid component, 99 mol% ethylene glycol component and 1 mol% diethylene glycol component as glycol components Resin (intrinsic viscosity 0.67).

(Polyester E)
Polybutylene terephthalate resin (intrinsic viscosity 1.22) in which the terephthalic component is 100 mol% as the dicarboxylic acid component and the 1,4-butanediol component is 100 mol% as the glycol component.

(Polypropylene A)
Prime polymer “Y-2045GP” (MFR = 24, containing 4% by mass of ethylene group) was used.

(Polypropylene B)
“R101” (MFR = 19) manufactured by Sumitomo Chemical was used.

(Polypropylene C)
“Z101A” (MFR = 22) manufactured by Sumitomo Chemical was used.

(Modified polypropylene A)
“Admer QE800” manufactured by Mitsui Chemicals was used.
* 275 ° C thermal mass reduction rate by method (4): 0.02%
(Modified polypropylene B)
“Orebak CA100” manufactured by Arkema was used.
* 275 ° C thermal mass reduction rate by method (4): 0.54%
(Modified polypropylene C)
“Yumex 1010” manufactured by Sanyo Chemical Co., Ltd. was used.
* 275 ° C thermal mass reduction rate by method (4): 2.2%
(Modified polypropylene D)
“Yumex 1001” manufactured by Sanyo Chemical Co., Ltd. was used.
* 275 ° C thermal weight loss rate by method (4): 1.3%
Example 1
Polyester A was fed to (Layer A) and a vent type twin screw extruder (L / D = 36) and melted at 275 ° C., and then passed through two vacuum vent portions. Next, the resin was passed through a leaf disk filter having a filtration accuracy of 30 μm and then supplied to a multi-manifold die.

  Further, polyolefin A and modified polyolefin A were mixed in the ratio shown in the table (layer B) and supplied to a vent type twin screw extruder (L / D = 36). After the supplied resin was melted at 270 ° C., it was passed through two vacuum vent portions. Next, the resin was passed through a leaf disk filter having a filtration accuracy of 30 μm and then supplied to a multi-manifold die.

  After each resin passed through the manifold in the die, two kinds of resins were laminated so as to be B layer / A layer / B layer, and extruded from a slit die to a sheet shape. Electrostatic application was applied to both ends of the extruded sheet using a needle-like edge pinning device, and the sheet was brought into close contact with the casting drum and cooled and solidified to obtain a laminated film of the present invention having a total thickness of 100 μm.

  The above evaluation was performed using the obtained laminated film.

  Next, a clear layer, a decorative layer, and an adhesive layer were formed in this order on one B layer of the laminated film to obtain a molding sheet of the present invention which is a transfer foil.

  As the clear layer, an ultraviolet curable acrylic resin (“LAROMER” (registered trademark) LR8983 manufactured by BASF Japan) was used to form a layer having a thickness of 60 μm.

  As the decorative layer, polyurethane resin gravure ink ("Hiramic" (registered trademark) manufactured by Dainichi Seika Kogyo Co., Ltd., main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow / 701R white) is used. A layer having a thickness of 50 μm was formed.

  As the adhesive layer, an acrylonitrile / butadiene / styrene (ABS) copolymer resin film (ABS film “Hiflex” (registered trademark) manufactured by Okamoto Co., Ltd.) was used to form a layer having a thickness of 50 μm.

  Using the transfer foil thus obtained, (10) evaluation of releasability was performed.

  Next, the obtained transfer foil was heated using a far-infrared heater at 400 ° C. using a vacuum molding machine so that the surface temperature became 100 ° C., and a mold (bottom diameter) heated to 50 ° C. Vacuum forming was performed along 50 mm: drawing ratio: 0.8). At this time, molding was performed so that the adhesive layer became the innermost outermost layer.

  Subsequently, acrylonitrile-butadiene-styrene (ABS) copolymer resin (ABS resin “Toyolac” (registered trademark) 930 manufactured by Toray Industries, Inc.) heated to 280 ° C. was poured into the molded body. After the ABS was cooled and solidified, the molded product obtained by injecting the ABS copolymer resin into the molded product was taken out from the mold, and the clear layer of the molded product was cured using ultraviolet light having a wavelength of 365 nm. Thereafter, peeling was performed between the laminated film / clear layer to obtain a decorative molded body.

(Examples 2-9, 11-15, 19, 20)
A laminated film of the present invention was obtained in the same manner as in Example 1 except that the composition of the laminated film was changed as shown in the table, and the same evaluation was performed. Further, a transfer foil was obtained in the same manner as in Example 1, and the same evaluation was performed. The transfer foil prepared in this example was good in both releasability and moldability.

(Example 10)
The laminated film of the present invention was obtained in the same manner as in Example 1 except that the laminated film was composed of two layers of A layer / B layer, and the same evaluation was performed. Further, a transfer foil was obtained in the same manner as in Example 1, and the same evaluation was performed.

(Examples 16 to 18)
A laminated film of the present invention was obtained in the same manner as in Example 1 except that the composition of the laminated film and the film thickness were changed as shown in the table, and the same evaluation was performed. Further, a transfer foil was obtained in the same manner as in Example 1, and the same evaluation was performed.

(Examples 21 and 22)
A laminated film of the present invention was obtained in the same manner as in Example 1 except that the composition of the laminated film and the lamination ratio were changed as shown in the table, and the same evaluation was performed. Further, a transfer foil was obtained in the same manner as in Example 1, and the same evaluation was performed.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the composition of the laminated film was changed as shown in the table. The laminated film prepared in this example had low interlayer adhesion between the polyolefin layer (B layer) and the aromatic polyester layer (A layer).

(Comparative Example 2)
Example 3 was repeated except that the lamination ratio of the laminated film was changed as shown in the table. In the laminated film prepared in this example, the lamination ratio of the A layer and the B layer was larger than B layer / total film = 0.5, and thus the shape retention was insufficient.

(Comparative Example 3)
Example 3 was repeated except that the lamination ratio of the laminated film was changed as shown in the table. In the laminated film prepared in this example, the lamination ratio of the A layer and the B layer was less than 0.05 because the lamination ratio of the B layer / the whole film was less than 0.05, and the solvent resistance was insufficient.

(Comparative Example 4)
Polyester A was fed to (Layer A) and a vent type twin screw extruder (L / D = 36) and melted at 275 ° C., and then passed through two vacuum vent portions. Next, the resin was passed through a leaf disk filter having a filtration accuracy of 30 μm, and then extruded from a slit-shaped die into a sheet. Electrostatic application was performed to both ends of the extruded sheet using a needle-like edge pinning device, and the sheet was brought into close contact with the casting drum and cooled and solidified to obtain a film having a total thickness of 100 μm. Since the obtained film was not laminated with a polyolefin layer (B layer), the solvent resistance and releasability were insufficient.

  According to the present invention, a laminated film excellent in releasability and printability can be obtained without including steps such as coating and extrusion lamination. More specifically, as for releasability, since it is excellent in releasability from the transfer target, peeling marks are hardly generated in the releasable process. Further, as for printability, various printing inks can be used because of excellent solvent resistance against solvents contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone and the like. The laminated film of the present invention is suitably used as a transfer foil in a decoration method such as in-mold transfer, and is suitably used in applications such as automotive interior / exterior parts, home appliance members, electronic equipment, building materials, and packaging containers.

Claims (6)

A laminated film formed by laminating a polyolefin layer (B layer) mainly comprising a polyolefin resin on at least one side of a polyester layer (A layer) mainly comprising an aromatic polyester resin,
The lamination ratio of the B layer in the whole film is B layer / whole film = 0.05 to 0.5,
A laminated film having an interlayer adhesion between the A layer and the B layer of 1 N / 25 mm or more and 30 N / 25 mm or less. A modified polyolefin resin is included as the polyolefin resin of the B layer,
The laminated film according to claim 1, comprising 5% by mass to 95% by mass of the modified polyolefin resin with respect to 100% by mass of the entire polyolefin layer (B layer).   The laminated film according to claim 2, wherein the modified polyolefin resin is a modified polyolefin resin with an unsaturated dicarboxylic acid.   Thermal mass reduction rate of B layer at 275 ° C. when thermal mass measurement (TG) of B layer was performed under the conditions of a measurement start temperature of 25 ° C., a heating rate of 10 ° C./min, and an ultimate temperature of 300 ° C. The laminated film according to claim 1, wherein is 3% by mass or less.   The laminated film according to any one of claims 1 to 4, wherein the elongation at break at 100 ° C is 300% or more.   The sheet | seat for shaping | molding which consists of a laminated | multilayer film in any one of Claims 1-5.