JP2006142640A - Composite film and method of manufacturing composite film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite film excellent in moldability, printability, and cost performance. <P>SOLUTION: In the composite film, a polyester layer is a polyester containing a dicarboxylic acid component (1) containing at least 90 mole% of naphthalene dicarboxylic acid and/or terephthalic acid and a glycol component (2) containing 20-99.9 mole% of an ethylene glycol component and 0.1-80 mole% of a 1,3-propanediol component and/or a 1,4-butanediol component, an adhesive layer (a) is an adhesive thermoplastic resin, the composition is the polyester layer/the adhesive layer/a polyolefin layer, and the surface orientation coefficient of the polyester layer is 0-0.05. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyester / polyolefin composite film excellent in printability and moldability.

  The use of a biaxially stretched polyester film has been proposed as a conventional transfer foil film and a molding film used after printing and molding (see, for example, Patent Document 1). For transfer foil applications, it is shown that polyester films with a specific range of molding stress are used, and polyesters with a lower molding stress than biaxially stretched PET, especially copolymer polyesters, are used for the purpose of improving moldability. (See Patent Document 2). However, the method using a biaxially stretched polyester film is insufficient in terms of moldability for transfer to a member having a complicated shape. In addition, although the method using a copolyester has good moldability, no particular consideration is given to printability, and the film surface smoothness deteriorates due to the solvent contained in the printing ink, such as ethyl acetate and methyl ethyl ketone. There is a problem that printing defects are likely to occur, and a film having excellent chemical resistance against various solvents contained in printing ink, that is, excellent printability and excellent moldability has been desired.

Therefore, a laminated film satisfying both moldability and printability has been developed by bonding a polyolefin film having excellent chemical resistance to a polyester film having excellent moldability (see Patent Document 3). Has a problem that the polyester film and the polyolefin film need to be bonded off-line and the manufacturing cost is high.
Japanese Patent Laid-Open No. 06-210799 Japanese Patent No. 3090911 JP 2004-188708 A

  The subject of this invention is providing the film which solves the trouble of the above-mentioned prior art, satisfies both formability and printability, and is excellent in cost performance.

The present invention employs the following means in order to solve such problems. That is, the composite film of the present invention is a composite film obtained by laminating a polyester layer and a polyolefin layer via an adhesive layer (a) made of a thermoplastic resin, and the polyester layer satisfies the following (1). It is a polyester film containing a dicarboxylic acid component and a glycol component satisfying the following (2), and the plane orientation coefficient of the polyester layer is in the range of 0 to 0.05.
(1) The dicarboxylic acid component contains 90% by mole or more of naphthalenedicarboxylic acid and / or terephthalic acid.
(2) The glycol component contains an ethylene glycol component in the range of 20-99.9 mol%, and the 1,3-propanediol component and / or 1,4-butanediol component is 0.1-80 mol%. Included in the range.

  According to the present invention, a composite film excellent in printability, moldability, peelability, and cost performance can be obtained. More specifically, various printing inks can be used because the printing property is excellent in solvent resistance against solvents contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone, and the like. In addition, the composite film of the present invention is excellent in moldability such as deep drawability and followability of the surface shape of the transfer object, so in-mold transfer foil used by printing and molding, further embossing and vacuum forming after printing. It is suitably used as a transfer foil for performing transfer processing of printing on a decorative sheet for building materials used in addition to automobile interior and exterior parts, bathroom panels, parts for home appliances, packaging containers, and the like.

  The polyester used for the polyester layer of the composite film of the present invention is preferably a polymer basically composed of a dicarboxylic acid component and a glycol component.

  Examples of the dicarboxylic acid component include isophthalic acid, terephthalic acid, diphenyl-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, Diphenoxyethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, malonic acid, 1,1-dimethylmalonic acid, succinic acid, glutaric acid, Adipic acid, sebacic acid, decamethylene dicarboxylic acid and the like can be used. The polyester used in the polyester layer of the composite film of the present invention is a polyester containing 90 mol% or more of a naphthalenedicarboxylic acid component and / or a terephthalic acid component in the dicarboxylic acid component from the viewpoint of heat resistance and productivity. is necessary. Other dicarboxylic acid components and those other than the above ranges are not preferable because heat resistance and productivity tend to be lowered.

  Examples of the glycol component include ethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, aliphatic glycols such as 1,3-propanediol, alicyclic glycols such as cyclohexanedimethanol, bisphenol-A, A glycol component such as an aromatic glycol such as bisphenol-S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a polyethylene glycol-propylene glycol copolymer, or the like can be used. The polyester used for the polyester layer of the composite film of the present invention has an ethylene glycol component in the range of 20 to 99.9 mol% in the glycol component and 1,3-propanediol from the viewpoint of moldability and productivity. And / or the 1,4-butanediol component needs to contain the range of 0.1-80 mol%. A glycol component other than the above and outside the above range is not preferable because moldability and productivity tend to be lowered. Examples of polyesters that can be preferably used include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate (PHT), polyethylene naphthalate (PEN), polycyclohexanedimethylene terephthalate ( PCT) and polyhydroxybenzoate (PHB). Two or more kinds of these polyesters can be used in combination.

  In producing the polyester used for the polyester layer of the composite film of the present invention, conventionally used reaction catalysts and anti-coloring agents can be used. Examples of the reaction catalyst include alkaline earth metal compounds, zinc A compound, a lead compound, a manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, or the like can be used. As a coloring inhibitor, for example, a phosphorus compound or the like can be used. Preferably, it is usually preferable to add an antimony compound, a germanium compound, or a titanium compound as a polymerization catalyst at an arbitrary stage before the production of the polyester is completed. As such a method, for example, when a germanium compound is taken as an example, a germanium compound powder is added as it is, or, as described in Japanese Patent Publication No. 54-22234, a glycosylated starting material for polyester. A method in which a germanium compound is dissolved and added to the component can be used.

  Examples of germanium compounds include germanium dioxide, germanium hydroxide containing crystal water, or germanium alkoxide compounds such as germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, germanium ethyleneglycoxide, germanium phenolate, germanium β- Germanium phenoxide compounds such as naphtholate, phosphorus-containing germanium compounds such as germanium phosphate and germanium phosphite, germanium acetate, and the like can be used. Of these, germanium dioxide is preferable.

  Although it does not specifically limit as an antimony compound, For example, antimony oxides, such as antimony trioxide, an antimony acetate, etc. can be used.

  The titanium compound is not particularly limited, but alkyl titanate compounds such as tetraethyl titanate and tetrabutyl titanate, and complex oxides of titanium and elements selected from silicon, zirconium and aluminum elements can be preferably used.

  The intrinsic viscosity of the polyester used for the polyester layer of the composite film of the present invention is preferably in the range of 0.6 to 1.3 dl / g. When the intrinsic viscosity is less than 0.6 dl / g, there is a tendency that particularly the deterioration of the moldability becomes remarkable. Moreover, it tends to be noticeable that the film forming property exceeds 1.3 dl / g, in particular, the film-forming property deteriorates and the thickness unevenness of the film becomes remarkable. The intrinsic viscosity of the polyester is more preferably in the range of 0.65 to 1.2 dl / g, particularly preferably in the range of 0.7 to 1.1 dl / g.

  It is preferable that melting | fusing point of polyester used for the polyester layer of the composite film of this invention is the range of 240-270 degreeC. A temperature lower than this range is not preferable because the heat resistance is particularly deteriorated. If the melting point exceeds this range, the moldability deteriorates, which is not preferable.

  A preferable means for setting the melting point of the polyester used in the polyester layer of the composite film of the present invention to the above range is not particularly limited. For example, a polyester resin having a melting point of 250 ° C. or higher is used, and a propylene terephthalate unit and / or butylene terephthalate is used. When the unit is contained, a method of mixing and using a polypropylene terephthalate resin and / or a polybutylene terephthalate resin can be mentioned.

  Here, the melting point in the present invention is a crystal melting peak caused by a polymer, and is determined from a DSC curve when the polymer is measured with a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min. This is the minimum point of the endothermic curve required for crystal melting, that is, the point at which the differential value becomes zero.

  In particular, when the polymer has a plurality of melting peaks, the main melting peak having the largest heat of fusion is defined as the melting point of the polymer.

  It is preferable that the polyester used for the polyester layer of the composite film of the present invention has a substantially single peak in the crystal melting curve of the polyester in DSC temperature rise measurement. If the crystal melting curve peak of the polyester shows two or more, the molecular structure is not uniform, and the moldability may be poor.

  Here, a shoulder peak (minimum peak) with a heat of fusion that partially overlaps one endothermic curve is 2 J / g or more is also considered as an independent crystal melting curve peak, and there are two (or more) peaks. It shall be.

  Furthermore, it is preferable that the carboxyl terminal group of the polyester used for the polyester layer of the composite film of this invention exists in the range of 30 eq / t or less. In such a preferable range, excellent transferability can be secured. More preferably, it is 25 eq / t or less, and particularly preferably 10 eq / t or less.

  In addition, when two or more kinds of polyesters are mixed and used as described above, the polyester satisfies M / P ≦ 1 in order to reduce variations in heat resistance, solvent resistance, printability, and quality. preferable. Here, M in the formula represents the concentration (mmol%) of the catalytic metal element remaining in the polyester, and P represents the concentration (mmol%) of the phosphorus element remaining in the polyester. These M and P are expressed as the concentration per unit (mole) of the repeating unit of the polyester.

  More preferably, M / P is 0.0001 or more and less than 1, and particularly preferably 0.001 or more and 0.8 or less.

  By controlling M / P ≦ 1, it is possible to increase the thermal stability, suppress the transesterification of the blend polymer, and suppress the lowering of the melting point due to heat treatment such as melt extrusion. As a result, the above-mentioned characteristics can be improved.

  Although the phosphorus compound added as a heat stabilizer to the polyester used for the polyester layer of the composite film of the present invention is not particularly limited, phosphoric acid, phosphorous acid, phosphoric acid ester and the like are preferable.

  In particular, a phosphorus compound having a molecular weight of 300 or more, particularly preferably 400 or more is preferably used from the viewpoint of suppressing bleeding out during film formation. Examples of phosphorus compounds having a molecular weight of 300 or more include stearyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and stearyl phosphate particularly suppresses bleed out. From the point of view, it is preferable.

  The content (addition amount) of the phosphorus compound added to the polyester used in the polyester layer of the composite film of the present invention is 20 to 1000 mmol% with the phosphorus compound as the phosphorus element amount from the viewpoint of thermal stability, color tone, and the like. Is preferable, more preferably 90 to 900 mmol%, particularly preferably 120 to 800 mmol%.

  Furthermore, as a method for adding the phosphorus compound, either a method of adding at the time of polymerization or a method of adding by adding to the extruder together with the polymer may be used. In general, when a large amount of a phosphorus compound is added during polymerization, the polymerization reaction is inhibited. Therefore, a method in which the polyester is added to an extruder together with a normal polyester in the range of M / P> 1 is preferable.

  It is preferable to add various antistatic agents to the polyester used in the polyester layer of the composite film of the present invention, copolymerize, or coat the polyester surface of the composite film. As the antistatic agent, various known anionic, cationic, nonionic and amphoteric ones can be used. Among these, from the viewpoint of heat resistance, it is preferable to use anionic antistatic agent Na alkyl sulfonate and Na alkylbenzene sulfonate.

  Moreover, when adding these antistatic agents at the time of superposition | polymerization, it is preferable from points, such as handling property, to add antioxidant together. As antioxidant, various well-known things, such as a phenolic antioxidant, a phosphite type antioxidant, a thioether type | system | group antioxidant, can be used, Furthermore, these compounds can also be used. .

The polyester layer of the composite film of the present invention needs to have a plane orientation coefficient in the range of 0 to 0.05, preferably in the range of 0 to 0.03, particularly from the viewpoint of moldability. Further, it is particularly preferable that the plane orientation coefficient is 0, that is, the polyester layer has an orientation degree corresponding to an unstretched film. Here, the plane orientation coefficient is fn represented by the following [Formula 1] and represents the degree of orientation of the film surface.
Plane orientation coefficient: fn = (Nx + Ny) / 2−Nz (Formula 1)

  Nx, Ny, and Nz represent the refractive index in the longitudinal direction, the refractive index in the width direction, and the refractive index in the thickness direction, and are values that can be measured using an Abbe refractometer or the like. In addition, when the refractive index is difficult to measure because the film is opaque, it is possible to convert the refractive index to the plane orientation coefficient by the measurement method of the degree of orientation using an infrared absorption spectrum or X-ray. .

  Various kinds of particles can be added to the polyester used in the polyester layer of the composite film of the present invention depending on the purpose and application. The particles to be added are not particularly limited as long as they are inert to the polyester, and examples thereof include inorganic particles, organic particles, crosslinked polymer particles, and internal particles generated in the polymerization system. Two or more kinds of these particles may be added. The addition amount of such particles is preferably 0.01 to 10% by mass, and more preferably 0.05 to 3% by mass.

  In particular, the number average particle diameter of the particles to be added is preferably 0.001 to 20 μm, and more preferably 0.01 to 10 μm, from the viewpoint of imparting easy lubricity of the film and improving handleability. When the number average particle diameter exceeds 20 μm, defects of the resin composition and the film are likely to occur, which may cause deterioration of moldability and the like. Moreover, if it is less than 0.001 micrometer, since sufficient slipperiness is not expressed, it is unpreferable.

  The type of inorganic particles is not particularly limited, but various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, various composite oxides such as kaolin and talc, lithium phosphate Various phosphates such as calcium phosphate and magnesium phosphate, various oxides such as aluminum oxide, silicon oxide, titanium oxide and zirconium oxide, and various salts such as lithium fluoride can be used.

  As the organic particles, terephthalate such as calcium oxalate, calcium, barium, zinc, manganese, and magnesium is used.

  Examples of the crosslinked polymer particles include homopolymers or copolymers of vinyl monomers such as divinylbenzene, styrene, acrylic acid, and methacrylic acid. In addition, organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.

  As the internal particles generated in the polymerization system, particles generated by a known method in which an alkali metal compound, an alkaline earth metal compound, or the like is added to the reaction system and a phosphorus compound is further added can be used.

  For the polyester used in the polyester layer of the composite film of the present invention, known additives such as flame retardants, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, plasticizers, and tackifiers are added as necessary. An appropriate amount of an agent, an organic lubricant such as a fatty acid ester or a wax, an antifoaming agent such as polysiloxane, or a coloring agent such as a pigment or a dye can be blended.

  In the composite film of the present invention, the elongation at break at 80 ° C. in terms of formability is preferably 500% or more, more preferably 800% or more, particularly preferably 1000% or more, and at 80 ° C. The stress at the time of 500% elongation is preferably 10 to 50 MPa, more preferably 15 to 30 MPa. That is, if the elongation at break and the stress at 500% elongation are less than the above ranges, the film does not have a stiffness at the time of molding, and printing misalignment is likely to occur. Exceeding the above range is not preferable because the pressure during molding may be increased.

  The composite film of the present invention needs to be laminated with polyolefin on at least one side from the viewpoint of chemical resistance to the solvent contained in the ink, that is, printability.

  The polyolefin used for the polyolefin layer of the composite film of the present invention is an α-olefin polymer such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like, and random Copolymers and block copolymers thereof can be used. As such a random 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. Thus, it 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.

  In addition, as the block copolymer, for example, in the case of a propylene / ethylene block copolymer, a copolymer comprising propylene in a range of 99 to 70% by mass and ethylene and / or α-olefin in a range of 1 to 30% by mass. A polymer part, a copolymer part composed of 1 to 30% by mass of propylene and 99 to 70% by mass of ethylene can be used as a block copolymer. 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.

  The melt flow index (MFI) of the polyolefin used for the polyolefin layer of the composite film of the present invention is preferably in the range of 1 to 10 g / 10 min, more preferably 2 to 5 g / 10 min in terms of impact resistance at low temperatures. It is.

  As the polyolefin used for the polyolefin layer of the composite film of the present invention, polyethylene alone, preferably low density polyethylene is preferably used, and among them, linear low density polyethylene is particularly preferably used. Further, in the random copolymer, a propylene / random copolymer is preferable, and a copolymer of propylene and ethylene or butene-1 is particularly preferably used, and the copolymerization ratio of the random copolymer is 2 to 2. A copolymer in which ethylene or butene-1 in a range of 15% by mass is randomly copolymerized with propylene is preferable. As the block copolymer, a polypropylene block copolymer is preferable, and a copolymer of propylene and ethylene or butene-1 is particularly preferably used. The copolymer of the block copolymer pair is preferably a copolymer in which ethylene or butene-1 in the range of 5 to 20% by mass is block copolymerized with propylene. The melting point of these polyolefins is preferably in the range of 110 to 165 ° C. from the viewpoint of heat resistance at the ink drying temperature and moldability.

  The polyolefin layer of the composite film of the present invention preferably has a plane orientation coefficient in the range of 0 to 0.01, particularly from the viewpoint of moldability. More preferably, the plane orientation coefficient is in the range of 0 to 0.005. Particularly preferably, the plane orientation coefficient is 0, that is, the polyolefin layer has an orientation degree corresponding to an unstretched film. Exceeding the above-mentioned preferable range is not preferable because followability with polyester tends to be deteriorated during molding, and moldability and printability are easily deteriorated.

  A thermoplastic elastomer can be added to the polyolefin used in the polyolefin layer of the composite film of the present invention. Thermoplastic elastomers are ethylene / propylene copolymers (hereinafter abbreviated as EPR), ethylene / butene copolymers (hereinafter abbreviated as EBR), ethylene / vinyl acetate copolymers (hereinafter abbreviated as EVA), hydrogenated It is preferable to add at least one thermoplastic elastomer such as a block copolymer in the range of 3 to 20 parts by weight. The range of 5 to 15 parts by weight is preferable. If it is less than the above range, the impact resistance at low temperatures is inferior, which is not preferable. If this range is exceeded, the amount of extraction with a solvent or the like tends to increase, which may cause a problem in food hygiene. The hydrogenated block copolymer is a polymer block (A) mainly composed of at least one vinyl aromatic compound and a copolymer block mainly composed of at least one hydrogenated conjugated diene compound ( B), for example, a hydrogenated block copolymer comprising ABA, BABA, BABA, and a mixture thereof. is there. And what contains 10-40 mass% of vinyl aromatic compounds can be used as this hydrogenated block copolymer.

  As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, styrene, α-methylstyrene and the like can be used, and styrene is particularly preferable. As the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound, for example, butadiene, isoprene, or 1-3 pentadiene can be used, and butadiene is particularly preferable. 80%, preferably 90% or more of the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is hydrogenated to form an olefin compound polymer block. Preferred as (B). As a typical copolymer example, styrene-ethylene-butylene-styrene copolymer (SEBS) can be mentioned, and the copolymerization amount of styrene is preferably 10 to 30% by mass. From the viewpoint of properties, those having 10 to 20% by mass are preferably used. In the case where the transparency is first, EPR and EBR are more preferable than EBS. The thermoplastic elastomer is preferably SEBS or EPR rather than EBS from the viewpoint of impact resistance. The melt flow index (MFI) of the thermoplastic elastomer is preferably 5 g / 10 min or less, and preferably 0.2 to 5 g / 10 min in terms of impact resistance at low temperatures.

  The composite film of the present invention is obtained by laminating a polyester layer and a polyolefin layer via an adhesive layer (a) made of a thermoplastic resin. The thermoplastic resin constituting the adhesive layer (a) needs to adhere the polyester layer and the polyolefin layer by using a thermoplastic resin excellent in adhesiveness to the polyester and polyolefin.

  Examples of such adhesive thermoplastic 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- Vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, Acid-modified polyolefin resins, poly (meth) acrylic resins, thermoplastic resins obtained by modifying polyolefin resins such as methylpentene polymer, polyethylene or polypropylene with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid or other unsaturated carboxylic acids Polyester Fat, such as a thermoplastic polyamide-based resin can be used. Among these adhesive thermoplastic resins, containing polar groups such as acid-modified polyolefin resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid or other unsaturated carboxylic acids Polyolefin is preferably used in terms of adhesion.

  The composite film of the present invention can be produced by a co-extrusion method, an extrusion lamination method, an extrusion coating method, a fusing method, a method combining these, and the like. The coextrusion method and / or the extrusion lamination method are preferably used.

  The co-extrusion method is a method for producing a composite film by supplying polyester, polyolefin, and adhesive layer (a) resin from a plurality of extruders to one die and simultaneously extruding them, and includes a T-die method and an inflation method.

  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. Can be manufactured by any of the flow method, die-in-layer method, and die-out-layer method, but uneven thickness in the width direction due to resin viscosity difference, adhesive layer (a) Temperature control when extruding resin, productivity In view of this, an in-die lamination method using a multi-manifold die can be preferably used. The composite film of the present invention can be produced by taking a multilayer sheet coextruded from a T-shaped multilayer multiple die on a cast roll.

  The inflation method is typically an in-die lamination method or an outside die lamination method. In the inflation method, the multi-layer parison co-extruded from the circular multi-layer dies is cooled, and the resulting tubular film can be folded into a flat film if necessary, or slit and wound into a roll. it can.

  When using the co-extrusion method, the composite film of the present invention can be produced by either the T-die method or the inflation method, but the T-die method is more preferably used from the viewpoint of productivity.

  When the composite film of the present invention is produced using the extrusion lamination method, a widely used method can be adopted as the extrusion lamination method itself. Specifically, a film to be a base material is formed in advance using an arbitrary resin, and the base film is traveled and supplied from a supply roll, or the base film is traveled and supplied inline while being optional. This resin is melted with a screw in an extruder, laminated (laminated) on the surface of a base film on which a molten film runs from a T die, and press-bonded with a roll to obtain a composite film.

  When the composite film of the present invention is produced using the extrusion lamination method, the surface of the base film on which the adhesive layer (a) is laminated is subjected to corona treatment for the purpose of enhancing the adhesive strength between the polyester layer and the polyolefin layer. It is preferable to do.

  When the composite film of the present invention is produced using the extrusion lamination method, the combination of the base film and the molten film is not limited as long as the composite film having the configuration of polyester layer / adhesive layer (a) / polyolefin layer can be produced. In general, the melting point of polyester film is higher than that of polyolefin and from the viewpoint of productivity, a polyester film is pre-formed as a base film, and a molten film in which an adhesive resin and polyolefin are laminated by a co-extrusion method is used to form an adhesive layer by an extrusion lamination method. The method of laminating so that (a) and the polyester layer are in contact is particularly preferably used.

  The composite film of the present invention can be manufactured by a co-extrusion method and / or an extrusion lamination method by using a thermoplastic resin for the adhesive layer (a), which greatly reduces the cost of the conventional manufacturing method. Can be achieved.

  The composite film of the present invention can further be provided with a release layer / topcoat layer / printing layer / adhesive layer (b) in this order on the polyolefin surface, and such a composite film can be used for a deep drawing transfer foil. it can. Here, the laminated film composed of a release layer / topcoat layer / printing layer / adhesive layer (b) is a laminated structure film for forming a coating film that forms a coating film on a molding resin by transfer.

  The composite film of the present invention is a composite film that satisfies both moldability and printability required for a deep-drawn transfer foil film, and further, for example, compared to a conventional laminated film such as JP-A-2004-188708. It is a composite film with excellent cost performance. For these reasons, the composite film of the present invention is preferably used as a film for transfer foils of complex parts surfaces such as automobile interior and exterior parts, building material decorative sheets, bathroom panels, household appliance parts, OA product parts, and the like. Can do.

  As the material for the release layer, known materials can be used, and at least one of melamine resin, silicone resin, fluororesin, cellulose derivative, urea resin, polyolefin resin, and paraffin release agent is preferably used. Examples of the method for forming the release layer include a coating method such as roll coating and spray coating, and a printing method such as gravure printing and screen printing.

  As the material for the top coat layer, known materials can be used, such as acrylic resins, polyester resins, polyvinyl chloride resins, cellulose resins, rubber resins, polyurethane resins, polyvinyl acetate resins, vinyl chloride. -It is preferable to use a vinyl acetate copolymer resin or an ethylene-vinyl acetate copolymer resin copolymer. Examples of the method for forming the topcoat layer include a coating method such as a roll coating method, a gravure coating method, and a comma coating method, and a printing method such as a gravure printing method and a screen printing.

  Since the top coat layer forms the surface of the molded product, a thermosetting resin, an ultraviolet curable resin, or a heat ray curable resin may be formed after peeling the composite film. Further, in order to improve the weather resistance, an ultraviolet absorber or an ultraviolet reflector may be added to the top coat layer. Further, in order to improve chemical resistance, a polyolefin resin may be coated.

  As the material for the printing layer, known materials can be used, such as polyurethane resins, vinyl resins, polyamide resins, polyester resins, acrylic resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, An alkyd resin, a thermoplastic elastomer resin, or the like is used. Further, a resin binder capable of producing a flexible film is preferably used, and it is particularly preferable to use a colored ink containing an appropriate color pigment or dye as a colorant.

  A known method can be used as a method for forming the print layer, and it is preferable to use a printing method such as an offset printing method, a gravure printing method, or a screen printing method. In particular, when multicolor printing or gradation colors are required, an offset printing method or a gravure printing method is preferably used. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, or a comma coating method may be employed. The printing method may be formed entirely or partially depending on the design.

  As the material for the adhesive layer (b) provided for the purpose of imparting adhesiveness to the molding resin, it is preferable to use a heat sensitive type or a pressure sensitive type. When the molding resin is an acrylic resin, it is preferable to use an acrylic resin. If the molding resin is a polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene resin, an acrylic resin, polystyrene resin, polyamide resin, or the like having an affinity for these resins may be used. It is preferable to use it. 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.

  As a method for forming the adhesive layer (b) provided for the purpose of imparting adhesiveness to the molding resin, a known method is used. For example, a coating method such as a roll coating method, a gravure coating method, a comma coating method, or a gravure printing method, for example. And printing methods such as screen printing are used.

  The molding resin is not particularly limited. For example, when used for automobile interior and exterior parts, polypropylene resin, acrylic resin, polystyrene resin, polyacrylonitrile / styrene resin, polyacrylonitrile / butadiene / styrene resin, etc. Is used.

  Depending on the purpose, a hard coat layer, a weather resistant layer, a flame retardant layer, an antifouling layer, an antibacterial layer, and the like can be formed on the polyolefin surface by a technique such as coating, coextrusion, thermal lamination, or dry lamination.

  In the composite film of the present invention, the preferred thickness is in the range of 10 to 600 μm, more preferably 20 to 400 μm, and particularly preferably 40 to 300 μm. The thickness of the polyester layer is preferably in the range of 5 to 300 μm, more preferably in the range of 10 to 200 μm, and the thickness of the polyolefin layer is preferably in the range of 5 to 300 μm, more preferably in the range of 10 to 200 μm. . If the thickness of each layer is less than the lower limit of the above range, the rigidity of the film, the film-forming stability and the flatness are deteriorated, and wrinkles are easily formed during molding, which is not preferable. In addition, if the upper limit of the above range is exceeded, handling properties and, in some cases, deterioration of moldability are caused, which is not preferable.

  In addition, the thickness of each layer of the release layer, topcoat layer, printing layer, and adhesive layer (b), which is a laminated structure film for forming a coating film to be further formed on the polyolefin surface, is the shape, material and size of the molded product. Thus, the thickness can be made appropriate.

  The thickness of the adhesive layer (a) formed between the polyester layer and the polyolefin layer is preferably in the range of 0.5 to 30 μm, more preferably in the range of 0.5 to 20 μm. If the thickness is less than the lower limit of the above range, sufficient adhesive strength cannot be obtained, and the polyester layer and the polyolefin layer are easily peeled off, which is not preferable. Moreover, since it will cause a deterioration of handleability and moldability when it exceeds the above upper limit, it is not preferable.

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

(1) Thickness When measuring the thickness of the entire film, the thickness at five arbitrary locations of each sample cut out from the film was measured using a dial gauge, and averaged. When measuring the layer thickness of the composite film, the cross section of the film was photographed using a transmission electron microscope (TEM) JEM-1200EX manufactured by JEOL Ltd. under conditions of a magnification of 1000 times and acceleration particles of 100 KV. The layer thickness of the film was measured.

(2) Melting point (Tm)
Using a differential scanning calorimeter DSCII type manufactured by Seiko Instrument Co., Ltd., the peak temperature of the endothermic melting curve when a sample was heated from room temperature at a heating rate of 10 ° C./min was defined as the melting point (Tm). .

(3) Intrinsic viscosity Polyester was dissolved in orthochlorophenol and measured at 25 ° C.

(4) Melt flow index (MFI)
It measured according to JIS-K-6758.

(5) Number average particle diameter The resin is removed from the film by a plasma low-temperature ashing method to expose the particles. The treatment conditions are such that the resin is incinerated but the particles are not damaged. This was observed with a scanning microscope for the number of particles of 5,000 to 10,000, and the number average particle diameter of the particle image was determined from the equivalent circle diameter with an image processing apparatus. When the particles are internal particles, the polymer cross section is cut to prepare ultrathin sections having a thickness of about 0.1 to 1 μm, and photographs are taken at a magnification of about 5,000 to 20,000 using a transmission electron microscope (10 Sheet: 25 cm × 25 cm), and the average dispersion diameter of the internal particles was calculated from the equivalent circle diameter.

(6) Plane orientation coefficient Using sodium D line (wavelength 589 nm) as a light source and using an Abbe refractometer, the longitudinal direction refractive index (Nx), width direction refractive index (Ny), and thickness direction refractive index (Nz) of the film are determined. The surface orientation coefficient (fn) was calculated from the following formula.
fn = (Nx + Ny) / 2−Nz.

(7) Stress at 500% elongation at 80 ° C. A sample having a length of 150 mm and a width of 10 mm is cut out from the composite film in two directions, the machine direction and the width direction, and in accordance with ASTM-D-882-81 (Method A). , And measured in an 80 ° C. atmosphere at a tensile speed of 100 mm / min. The stress at 500% elongation was determined.

(8) Chemical resistance After 3 ml of toluene was dropped on the film surface and allowed to stand for 6 hours, the toluene was wiped clean, and the surface state was visually observed and judged according to the following evaluation criteria. ○ and △ are acceptable levels.
○: No whitening, shrinkage, deformation, or trace of solvent is observed.
Δ: Whitening, shrinkage, and deformation are relatively light.
X: Whitening, shrinkage, or deformation is observed.

(9) Printability Printed on the film surface with gravure ink (“Hilamic”, manufactured by Dainichi Seika Kogyo Co., Ltd., main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow) mainly composed of polyurethane resin (50% yellow) Area) and dried at 50 ° C. Furthermore, gravure ink (“HIRAMIC” manufactured by Dainichi Seika Kogyo Co., Ltd., main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 701R white), which is mainly composed of polyurethane resin, is printed on the film surface (white 50% area), Dry at 70 ° C. The printing plate used was a 175-line 35 μm solid plate. The state of the printing film was visually observed and judged according to the following evaluation criteria from the viewpoint of printing defects, turbidity, wrinkles and the like. ○ and △ are acceptable levels.
○: Very clean and free from printing defects, wrinkles, turbidity.
Δ: Printing is relatively good, but slight turbidity and very slight wrinkles are observed.
X: Print quality is poor, and printing defects or turbidity and wrinkles that affect printing are observed.

(10) Formability Formability was evaluated under a temperature condition of 80 to 120 ° C using a cup type vacuum forming machine. Molding was performed using a cup shape with a diameter of 50 mm under the condition of a drawing ratio of 1.0, and the state when molded under the best temperature condition was determined as follows. ○ and △ are acceptable levels.
○: Corners were also sharply shaped and the thickness after molding was uniform.
Δ: Slightly rounded corners and slightly non-uniform thickness after molding.
X: The thickness after molding was uneven, and wrinkles and tearing occurred.

(11) Comprehensive evaluation Based on the evaluation results of chemical resistance, printability, and moldability, the determination was made as follows. ○ and △ are acceptable levels.
A: It can be preferably used as a film for transfer foil.
(Triangle | delta): Although a slight defect is recognized, it can be used as a film for transfer foil.
X: It cannot endure practical use as a film for transfer foil.

  The following polyesters and particle masters were used in Examples and Comparative Examples.

[Polyethylene terephthalate A (PET-A)]
To a mixture of 100% by mass of dimethyl terephthalate and 60% by mass of ethylene glycol, 0.09% by mass of magnesium acetate and 0.03% by mass of antimony trioxide are added to the amount of dimethyl terephthalate, and the temperature is increased by a conventional method. Then, a transesterification reaction was performed. Subsequently, after adding 0.020 mass% of 85% aqueous solution of phosphoric acid to the amount of dimethyl terephthalate, the transesterification reaction product is transferred to a polycondensation reaction tank. Subsequently, the reaction system was gradually depressurized while being heated, and a polycondensation reaction was carried out at 290 ° C. under a reduced pressure of 1 mmHg by a conventional method to obtain a polyethylene terephthalate resin having a melting point of 257 ° C. and an intrinsic viscosity of 0.65 dl / g. .

[Antistatic agent and particle master B (PET-B)]
During polymerization of PET-A, 6% by mass of sodium dodecylbenzenesulfonate and 4% by mass of polyethylene glycol (molecular weight 4000) as antistatic agents, and Irganox 1010 (manufactured by Ciba Specialty Chemicals) 0.10 as antioxidants A polyethylene terephthalate resin (inherent viscosity 0.65 dl / g, melting point 264 ° C.) to which 6% by mass and further 6% by mass of agglomerated silica particles (Fuji Divison particle size 2.5 μm) obtained by the following method was added was obtained.

  Aggregated silica particles: 1 equivalent of oxygen and 1 equivalent of hydrogen were vaporized in a vaporizer with respect to 1 equivalent of silicon tetrachloride, and hydrolyzed at 1000 ° C. in an oxyhydrogen flame to obtain silicon oxide particles. Further, agglomerated silica having a desired number average particle size was obtained by pulverizing with a wet sand mill using beads having a diameter of 0.5 mm.

[Isophthalic acid copolymerized polyterephthalate C (PET-C)]
11 mol% copolymerized polyethylene terephthalate (inherent viscosity 0.60 dl / g, melting point 229) as in PET-A, except that dimethyl terephthalate 89 mol% and dimethyl isophthalate 11 mol% were 100 mass%. C).

[1,4-Cyclohexanedimethanol copolymer polyterephthalate D (PET-D)]
Product name: “6763” (melting point: 190 ° C., intrinsic viscosity: 0.72) manufactured by Eastman Chemical Co., Ltd. was used.

[Polyethylene naphthalate A (PEN-A)]
A polyethylene naphthalate resin (melting point: 270 ° C., intrinsic viscosity: 0.69 dl / g) was obtained in the same manner as PET-A, except that dimethyl 2,6-naphthalenedicarboxylate was changed to 100% by mass instead of dimethyl terephthalate. It was.

[Polybutylene terephthalate A (PBT-A)]
Polybutylene terephthalate (melting point: 228 ° C., intrinsic viscosity: 1.26 dl / g) having a trade name of “Toraycon” 1200S manufactured by Toray Industries, Inc. was used.

[Polypropylene terephthalate A (PPT-A)]
Polypropylene terephthalate (inherent viscosity: 0.9 dl / g, melting point: 222 ° C.) having a trade name of “Corterra” CP509201 manufactured by Shell Chemical Co., Ltd. was used.

Example 1
The polyester used for the polyester layer was mixed according to the formulation shown in Table 1. Furthermore, 0.1% by mass of stearyl phosphoric acid {Asahi Denka Co., Ltd. (Adeka Stub AX-71)} was added separately and supplied to a vent type twin screw extruder (L / D = 36). The supplied resin was melted at 280 ° C. and then passed through two vacuum vent portions. Next, after passing through a leaf disk filter having a filtration accuracy of 30 μm, the filter was supplied to a multi-manifold die. An ethylene / butene / propylene copolymer (“FL6633A” manufactured by Sumitomo Chemical Co., Ltd., ethylene content = 2.1%, butene content = 5.5%, MI = 6 g / min, melting point = 137 ° C.) is used for the polyolefin layer. , Fed to a vent type twin screw extruder (L / D = 36), melted at 230 ° C., passed through two vacuum vents, then passed through a leaf disk filter with a filtration accuracy of 30 μm, Supplied to a manifold die. The adhesive layer (a) is made of a polar group-containing polyolefin (“Admer” SF715, manufactured by Mitsui Chemicals), supplied to a vented twin screw extruder (L / D = 36) and melted at 220 ° C., and then a vacuum vent part The solution was passed through two locations, then passed through a leaf disk filter having a filtration accuracy of 30 μm, and then supplied to a multi-manifold die whose temperature was adjusted to 280 ° C.

  After each resin passed through the manifold in the die, three kinds of resins were laminated on the polyester layer / adhesive layer (a) / polyolefin layer and extruded from the slit die into a sheet shape. A composite film of the present invention having a thickness of 170 μm is obtained by applying electrostatic force to both ends of the extruded sheet using a needle-like edge pinning device, closely contacting a mirror casting drum adjusted to a surface temperature of 50 ° C., and cooling and solidifying from a molten state. Obtained.

  On the polyolefin surface side of the obtained composite film, a release layer, a topcoat layer, a printed layer, and an adhesive layer (b) were sequentially formed.

  Here, as a release layer, a silicone resin release agent {“SH7028A” manufactured by Toray Dow Corning Silicone Co., Ltd.) is coated as a solid content with a bar coat to a thickness of 1 μm, and an ultraviolet curable acrylic resin is used as a top coat layer. {BASF Japan "LAROMER" LR8983} as a printing layer, polyurethane-based resin gravure ink as printing layer ("Hiramic" main solvent: Toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow / 701R white) As an adhesive layer (b), 100 μm of acrylonitrile-butadiene-styrene (ABS) copolymer resin film (ABS film “Hiflex” manufactured by Okamoto) was used.

  Next, a film for deep drawing transfer foil having a release layer, topcoat layer, printing layer, and adhesive layer (b) formed on the polyolefin surface side is heated to a temperature of 80 ° C. to obtain a drawing ratio of 1.0 and a 50 mm diameter cup. Using a concave mold and a vacuum molding machine, a cup-shaped molded body was produced at a temperature of 85 ° C., and a acrylonitrile-butadiene-styrene (ABS) copolymer resin heated to 280 ° C. (ABS resin “Toyolac manufactured by Toray Industries, Inc.) was used as the molding resin. "930) was injected into the cup-shaped molded body. After the ABS was cooled and solidified, the cup-shaped molded product was taken out from the mold, and the composite film was peeled off. Then, the top coat layer of the cup-shaped molded product was UV cured using a wavelength of 365 nm.

(Example 2)
The polyester was mixed with the formulation in Table 1. Furthermore, 0.1% by mass of stearyl phosphoric acid {Asahi Denka Co., Ltd. (Adeka Stub AX-71)} was added separately and supplied to a vent type twin screw extruder (L / D = 36). The supplied resin was melted at 280 ° C. and then passed through two vacuum vent portions. Next, after passing through a leaf disk filter having a filtration accuracy of 30 μm, the sheet was extruded from a slit-shaped die. Electrostatically applied to both ends of the extruded sheet using a needle-like edge pinning device, and brought into close contact with a mirror casting drum adjusted to a surface temperature of 50 ° C., cooled and solidified from the molten state to obtain a polyester unstretched film. On the other hand, linear low density polyethylene (“Novatech LL” UF240 manufactured by Nippon Polyethylene Co., Ltd.) is supplied to a vent type twin screw extruder (L / D = 36) as a polyolefin layer and melted at 230 ° C. The two parts were passed, and then passed through a leaf disk filter having a filtration accuracy of 30 μm, and then supplied to the feed block. In addition, a polar group-containing polyolefin (“Admer” SF715, manufactured by Mitsui Chemicals, Inc.) is used as the adhesive layer (a), which is supplied to a vent type twin screw extruder (L / D = 36) and melted at 230 ° C. The two parts were passed, and then passed through a leaf disk filter having a filtration accuracy of 30 μm, and then supplied to the feed block. The polyolefin layer and the adhesive layer (a) were merged in the feed block, and the molten sheet laminated on the polyolefin layer / adhesive layer (a) was extruded from a single manifold die. Therefore, the above polyester unstretched film is run and supplied as a base material, and on the other hand, it is laminated on the surface of the base film that runs the molten film from the T-die so that it has a structure of polyester layer / adhesive layer (a) / polyolefin layer. (Lamination) and pressure bonding with a roll to obtain a composite film of the present invention having a thickness of 240 μm.

  A release layer, a topcoat layer, a printing layer, and an adhesive layer (b) were formed on the obtained composite film in the same manner as in Example 1 to obtain a deep drawing transfer foil film.

  The characteristics of the obtained film were as shown in Table 1, and particularly excellent in moldability.

(Example 3)
The composition of the polyester layer was changed as shown in Table 1, polar group-containing polyolefin (“Admer” SF731 manufactured by Mitsui Chemicals) as the adhesive layer (a), and olefin-based thermoplastic containing ethylene / propylene copolymer as the polyolefin layer. Using a mixture of 50 parts by weight of an elastomer (“Tafmer P” 0280G manufactured by Mitsui Chemicals) and 50 parts by weight of polyethylene (low density polyethylene “J-REX807A” manufactured by Nippon Polyolefin Co., Ltd.) The same as in Example 1 except that the end electrostatic application method using the needle-like edge pinning device is changed to the whole surface electrostatic application method using the wire, and the melting temperature of the polyester layer and the temperature of the die are set to 290 ° C. The composite film of the present invention having a thickness of 200 μm was obtained by the method described above.

  A release layer, a topcoat layer, a printing layer, and an adhesive layer (b) were formed on the polyolefin surface of the obtained composite film in the same manner as in Example 1 to obtain a deep drawing transfer foil film.

  Although the properties of the obtained film were slightly inferior in printability, they were acceptable levels, and excellent in moldability.

Example 4
The composition of the polyester layer was changed as shown in Table 1, polar group-containing polyolefin (“Admer” SE800 manufactured by Mitsui Chemicals) as the adhesive layer (a), and ethylene / butene / propylene copolymer (manufactured by Sumitomo Chemical Co., Ltd.) as the polyolefin layer. FL6633A ″, ethylene content = 2.1 mass%, butene content = 5.5 mass%, MI = 6 g / min, melting point = 137 ° C.) and a casting drum in the process of obtaining a polyester film as a base film A composite film of the present invention having a thickness of 180 μm was obtained in the same manner as in Example 2 except that the temperature was 20 ° C.

  A release layer, a topcoat layer, a printed layer, and an adhesive layer (b) were formed on the polyolefin surface of the obtained composite film by the same method as in Example 2 to obtain a deep drawing transfer foil film.

  The obtained film characteristics are as shown in Table 2. Although some wrinkles were observed after printing and drying, the film was at an acceptable level, and particularly excellent in moldability.

(Example 5)
As a base film, a polypropylene biaxially stretched film having a thickness of 60 μm (“Torphan BO” type 2500 manufactured by Toray Industries, Inc.) is used. On the other hand, the polyesters shown in Table 1 are melted and bonded at 280 ° C. as a polyester layer. Melting at 230 ° C. using a polar group-containing polyolefin (“Admer” SE800 manufactured by Mitsui Chemicals) as the layer (a), melting on the polyester layer / adhesive layer (a) using a multi-manifold die adjusted to 280 ° C. A composite film of the present invention having a thickness of 188 μm was obtained in the same manner as in Example 2 except that the sheet was extruded and laminated on a base film.

  A release layer, a topcoat layer, a printed layer, and an adhesive layer (b) were formed on the base film surface of the obtained composite film by the same method as in Example 2 to produce a deep drawing transfer foil film. .

  The obtained film was excellent in chemical resistance and printability, but was slightly rounded at the corners of the molded product and slightly inferior in moldability. However, it was a passing level.

(Comparative Example 1)
An unstretched composite film was obtained in the same manner as in Example 1 except that the composition of the polyester layer was as shown in Table 1. The obtained unstretched composite film was stretched 3.4 times in the longitudinal direction at a temperature of 95 ° C., tenter stretched in the width direction at a stretching temperature of 115 ° C. and 3.05 times, and then relaxed at 200 ° C. with 5% relaxation, 5% A biaxially stretched composite film having a thickness of 200 μm was prepared by heat treatment for 2 seconds. In the obtained biaxially stretched composite film, the plane orientation coefficient of the polyester surface was 0.16, and the plane orientation coefficient of the polyolefin surface was 0.011. A release layer, a topcoat layer, a printing layer, and an adhesive layer (b) were formed on this biaxially stretched composite film in the same manner as in Example 1.

(Comparative Example 2)
Polyester blending was as shown in Table 1, and an unstretched polyester film having a thickness of 100 μm was obtained in the same manner as the base film of Example 2. The obtained polyester unstretched film was preheated at 90 ° C., stretched 3.1 times in the longitudinal direction with a 95 ° C. heating roll, further preheated at 110 ° C., and stretched 3.3 times at 115 ° C. in the width direction. Thereafter, a polyester biaxially stretched film having a thickness of 120 μm was prepared by using 5% relaxation in the width direction at a film temperature of 155 ° C. for 5 seconds, and used as a base film. The plane orientation coefficient of the obtained polyester base film was 0.158. As the molten film, both the polyolefin layer and the adhesive layer (b) were laminated by the same method as in Example 2 using the same resin as in Example 2 to obtain a composite film having a thickness of 250 μm. Further, a release layer, a topcoat layer, a printing layer, and an adhesive layer (b) were formed on the polyolefin surface of the composite film by the same method as in Example 1.

(Comparative Example 3)
The polyester composition was as shown in Table 1, and a polyester film having a thickness of 120 μm was obtained in the same manner as the base film of Example 2. The polyester film is not provided with an adhesive layer (a) and a polyolefin layer, and a release layer, a topcoat layer, a printed layer, and an adhesive layer (b) are formed by the same method as in Example 1, and used as a transfer foil film. evaluated.

(Comparative Example 4)
The polyester composition was as shown in Table 1, and a polyester film having a thickness of 100 μm was obtained in the same manner as the base film of Example 2. The polyester film is not provided with an adhesive layer (a) and a polyolefin layer, and a release layer, a topcoat layer, a printed layer, and an adhesive layer (b) are formed by the same method as in Example 1, and used as a transfer foil film. evaluated.

  The characteristics of the films obtained in Examples 1 to 4 were as shown in Table 1, and were excellent in solvent resistance, printability and moldability. In addition, the film obtained in Example 5 was inferior in moldability, but at a pass level, and was excellent in solvent resistance and printability.

  On the other hand, the films obtained in Comparative Example 1 and Comparative Example 2 were very inferior in moldability and could not withstand practical use. Moreover, although the film obtained in Comparative Example 3 and Comparative Example 4 was excellent in moldability, the solvent resistance was inferior, printing distortion was recognized, and the film could not be put into practical use.

The abbreviations in the table are as follows: PET: Polyethylene terephthalate PBT: Polybutylene terephthalate PEN: Polyethylene naphthalate PPT: Polypropylene terephthalate CPP: Ethylene / propylene copolymer LLD-PE: Linear low density polyethylene b- EPC: Block type-ethylene / propylene copolymer PP: Polypropylene NDC amount: Ratio of 2,6-naphthalenedicarboxylic acid component in all dicarboxylic acid components (mol%)
DMT amount: ratio of terephthalic acid component to total dicarboxylic acid component (mol%)
EG amount: Ratio of ethylene glycol component in all glycol components (mol%)
PG amount: Ratio of 1,3-propanediol component in all glycol components (mol%)
BG amount: Ratio of 1,4-butanediol component in all glycol components (mol%)
F500 value: Stress at 500% elongation at a temperature of 80 ° C

Claims (7)

The polyester layer is a polyester containing a dicarboxylic acid component satisfying the following (1) and a glycol component satisfying the following (2), and the adhesive layer (a) is an adhesive thermoplastic resin, and the film configuration is polyester layer / A composite film having a constitution of adhesive layer (a) / polyolefin layer, wherein the plane orientation coefficient of the polyester layer is in the range of 0 to 0.05.
(1) The dicarboxylic acid component contains 90% by mole or more of naphthalenedicarboxylic acid and / or terephthalic acid.
(2) The glycol component contains an ethylene glycol component in a range of 20 to 99.9 mol%, and a 1,3-propanediol component and / or a 1,4-butanediol component is 0.1 to 80 mol%. Included in the range.   The composite film according to claim 1, wherein the elongation at break at 80 ° C. is 500% or more, and the stress at the time of 500% elongation is in the range of 10 to 50 MPa.   The composite film according to claim 1 or 2, wherein the polyolefin layer is made of a polypropylene copolymer or polyethylene and has a plane orientation coefficient in the range of 0 to 0.05.   The composite film according to claim 1, wherein the adhesive thermoplastic resin used for the adhesive layer (a) is a polar group-containing polyolefin.   The release layer / topcoat layer / printing layer / adhesion layer (b) is further provided on the polyolefin layer side in this order so that the polyolefin layer and the release layer are in contact with each other. The composite film in any one of 1-4.   The composite film according to claim 1, which is used for transfer foil applications.   The manufacturing method which manufactures the composite film in any one of Claims 1-4 by the coextrusion method and / or the extrusion lamination method.