JP2006103176A - Laminate film for transfer foil and transfer foil using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate film for a transfer foil which is excellent in design property, moldability, peeling and a printing property. <P>SOLUTION: The laminated film for a transfer foil in which a polyolefin film is laminated at least on one side of a polyester non-oriented film and the surface side of the polyolefin film is embossed, has an average irregularity depth formed by embossing of 0.02-1.0 mm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminated film for transfer foil, which is excellent in printability, moldability, mold release property, and designability, and for transfer foil. In particular, the present invention is excellent in moldability such as deep drawability and followability to the surface shape of the transferred material, and also has excellent printability, and therefore is suitable for in-mold transfer foil used for printing and molding. The present invention relates to a film, and a film suitable for use as a transfer foil for performing printing of a decorative sheet for building materials, a packaging container, and the like, which are further vacuum-formed after printing.

  Conventionally, biaxially stretched polyester films have been used as transfer foil films that are printed and molded (see, for example, Patent Document 1 and Patent Document 2).

  In addition, a transfer foil using a copolyester film having a lower molding stress than a biaxially stretched polyester film has been proposed for the purpose of improving moldability (see Patent Document 3). In addition, it has been proposed to use a polyester film containing a specific glycol component such as butanediol as a glycol component constituting polyester for molding, processing, printing products, and the like (see Patent Document 4). In addition, a surface-treated polyester film and its transfer foil have been proposed for the purpose of improving design and moldability (see Patent Document 5).

  However, a transfer foil using a biaxially stretched polyester film is insufficient in terms of moldability for transfer to a member having a complicated shape. Moreover, the transfer foil using the above-mentioned copolymerized polyester film, the polyester film containing a specific glycol component such as butanediol, and the transfer foil using the surface-treated polyester film have good moldability, but particularly with respect to printability. There is a problem that the film surface smoothness deteriorates and printing defects are likely to occur due to solvents such as ethyl acetate, methyl ethyl ketone, and toluene contained in the printing ink. Moreover, the transfer foil using the surface-treated polyester film has a shallow surface processing depth, and a deep design property cannot be obtained.

Therefore, embossing is possible, and when transferred to a molded product, a deep design can be obtained, and a film with excellent chemical resistance to various solvents contained in printing ink, that is, printability and excellent moldability can be obtained. It was desired for a transfer foil.
JP-A-6-210799 JP 2000-344909 A Japanese Patent No. 3090911 JP 2002-97261 A JP 2004-231727 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, satisfy both the moldability and printability characteristics required for the transfer foil, and perform embossing, and transfer it to a molded product. When it does, it is providing the laminated film for transfer foil and transfer foil from which the design property with a depth is acquired.

  In order to solve the above-mentioned problems, the laminated film for transfer foil and the transfer foil of the present invention are specified mainly from the following matters.

  That is, it is a laminated film for transfer foil in which a polyolefin film is bonded to at least one surface of an unstretched polyester film and embossed on the polyolefin film surface side, and an average unevenness depth formed by embossing is 0. A laminated film for transfer foil, characterized in that it is 02 to 1.0 mm.

  Moreover, it is a transfer foil in which at least a top coat layer, a printing layer, and an adhesive layer are sequentially laminated on the embossed surface side of the transfer foil laminated film.

  According to the present invention, a transfer film laminated film suitable for a transfer foil excellent in design, printability, moldability, and peelability can be obtained as described below. More specifically, by embossing the polyolefin surface, at least a topcoat layer, a printing layer, and an adhesive layer are laminated on the embossed surface to form a transfer foil. A molded product having excellent design properties can be obtained. Moreover, since the embossed surface is excellent in solvent resistance against a solvent contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone, toluene, etc., it can be printed beautifully using various printing inks. In addition, because it has excellent moldability such as deep drawability and followability to the surface shape of molded products, it can be used for transfer processing of printing on decorative sheets for building materials, automotive interior / exterior parts, bathroom panels, parts for home appliances, packaging containers, etc. It is suitably used as a film for transfer foil for carrying out.

  The polyester film used for the laminated film for transfer foil of the present invention is mainly composed of polyester, and this polyester is a polymer having a basic constituent unit 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. In the polyester of the present invention, from the viewpoint of heat resistance and productivity, a naphthalenedicarboxylic acid component and / or a terephthalic acid component as a dicarboxylic acid component, which is an essential component, and a naphthalenedicarboxylic acid component and a terephthalic acid component as one optional component Is preferably contained in an amount of 90 mol% or more based on the dicarboxylic acid. When the dicarboxylic acid component other than those is contained in an amount exceeding 10 mol%, the heat resistance and productivity are likely to be lowered.

  Examples of the glycol component include aliphatic glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexamethylene glycol and neopentyl glycol, and alicyclic glycols such as cyclohexanedimethanol, A glycol component such as aromatic glycol such as bisphenol A or bisphenol S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-propylene glycol copolymer, or the like can be used. In the polyester of the present invention, from the viewpoint of moldability and productivity, the proportion of the ethylene glycol component in the glycol component is in the range of 20 to 99.9 mol%, and the 1,3-propanediol component and 1,4 One of the -butanediol components is an essential component, one is an optional component, and the proportion of the 1,3-propanediol component and the 1,4-butanediol component is in the range of 0.1 to 80 mol% preferable. More preferably, the ethylene glycol component is in the range of 50 to 99.9 mol%, and the sum of the 1,3-propanediol component and the 1,4-butanediol component, any of which are optional components, is 0.1 to 50 A range of mol% is preferred. Particularly preferably, the ethylene glycol component is in the range of 80 to 99.9 mol%, and the sum of the 1,3-propanediol component and the 1,4-butanediol component, any of which is an optional component, is 0.1 to 20 A range of mol% is preferred.

  If the above-mentioned glycol component conditions specified in the present invention are satisfied, other glycol components may be included, but if the above-mentioned glycol component conditions are not satisfied, moldability and productivity are likely 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), and polycyclohexanediene. Examples include methylene terephthalate (PCT) and polyhydroxybenzoate (PHB). In order to satisfy the glycol component conditions specified in the present invention, it is preferable to use two or more of these polyesters in combination. Moreover, the copolyester which satisfies the glycol component conditions and dicarboxylic acid conditions specified by this invention can also be used.

  When producing the polyester used in 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. 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 these polyesters is preferably in the range of 0.6 to 1.3 dl / g. When it is less than 0.6 dl / g, the deterioration of the moldability is particularly remarkable, and when it is 1.3 dl / g or more, the deterioration of the film forming property and the uneven thickness of the film are particularly 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.

  The melting point of these polyesters is preferably in the range of 240 to 270 ° C. If the temperature is lower than this range, the heat resistance may be insufficient. On the other hand, if the melting point exceeds this range, the moldability tends to decrease.

  The preferred means for setting the melting point to the above range is not particularly limited. For example, a polypropylene terephthalate resin and / or a polybutylene terephthalate resin is placed on a polyester resin having an melting point of 250 ° C. or higher composed of ethylene terephthalate units and / or ethylene naphthalate units. A method in which propylene terephthalate units and / or butylene terephthalate units are incorporated by quantitative mixing is exemplified.

  Here, the melting point in the present invention is the temperature of the crystal melting peak caused by the polymer. That is, an endothermic curve at the time of crystal melting is obtained 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, and the minimum point in this endothermic curve, This is the temperature at which the differential value becomes zero. When the polymer has a plurality of melting peaks, the main melting peak having the largest heat of fusion is taken as the melting point of the polymer.

  The polyester film constituting the laminated film for transfer foil of the present invention preferably has a substantially single peak in the crystal melting curve of the film in DSC temperature rise measurement. If two or more peaks of the crystal melting curve of polyester are shown, the molecular structure is not uniform, and the moldability may be poor. Here, a shoulder peak (minimum peak) with a heat of fusion partially overlapping one endothermic curve of 2 J / g or more is also regarded as an independent crystal melting curve peak, and two (or more) peaks exist. It shall be.

  Further, the carboxyl end group of the polyester is preferably in the range of 30 eq / t or less in order to ensure excellent transferability. 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 polyester are mixed and used as described above, the polyester satisfies the condition of M / P ≦ 1, which improves heat resistance, solvent resistance, and printability, and improves quality. This is preferable for reducing variation. 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 represent 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 setting M / P ≦ 1, thermal stability is increased, transesterification in the blend polymer is suppressed, and a decrease in melting point due to heat treatment can be suppressed. As a result, the above-described characteristics can be improved.

  Although the phosphorus compound which can be added to the polyester in the present invention as a heat stabilizer 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 is preferably 20 to 1000 mmol%, more preferably 90 to 900, based on the phosphorus compound as the phosphorus element amount from the viewpoint of thermal stability, color tone, and the like. It is in the range of 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 the polymerization, the polymerization reaction is inhibited. Therefore, a method of adding to an extruder together with a normal polyester having M / P> 1 is preferable.

  Various antistatic agents may be added to the polyester film. This antistatic agent is added by a method of adding to polyester, a method of copolymerizing in polyester, or a method of coating on a film. As the antistatic agent, various known anionic, cationic, nonionic and amphoteric ones can be used. Of these, anionic antistatic agents such as sodium alkylsulfonate and sodium alkylbenzenesulfonate are particularly preferred from the standpoint of heat resistance.

  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 film constituting the film for transfer foil in the present invention needs to be an unstretched film particularly from the viewpoint of moldability. Being an unstretched film can be expressed by having a plane orientation coefficient in the range of 0 to 0.05, preferably in the range of 0 to 0.03. When the plane orientation coefficient exceeds the above range, a molded product having a large molding drawing ratio may be difficult to mold, and the moldability is poor. Here, the plane orientation coefficient is fn represented by the following [Formula 1] and represents the degree of orientation of the film.

Plane orientation coefficient: fn = (Nx + Ny) / 2−Nz [Formula 1]
In Equation 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. When the refractive index is difficult to measure because the film is opaque, the degree of orientation obtained by a measuring method such as an infrared absorption spectrum or X-ray may be converted into a plane orientation coefficient based on the refractive index.

  Various particles can be added to the polyester film constituting the embossed bonded film in 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 amount of such particles added is preferably 0.01 to 10% by weight, more preferably 0.05 to 3% by weight.

  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 slipperiness to the film and improving handleability. When the number average particle diameter exceeds 20 μm, defects in the film are likely to occur, which may cause deterioration of moldability. If it is less than 0.001 μm, sufficient slipperiness may not be exhibited.

  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, calcium oxalate, terephthalate such as calcium, barium, zinc, manganese, magnesium, etc. are 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.

  Examples of the internal particles generated in the polymerization system include 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.

  In the polyester film constituting the laminated film for transfer foil in the present invention, known additives, for example, flame retardant, heat stabilizer, antioxidant, ultraviolet absorber, antistatic agent, plasticizer, An appropriate amount of a tackifier, an organic lubricant such as a fatty acid ester or wax, an antifoaming agent such as polysiloxane, or a colorant such as a pigment or dye can be blended.

  In the present invention, the polyester film constituting the laminated film for transfer foil has a break elongation at 80 ° C. of 500% or more, more preferably 800% or more, more preferably 1000% or more, in terms of moldability. It is. There is no upper limit in the preferred range, but the larger the better, the better the moldability, and the upper limit in the usual range is about 2000%. Moreover, the stress at 500% elongation at 80 ° C. is preferably in the range of 10 to 50 MPa. Especially preferably, it is 15-30 Mpa. If it is less than the above range, there is a case where the film does not have a slack at the time of molding and printing misalignment may occur. When the above range is exceeded, the pressure during molding may be required to be high. Moreover, in the elongation (S) -stress (S) curve obtained by 80 degreeC tension measurement, the curve from which a yield point is not obtained is preferable. If there is a yield point on the SS curve, after transfer to the molding object, stress remains on the film, and various laminates such as a film and a printed layer may be peeled off from the molding.

  The laminated film for transfer foil of the present invention can be bonded to a polyolefin film on at least one surface of a polyester film from the viewpoint of chemical resistance to a solvent contained in the ink, that is, printability and releasability such as a printing layer. is necessary. The polyolefin film is composed of a polymer from an α-olefin monomer such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like. Copolymers and block copolymers are also used.

  For example, in the case of a propylene copolymer, the random copolymer is a polymer obtained by randomly copolymerizing propylene and one or more α-olefin monomers excluding propylene from the α-olefin monomer. Examples thereof include polypropylene obtained by copolymerizing one or more α-olefin monomers in a range of 2 to 15% by weight by a known method. The melt flow index (MFI) 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.

  In the case of a propylene / ethylene / block copolymer, for example, the block copolymer is a copolymer portion comprising a large amount of propylene and a small amount of ethylene and / or other α-olefin, and a small amount of propylene. And a copolymer portion composed of an abundant amount of ethylene are copolymerized in a block manner. The composition of each copolymer component, the molecular weight of each block, etc. 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. The melting point can be varied by the amount of polypropylene component in the copolymer portion consisting of abundant amounts of propylene and small amounts of ethylene and / or other α-olefins. Further, the amount of ethylene and / or other α-olefin component in the propylene / ethylene block copolymer is preferably 5 to 20% by weight, more preferably 5 to 15% in terms of impact resistance of the film. %.

  When the polyolefin film in the present invention is made of a homopolymer, it is preferable to use polyethylene, particularly low density polyethylene, and further linear low density polyethylene. In the case of a random copolymer, a propylene / random copolymer is preferable, and a copolymer obtained by copolymerizing propylene with ethylene or butene-1 is particularly preferable. The ratio of the copolymer component is 2 to 15% by weight. The range of is preferable. In the case of a block copolymer, a polypropylene block copolymer is preferable, and a copolymer obtained by copolymerizing polypropylene and ethylene and butene-1 is particularly preferable. The proportion of the copolymer component is 5 to 20% by weight. The range of is preferable. The melting point of these polyolefin films is preferably in the range of 110 to 165 ° C. from the viewpoint of heat resistance at the ink drying temperature.

  The polyolefin film in the present invention is preferably an unstretched film particularly from the viewpoint of moldability. The unstretched polyolefin film has a plane orientation coefficient in the range of 0 to 0.01, preferably in the range of 0 to 0.005. If the plane orientation coefficient exceeds the above range, the followability with the bonded polyester film tends to be poor, so printing distortion and moldability tend to deteriorate, which is not preferable.

  A thermoplastic elastomer can be added to the polyolefin film constituting the laminated film for transfer foil. Thermoplastic elastomers include ethylene / propylene copolymers (hereinafter abbreviated as EPR), ethylene / butene copolymers (hereinafter abbreviated as EBR), ethylene / vinyl acetate copolymers (hereinafter abbreviated as EVA), water, An additive block copolymer is exemplified, and it is preferable to add one or more thermoplastic elastomers in the range of 3 to 20 parts by weight. Furthermore, the range of 5-15 weight part is preferable. If it is less than the above range, the impact resistance at low temperatures is inferior, which is not preferable, and if it exceeds the above range, the amount of extraction with a solvent or the like tends to increase. There is a case.

  The hydrogenated block copolymer is composed of a polymer block (A) having at least one vinyl aromatic compound as a main component and a copolymer block having at least one hydrogenated conjugated diene compound as a main component ( B), for example, a hydrogenated block having a structure consisting of ABA, BABA, BABA, and a mixture thereof. It is a polymer. And as this hydrogenated block copolymer, what contains 10 to 40 weight% of vinyl aromatic compounds can be used.

  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 bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated to give an olefinic compound polymer block B.

  A typical example of the copolymer is styrene-ethylene-butylene-styrene copolymer (SEBS), and the copolymerization amount of styrene is preferably 10 to 30% by weight. From the viewpoint of transparency, those having a styrene copolymerization amount of 10 to 20% by weight are preferred, and EPR and EBR are more preferred. The thermoplastic elastomer is preferably SEBS or EPR from the viewpoint of impact resistance. The melt flow index (MI) of the thermoplastic elastomer is preferably 5 g / 10 min or less, more preferably 0.2 to 5 g / 10 min in terms of impact resistance at low temperatures.

  An adhesive is preferably used for bonding the polyester film and the polyolefin film. The adhesive may be a thermosetting type or a thermoplastic type, but is preferably a thermosetting type. For example, polyurethane resins, polyester resins, polyvinyl chloride resins, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, methyl methacrylate-butadiene copolymers, rubber resins such as chloroprene and polybutadiene, poly From acrylic ester resins, polyvinylidene chloride resins, polybutadiene, or carboxyl modified products of these resins, epoxy resins, cellulose derivatives, ethylene vinyl acetate copolymers, polyethylene oxide, acrylic resins, lignin derivatives, etc. The adhesive which becomes is mentioned. From the viewpoint of adhesion between the polyester film and the polyolefin film, an adhesive composed of a polyurethane resin or a polyester resin is preferable. Further, for bonding the polyester film and the polyolefin film, an adhesive resin layer may be provided on the polyester film, and the polyolefin resin may be subjected to melt extrusion lamination.

  The laminated film for transfer foil of the present invention may be embossed on the polyester film side, but from the viewpoint of improving the solvent resistance to various coating agents in the subsequent process and the design of the molded product to be transferred. It is necessary to emboss the polyolefin film surface side. Examples of the embossing method include a hot needle method for passing a film through a perforator (perforating machine), a method for passing it through a stamping roll, a method for passing it through a chilled roll, and a method for embossing immediately after melt extrusion, It is preferable to obtain the embossed pattern of the roll by transferring the embossed pattern of the roll to the polyolefin film surface side by passing a laminated film between the metal roll containing the embossed pattern and a paper or rubber roll and applying pressure. The embossed pattern can be selected from various patterns such as a random mat, a square, a diamond type, a deep drawing type, and a grain pattern. For better embossability, the metal roll temperature is heated above the glass transition temperature of the polyester film, pressed to transfer the embossed pattern, and then quenched and solidified below the glass transition temperature of the polyester film. The shape can be maintained.

  Also, when a polyolefin film is made into a sheet by melt extrusion by the T-die method, a method is used in which a surface irregularity pattern is transferred to the film surface by pressing between the cooling drum and a nip roll using a cooling drum having an irregular surface. It may be.

  Further, as other processing methods for embossing, hairline processing, satin processing, sandblasting, and the like can be mentioned. Preferably, embossing is preferable in order to obtain a deep and excellent design. Also, before embossing, hairline processing, satin processing, sandblasting, or the like may be performed in advance.

  Thus, it is preferable that the average uneven | corrugated depth of the surface obtained by embossing is the range of 0.02-1.0 mm. When it is less than the range, it is not preferable that the surface of the molded product is difficult to obtain with a deep design when it is transferred to the molded product. On the other hand, if the range is exceeded, the average uneven depth is too deep, and film breakage or the like may occur during molding, which is not preferable.

  The transfer foil laminated film of the present invention is formed by laminating at least a topcoat layer and a printing layer sequentially on the embossed surface, and then laminating an adhesive layer thereon as necessary. can do. When the transfer foil is used for press molding, the printing foil is bonded to a resin plate or a steel plate via an adhesive or an adhesive film and molded. Or when using for vacuum forming and in-mold shaping | molding, the adhesive layer which consists of an adhesive agent or an adhesive film is laminated | stacked on the printing layer surface of transfer foil, and simultaneous integral molding with molding resin is performed. After these moldings, the polyester film / polyolefin film part is peeled and removed, so that the top coat layer and the printed layer are transferred to the surface of the molded product, and the surface is excellent in design with a depth by embossing. A molded product can be obtained.

  As the material of the top coat layer, acrylic resin, polyester resin, polyvinyl chloride resin, cellulose resin, rubber resin, polyurethane resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, An ethylene-vinyl acetate copolymer resin copolymer is preferred. As a method of laminating the top coat layer, there are a coating method such as a roll coating method, a gravure coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing. Since the top coat layer is the layer that forms the outer surface of the molded product after transfer, it must be cured by heat, UV, or heat ray before or after removing the polyester film / polyolefin film. A resin that can be used as a top coat layer may be laminated. Further, in order to improve the weather resistance, an ultraviolet absorber or an ultraviolet reflector may be added to the top coat layer. In order to improve chemical resistance, a polyolefin resin may be used as the top coat layer.

  In order to further improve the design properties, a printing layer may be laminated. The binder resin material for the printing layer includes polyurethane resins, vinyl resins, polyamide resins, polyester resins, acrylic resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and thermoplastics. Elastomeric resins and the like are preferable, and among them, a resin capable of producing a flexible film is preferable, and it is preferable to add a colored ink containing a pigment or dye of an appropriate color as a colorant. Further, a resin that can be heat-cured, ultraviolet-cured, or heat-ray-cured may be laminated as a printed layer before or after the polyester film / polyolefin film is peeled and removed. It is preferable to use a printing method such as an offset printing method, a gravure printing method, or a screen printing method as a method for laminating the printing layers. In particular, when multicolor printing or gradation colors are required, the offset printing method and the gravure printing method are preferable. 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. Depending on the design, a printing method in which a printing layer is laminated on the entire surface or a printing method in which a printing layer is partially laminated may be used.

  When integrally forming the transfer foil and the molding resin of the present invention by vacuum molding, in-mold molding, or the like, it is preferable to laminate an adhesive layer on the printed layer surface. As the material for the adhesive layer, it is preferable to use a heat-sensitive type or a pressure-sensitive type. When the molding resin is an acrylic resin, an acrylic resin adhesive is preferable. In addition, when the molding resin is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene resin, acrylic resin, polystyrene resin, polyamide resin, etc. that have an affinity for these resins An adhesive is preferred. When the molding resin is a polypropylene resin, a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone indene resin adhesive is preferable. Examples of the method for laminating the adhesive layer include coating methods such as a roll coating method, a gravure coating method, and a comma coating method, a printing method such as a gravure printing method, and screen printing.

  The molding resin is not particularly limited. For example, in the case of producing a molded product used for automobile interior and exterior parts, polypropylene resin, acrylic resin, polystyrene resin, polyacrylonitrile / styrene resin, polyacrylonitrile / butadiene.・ Styrene resins are used.

  In addition, according to the purpose, the transfer foil of the present invention is provided with a release layer, a weather resistant layer, a flame retardant layer, an antifouling layer, an antibacterial layer, and the like by a method such as coating, coextrusion, thermal lamination, and dry lamination. It can also be laminated on the processed surface.

  In the laminated film for transfer foil of the present invention, the thickness of the laminated film is preferably 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 film is in the range of 5 to 300 μm, preferably in the range of 10 to 200 μm, and the thickness of the polyolefin film is in the range of 5 to 300 μm, preferably in the range of 10 to 200 μm. If it is less than this range, the rigidity, film-forming stability and flatness of the film deteriorate, and wrinkles and the like are liable to occur during molding, which is not preferable. On the other hand, when the above range is exceeded, handling properties and, in some cases, deterioration of moldability are caused, which is not preferable. More preferably, the ratio of the thickness of the polyester film to the thickness of the polyolefin film is preferably in the range of 3 to 7: 7 to 3 from the viewpoints of moldability, transferability and handleability. The thicknesses of the top coat layer, the printed layer, and the adhesive layer formed on the surface processed surface can be set to appropriate thicknesses depending on the shape, material, and size of the molded product.

  Since the laminated film for transfer foil of the present invention can be molded into a three-dimensional shape and has a deep and excellent design, the surface of a component having a complicated shape, for example, an automotive interior / exterior component, a decorative sheet for building materials, etc. It can be preferably used as a transfer foil for bathroom panels, home appliance parts, OA product parts, packaging containers and the like.

  Hereinafter, the present invention will be described in detail by way of examples. Various characteristics were measured and evaluated by the following methods.

(1) Melting point (Tm)
Using a differential scanning calorimeter DSCII type manufactured by Seiko Instrument Co., Ltd., the melting point (Tm) is the peak temperature of the endothermic melting curve when 5 mg of the sample was heated from room temperature at a heating rate of 10 ° C./min. did.

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

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

(4) 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), the width direction refractive index (Ny), and the thickness direction refractive index (Nz) of the film The surface orientation coefficient (fn) was calculated from the following formula.
fn = (Nx + Ny) / 2−Nz.

(5) Breaking elongation at 80 ° C., stress at 500% elongation From the polyester film before bonding, a sample having a machine direction (MD) or a width direction (TD) as a longitudinal direction (length 150 mm, width 10 mm) Was measured according to ASTM-D-882-81 (Method A) in an 80 ° C. atmosphere at a tensile rate of 100 mm / min. The elongation at break and the stress at 500% elongation were determined.

(6) Average unevenness depth Using a laser microscope VK8510 manufactured by KEYENCE, measured the profile of 6 embossed films embossed at a magnification of 10 times, profile (plurality) mode, measurement length of 1490 μm, and pitch of 0.1 μm. Using the profile corresponding to one emboss, the lowest value is the MIN depth, the highest value is the MAX depth, and the height difference value (= MAX depth-MIN depth) is obtained, and the height obtained from each profile The average value of the difference values was defined as the average unevenness depth.

(7) Chemical resistance 3 ml each of toluene, ethyl acetate, and methyl ethyl ketone was dropped on the surface of the laminated film on the polyolefin film side and left for 6 hours. Then, each solvent was wiped clean, and the surface condition was visually observed. Judgment was made according to the following criteria.
○: 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.

(8) Formability On the polyolefin film surface side of the laminated film, it is passed at a speed of 1 m / min between a 300 mm depth heated to 120 ° C and a 0.4 mm square engraved roll and a paper roll at a pressure of 200 MPa. Pressurized, quenched to room temperature and embossed.

Next, a top coat layer, a printing layer, and an adhesive layer were formed in this order on the embossed surface to produce a transfer foil. As a top coat layer, an ultraviolet curable acrylic resin {"LAROMER" LR8983} manufactured by BASF Japan Co., Ltd. with a thickness of 60 μm, and as a printing layer, a polyurethane resin gravure ink ("Hiramic" manufactured by Dainichi Seika Kogyo Co., Ltd.), Main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow / 701R white) is formed with a thickness of 70 μm, and an acrylonitrile / butadiene / styrene (ABS) copolymer resin film (ABS film manufactured by Okamoto Co., Ltd.) as an adhesive layer. “High Flex”, thickness 100 μm) was used. In order to cure the printed layer, aging was performed at a temperature of 40 ° C. for 72 hours. Further, the transfer foil was heated to a temperature of 80 ° C., and an ABS copolymer resin cup-shaped molded product was arranged on the adhesive layer surface side of the transfer foil, and transfer molded at a temperature of 85 ° C. using a pressure forming machine. After releasing the pressure, the top coat layer was UV-cured using UV light having a wavelength of 365 nm while the transfer foil was stuck. The molded state of the transfer foil was visually observed and judged according to the following criteria.
○: Corners of the molded product were also sharply shaped and the thickness after molding was uniform.
Δ: The corner of the molded product was slightly rounded, and the thickness after molding was slightly non-uniform.
X: The thickness after molding was uneven, and wrinkles or tears occurred.

(9) Peelability Using the transfer foil-bonded ABS resin cup-shaped molded product obtained by the moldability of (9) above, the ABS resin can be seen from the outer surface by peeling the laminated film layer on the outer surface. A cup-shaped molded product was produced. The peeled state of the laminated film was visually observed, and the peelability was determined according to the following criteria.
◯: A material that is neatly transferred to a molded product and excellent in releasability.
Δ: A part of the molded product is not transferred and the peelability is slightly inferior, but there is no practical problem.
X: A part is not transferred to the molded product, the peelability is inferior, and this is a practical problem.

(10) Designability Using the ABS resin cup-shaped molded product obtained in the peelability of (9) above, the surface state of the molded product was observed visually, and the designability was determined according to the following criteria.
◯: Good surface processability and deep design.
Δ: Surface workability is slightly insufficient and design is slightly inferior, but there is no practical problem.
X: The surface is glaring and has poor design properties.

(11) Comprehensive evaluation With regard to surface workability, chemical resistance, moldability, peelability, and practicality as designability, an excellent one was evaluated as ◯, a slightly inferior one was evaluated as Δ, and an inferior one was evaluated as ×.

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

[Polyethylene terephthalate A (PET-A)]
To a mixture of 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.09% by weight of magnesium acetate and 0.03% by weight of antimony trioxide are added to the amount of dimethyl terephthalate, and heated by a conventional method. The ester exchange reaction was carried out with warming. Next, 0.020% by weight of 85% aqueous phosphoric acid solution is added to the transesterification product with respect to the amount of dimethyl terephthalate, and then 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-containing polyethylene terephthalate master B (PET-B)]
During polymerization of PET-A, 6% by weight of sodium dodecylbenzenesulfonate and 4% by weight of polyethylene glycol (molecular weight 4000) as an antistatic agent, “Irganox” 1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant 0 10% by weight, and further 6% by weight of aggregated silica particles (Fuji Divison Co., Ltd., several particle diameter 2.5 μm) obtained by the following method were added and polymerized in the same manner as in the above PET-A, A polyethylene terephthalate master resin (inherent viscosity 0.65 dl / g, melting point 264 ° C.) containing an antistatic agent and particles was prepared.

  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 1,000 ° C. in an oxyhydrogen flame to obtain silicon oxide particles. Further, agglomerated silica having a desired average particle size was obtained by pulverization with a wet sand mill using beads having a diameter of 0.5 mm.

[Isophthalic acid copolymerized polyethylene terephthalate C (PET-C)]
11 mol of isophthalic acid was the same as PET-A except that 100 parts by weight of dimethyl terephthalate was changed to 100 parts by weight of a dicarboxylic acid monomer composed of 89 mol% of dimethyl terephthalate and 11 mol% of dimethyl isophthalate. % Copolymerized polyethylene terephthalate (inherent viscosity 0.60 dl / g, melting point 229 ° C.) was prepared.

[1,4-Cyclohexanedimethanol copolymerized polyethylene terephthalate D (PET-D)]
The product name: 6763 ″ (melting point: 190 ° C., intrinsic viscosity: 0.72) manufactured by Eastman Chemical Co. was used. The copolymerization ratio of 1,4-cyclohexanedimethanol was 30 mol%.

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

[Polybutylene terephthalate A (PBT-A)]
Polybutylene terephthalate (melting point: 228 ° C., intrinsic viscosity: 1.26 dl / g) manufactured by Toray Industries, Inc., trade name “Trecon” 1200S 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
Polyesters of PET-A, PBT-A and PET-B were mixed according to the formulation shown in Table 1. Furthermore, 0.1% by weight of stearyl phosphoric acid (Adeka Stub “AX-71” manufactured by Asahi Denka Co., Ltd.) 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, brought into close contact with a mirror casting drum (CD) adjusted to a surface temperature of 50 ° C., cooled and solidified from the molten state, and 100 μm thick polyester A stretched film was obtained.

  Polyurethane adhesive {Make Takeda Chemical Co., Ltd. “Takelac” A610 (concentration 35-45%) / Mitsui Takeda Chemical Co., Ltd. “Takenate” A50 (concentration 20-30%) = 9 / 1 (mixed weight ratio), 25 wt% ethyl acetate solution}, a polypropylene-based unstretched film of ethylene / propylene copolymer (“Torphan NO” 3501T, thickness 60 μm manufactured by Toray Synthetic Film Co., Ltd.) A laminated film was prepared by laminating.

  The obtained laminated film was passed through the polyolefin film side of the laminated film at a depth of 300 μm heated to 120 ° C. and a size of 0.4 mm between a square stamping roll and a paper roll at a speed of 1 m / min. It was pressed and rapidly cooled to room temperature, embossed with an average unevenness depth of 135 μm, and a laminated film for transfer foil of the present invention was produced.

  Next, a top coat layer, a printing layer, and an adhesive layer were formed in this order on the embossed surface of the obtained laminated film for transfer foil to produce a transfer foil. As a top coat layer, an ultraviolet curable acrylic resin {"LAROMER" LR8983} manufactured by BASF Japan Co., Ltd. with a thickness of 60 μm, and as a printing layer, a polyurethane resin gravure ink ("Hiramic" manufactured by Dainichi Seika Kogyo Co., Ltd.), Main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow / 701R white) is formed with a thickness of 70 μm, and acrylonitrile / butadiene / styrene (ABS) copolymer resin film (ABS manufactured by Okamoto Co., Ltd.) is used as an adhesive layer. The film “Hiflex”, thickness 100 μm) was used. In order to cure the printed layer, aging was performed at a temperature of 40 ° C. for 72 hours.

  Next, an acrylonitrile / butadiene / styrene (ABS) copolymer resin (manufactured by Toray Industries, Inc., ABS resin “Toyolac” 930) is used as a draw ratio 1.0, a 50 mm diameter cup concave mold, an injection molding machine, and a molding resin. It was used and injection-molded to produce an ABS copolymer resin cup-shaped molded product.

  Further, the transfer foil was heated to a temperature of 80 ° C., and an ABS copolymer resin cup-shaped molded product was arranged on the adhesive layer surface side of the transfer foil, and transfer molded at a temperature of 85 ° C. using a pressure forming machine. After releasing the pressure, with the transfer foil attached, the top coat layer is cured with ultraviolet rays using a wavelength of 365 nm, and then the bonded film layer on the outer surface is peeled off, and the ABS resin cup is visible from the outer surface. A molded product was produced.

  The obtained molded article made of ABS copolymer resin had an excellent design with deep embossed printing on the surface, and a clean shape.

(Example 2)
A polyester unstretched film was obtained in the same manner as in Example 1 except that the composition of the polyester was changed as shown in Table 1. A linear low-density polyethylene unstretched film (“LL film” 4801 manufactured by Toray Synthetic Film Co., Ltd., thickness 100 μm) is bonded to the obtained polyester unstretched film by the same method as in Example 1 and bonded. A film was obtained.

  Next, the film was pressed against the surface of the metal roll (polishing cloth) wound with a polishing cloth (Nippon Kenshi Co., Ltd. “resin cloth” SRCX-S16) with a free roll, and the film was allowed to run in that state, and The metal roll was rotated in the direction opposite to the film running direction, and a hairline process was applied to one surface of the film. Furthermore, embossing with an average concavo-convex depth of 60 μm was performed in the same manner as in Example 1 to prepare a laminated film for transfer foil of the present invention.

  Next, a top coat layer, a print layer, and an adhesive layer were laminated on the embossed surface of the obtained laminated film for transfer foil by the same method as in Example 1. As the ink for the printing layer, polyurethane resin gravure ink (Daiichi Seika Kogyo Co., Ltd. “NT-Hilamic”, main solvent: ethyl acetate / methyl ethyl ketone / isopropyl alcohol, ink: 12 silver) was used. Were sequentially laminated to prepare a transfer foil.

Next, using the obtained transfer foil, transfer molding was performed in the same manner as in Example 1 to prepare an ABS copolymer resin cup-shaped molded product.
The obtained ABS copolymer resin molded product had excellent design and a clean shape, with a silvery print appearing on the surface, deep in hairline semi-glossy metal background printing.

(Example 3)
The composition of polyester was changed as shown in Table 1, and the method of close contact with the mirror casting drum was changed from the edge electrostatic application method using a needle-like edge pinning device to the whole surface electrostatic application method using a wire. Further, a polyester unstretched film was produced by the same method as in Example 1 except that the extrusion temperature was changed to 290 ° C. To the obtained polyester unstretched film, a block-type ethylene / propylene copolymer polypropylene-based unstretched film (“Torephan NO” ZK93K manufactured by Toray Synthetic Film Co., Ltd., thickness 100 μm) was applied in the same manner as in Example 1. By bonding, a bonded film was obtained. The embossing was carried out in the same manner as in Example 1, and an embossing with an average unevenness depth of 130 μm was performed to produce a laminated film for transfer foil of the present invention.

  Next, a top coat layer, a printing layer, and an adhesive layer are laminated on the embossed surface of the obtained transfer foil laminated film by the same method as in Example 1, to obtain a transfer foil, transfer molding, and ABS. A molded product made of a copolymer resin was obtained.

  The resulting ABS copolymer resin molded product is a print with embossing on the surface, a matte semi-glossy print, and a deep, excellent design and shape. Was also beautiful.

Example 4
A polyester unstretched film was produced in the same manner as in Example 3 except that the composition of the polyester was changed as shown in Table 1 and the temperature of the casting drum was changed to 20 ° C. A polypropylene-based unstretched film of ethylene / propylene copolymer (“Trephan NO” 3951 manufactured by Toray Synthetic Films Co., Ltd., thickness 100 μm) is bonded to the obtained polyester unstretched film by the same method as in Example 1. Thus, a laminated film was obtained. Next, air blower "MYBLAST" MY-30A made by Shinto Blator is used on the surface of polypropylene-based unstretched film, and sprayed uniformly over the film surface for 3 seconds with ceramic-based spray material with a particle size of 10-200 µm and compressed air of 0.5 MPa. , Sandblasted. Further, a laminated film for transfer foil of the present invention having a sandblast surface with an average unevenness depth of 0.4 μm and an embossed surface with an average unevenness depth of 100 μm was prepared by the same method as in Example 1.

  Next, a top coat layer, a printing layer, and an adhesive layer are laminated on the embossed surface of the obtained transfer foil laminated film by the same method as in Example 1, to obtain a transfer foil, transfer molding, and ABS. A molded product made of a copolymer resin was obtained.

  The obtained ABS copolymer resin molded product had excellent design and a beautiful shape with a semi-glossy printing on the surface and a deep design.

(Example 5)
The composition of the polyester was changed as shown in Table 1, and a polyester unstretched film having a thickness of 100 μm was obtained in the same manner as in Example 1. As the polyolefin film, an ethylene / butane / propylene copolymer (FL6633A, ethylene content = 2.1%, butane content = 5.5%, MI = 6 g / min, melting point = 137 ° C.) manufactured by Sumitomo Chemical Co., Ltd., bent type It supplied to the twin-screw extruder (L / D = 36). The supplied resin was melted at 230 ° 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. Both ends of the extruded sheet were brought into close contact with a satin casting drum adjusted to a surface temperature of 20 ° C. with 50 MPa compressed air, cooled and solidified from a molten state, and a surface-treated polyolefin unstretched film having a thickness of 100 μm was obtained.

  The polyester unstretched film obtained previously and the opposite surface of the polyolefin unstretched film to the CD surface were bonded together in the same manner as in Example 1. Further, the laminated film for transfer foil of the present invention having a textured surface with an average unevenness depth of 0.4 μm and an embossed surface with an average unevenness depth of 50 μm is prepared on the bonded non-stretched film surface by the same method as in Example 1. did.

  Next, a top coat layer, a printing layer, and an adhesive layer are laminated on the embossed surface of the obtained transfer foil laminated film by the same method as in Example 1, to obtain a transfer foil, transfer molding, and ABS. A molded product made of a copolymer resin was obtained.

  The obtained ABS copolymer resin molded product had excellent design and a beautiful shape, with the printing appearing on the surface being deep and semi-glossy textured printing.

(Comparative Example 1)
A polyolefin film was obtained in the same manner as in Example 5 except that the thickness was 200 μm. Using this film, embossing is performed in the same manner as in Example 1, an embossed film is obtained, and a topcoat layer, a printing layer, and an adhesive layer are laminated on the embossed surface in the same manner as in Example 1. Transfer molding was performed to obtain an ABS copolymer resin molded product.

(Comparative Example 2)
An unstretched film was prepared in the same manner as in Example 1 except that the composition of the polyester was changed as shown in Table 1. After preheating at 90 ° C., the film was stretched 3.0 times in the longitudinal direction at 95 ° C. Further, after preheating at 110 ° C., tenter-stretching was performed 3.3 times at 115 ° C. in the width direction, followed by heat treatment at 230 ° C. for 5% for 5 seconds to produce a polyester biaxially stretched film whose thickness was adjusted to 50 μm. did. The plane orientation coefficient of the obtained film was 0.16. The obtained polyester biaxially stretched film was bonded to a polyolefin film by the same method as in Example 1 to obtain a bonded film. Next, the film was pressed against the surface of the metal roll (polishing cloth) wound with a polishing cloth (Nippon Kenshi Co., Ltd. “resin cloth” SRCX-S16) with a free roll, and the film was allowed to run in that state, and The metal roll was rotated in the direction opposite to the film running direction, and the polyolefin surface was subjected to hairline processing to produce a surface processed film having an average unevenness depth of 0.9 μm. A top coat layer, a printing layer, and an adhesive layer were laminated on the hairline processed surface, and transfer molded to obtain an ABS copolymer resin molded product.

(Comparative Example 3)
An unstretched film was prepared in the same manner as in Example 1 except that the composition of the polyester was changed as shown in Table 1. After preheating at 85 ° C., the film was stretched 3.1 times in the longitudinal direction at 90 ° C. Furthermore, after preheating at 110 ° C., tenter stretching was performed 3.3 times at 115 ° C. in the width direction, and then the heat treatment was changed to 5% relaxation in the width direction at a film temperature of 200 ° C. for 5 seconds. A polyester biaxially stretched film (thickness 50 μm) was obtained in the same manner as in Comparative Example 1. In addition, a polyolefin film is bonded by the same method as in Example 1 to obtain a bonded film, and the unstretched polyester film surface is embossed by the same method as in Example 1. A top coat layer, a printing layer, and an adhesive layer were laminated by the same method, and transfer molded to obtain an ABS copolymer resin molded product.

(Comparative Example 4)
A polyester non-stretched film having a thickness of 120 μm was obtained in the same manner as in Example 1 except that the composition of the polyester was changed as shown in Table 1. Next, air blaster “MYBLAST” MY-30A made by Shinto Blator is used on the surface of polypropylene-based unstretched film, and the film surface is uniformly applied to the film surface for 3 seconds with a ceramic-based spray material having a particle diameter of 10 to 200 μm and compressed air of 0.5 MPa. By spraying and sandblasting, a surface processed film having an average unevenness depth of 0.4 μm was produced. A top coat layer, a printing layer, and an adhesive layer were laminated on the sandblasted surface, and transfer molded to obtain an ABS copolymer resin molded product.
(Comparative Example 5)
A polyester non-stretched film having a thickness of 90 μm was obtained in the same manner as in Example 1 except that the composition of the polyester was changed as shown in Table 1. In addition, the polyolefin film is bonded to Toray “Trephan” 2500S (thickness 60 μm) as a polyolefin film by the same method as in Example 1 to obtain a bonded film, and the polyolefin film surface is embossed by the same method as in Example 1. Then, a top coat layer, a printing layer, and an adhesive layer were laminated on the embossed surface, and transfer molded to obtain an ABS copolymer resin molded product.

(Comparative Example 6)
Toray “Lumirror” T60 (thickness 100 μm) is used as the polyester film, and Toray “Torephan” 2500S (thickness 60 μm) is laminated as a polyolefin film in the same manner as in Example 1 to obtain a laminated film. The polyolefin film surface was embossed in the same manner as in Example 1, and a topcoat layer, a printing layer, and an adhesive layer were laminated on the embossed surface, and transfer molded to obtain an ABS copolymer resin molded product.

  The characteristics of the laminated films for transfer foils obtained in Examples 1 to 5 were as shown in Table 1, and both surface processability and chemical resistance were excellent. Further, when the transfer foil was transferred to the ABS copolymer resin molded product, an excellent design property with excellent moldability and releasability was obtained.

  On the other hand, the film obtained in Comparative Example 1 was excellent in chemical resistance and peelability and slightly inferior in surface workability, but was inferior in moldability and could not be put into practical use as a transfer foil. Moreover, although the films obtained in Comparative Examples 2-3 and Comparative Examples 5-6 are excellent in chemical resistance and peelability, they have extremely poor surface processability, moldability, and designability, and can be used practically as transfer foils. It was not possible. Furthermore, the film obtained in Comparative Example 4 was inferior in solvent resistance and peelability, and was not preferable as a transfer foil. In addition, the film obtained in Comparative Example 2 for hairline processing and Comparative Example 4 for sandblasting had a shallow average unevenness, and a deep design was not obtained.

  However, the abbreviations in the table are as follows.

PET: Polyethylene terephthalate PBT: Polybutylene terephthalate PEN: Polyethylene naphthalate PPT: Polypropylene terephthalate CPP: Polypropylene unstretched film LLD-PE: Linear low density polyethylene unstretched film b-EPC: Block-ethylene-propylene copolymer Unstretched film PP-BO: Polypropylene biaxially stretched film 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 diol components (mol%)
PG amount: Ratio of 1,3-propanediol component to all diol components (mol%)
BG amount: Ratio of 1,4-butanediol component in all diol components (mol%)
F500 value: Stress at 500% elongation

  The transfer foil laminated film of the present invention is excellent in printability, moldability, and peelability, and therefore can be used as a transfer foil film. When the transfer foil is transferred to a molded product, the transferred surface is deep. Since a certain excellent molded article can be obtained, it can be suitably used for a decorative sheet for building materials, automotive interior / exterior parts, bathroom panels, parts for home appliances, packaging containers, and the like.

Claims (5)

A laminated film for transfer foil in which a polyolefin film is bonded to at least one surface of a polyester unstretched film and embossed on the polyolefin film surface side, and the average unevenness depth formed by embossing is 0.02 to 0.02 A laminated film for transfer foil, which is 1.0 mm. The polyester constituting the polyester unstretched film contains 90 mol% or more of naphthalenedicarboxylic acid and / or terephthalic acid as the dicarboxylic acid component, and 20 to 99.9 mol% of the ethylene glycol component as the diol component, A laminated film for transfer foil, which is a polyester comprising a monomer composition containing 0.1 to 80 mol% of a 3-propanediol component and / or 1,4-butanediol component. The lamination for transfer foil according to claim 1 or 2, wherein the unstretched polyester film has a breaking elongation at 80 ° C of 500% or more and a stress at the time of 500% elongation is in the range of 10 to 50 MPa. the film. The laminated film for transfer foil according to claim 1, wherein the polyolefin film is an unstretched film made of a polypropylene copolymer or polyethylene. A transfer foil comprising at least a topcoat layer, a printing layer, and an adhesive layer sequentially laminated on the embossed surface side of the transfer foil laminated film according to claim 1.