JP4765567B2 - Laminated film for transfer foil and transfer foil using the same - Google Patents

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. More specifically, it is excellent in moldability such as deep drawability and followability to the surface shape of the transfer object, and also has excellent printability, so that it is suitable for in-mold transfer foil used for printing and molding. Further, the present invention relates to a film suitable as a transfer foil for performing printing of a decorative sheet for building material, a packaging container, and the like used by further vacuum forming after printing.

  As a film for transfer foil used by printing and molding, a biaxially stretched polyester film (for example, see Patent Document 1 and Patent Document 2) has been used, and this biaxially stretched polyester film was used. The transfer foil is insufficient in terms of formability for transfer to a member having a complicated shape.

  Moreover, as a polyester film aiming at the improvement of a moldability, the transfer foil (for example, refer patent document 3) using the copolyester film whose molding stress is low compared with a biaxially stretched polyester film, and polyester are comprised. Polyester films for molding, processing, printing products and the like containing a specific glycol component such as butanediol as a glycol component have been proposed (for example, see Patent Document 4). Transfer foils using these polyester films are Although the moldability is good, the printability is not particularly considered, and the smoothness of the film surface is deteriorated and printing defects are likely to occur due to solvents such as ethyl acetate, methyl ethyl ketone, and toluene contained in the printing ink. There were problems such as.

  Furthermore, a surface-treated polyester film for the purpose of improving design properties and moldability, and a transfer foil thereof (for example, refer to Patent Document 5) have been proposed. When the coating was applied, the lubricant in the polyolefin bleeded out, and problems such as peeling off of the coating agent applied due to aging or preheating during molding occurred. Further, when the thickness variation of the polyolefin film is large, when the coating material for transfer foil is applied, the thickness of the coating material cannot be applied uniformly, resulting in a problem that the design of the transferred molded product is inferior.

Therefore, the coating agent can be applied uniformly, and the embossing is possible without causing problems such as peeling of the coating agent applied with time or preheating at the time of molding, and excellent when transferred to a molded product There has been a demand for the realization of a film for transfer foil that has a design property and is excellent in chemical resistance to various solvents contained in the printing ink, that is, excellent in printability and excellent in moldability.
JP-A-6-210799 JP 2000-344909 A Japanese Patent No. 3090911 JP 2002-97261 A JP 2004-188708 A

  The present invention has been achieved as a result of examining the solution of the problems in the conventional techniques described above as an issue.

  Therefore, the object of the present invention is to satisfy both the moldability and printability characteristics required for the transfer foil and to be embossed, and to obtain a deep design when transferred to a molded product. It is providing the laminated film for transfer foil, and a transfer foil.

In order to achieve the above object, according to the present invention, there is provided a laminated film for transfer foil in which a polyolefin film is laminated on at least one surface of an unstretched polyester film, wherein the polyolefin film is a fatty acid amide as an organic lubricant. transfer foil 01 contains 0.05 wt%, and the thickness of this range near thickness irregularity of ± 5% of the polyolefin film is, and laminated for transfer foil film is characterized 200~600μm der Rukoto A laminated film for use is provided.

In addition, in the laminated film for transfer foil of the present invention,
The fatty acid amide is at least one selected from oleic acid amide, stearic acid amide and erucic acid amide;
The polyolefin film surface side is embossed, and the average unevenness depth formed by embossing is 0.02 to 1.0 mm,
The polyester constituting the polyester unstretched film contains 90% by mole or more of naphthalenedicarboxylic acid and / or terephthalic acid as a dicarboxylic acid component, and 20 to 99.9% by mole of an ethylene glycol component as a diol component; A polyester comprising a monomer composition containing 0.1 to 80 mol% of 3-propanediol component and / or 1,4-butanediol component;
The elongation at break of the polyester unstretched film 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, and the polyolefin film is made of a polypropylene copolymer or polyethylene. Any non-stretched film can be mentioned as a preferable condition.

  The transfer foil of the present invention is characterized in that at least a top coat layer, a print layer, and an adhesive layer are sequentially laminated on the polyolefin film surface side of the above-mentioned transfer foil laminated film.

  According to the present invention, as described below, it is possible to obtain a laminated film for transfer foil which is excellent in printability, moldability, mold release property, and design property and suitable for transfer foil.

  More specifically, the amount of fatty acid amide contained in the polyolefin film and the thickness unevenness of the polyolefin film are specified, and further, by embossing the polyolefin film surface, at least the topcoat layer and the printing on the embossed surface When the layer and adhesive layer are laminated to form a transfer foil and transferred to a molded product, the coating material does not peel off over time and with preheating, and the coating surface with a uniform thickness is excellent in deep design. A molded product can be obtained. In addition, the polyolefin surface is excellent in solvent resistance against a solvent contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone, toluene and the like, and therefore 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.

  Hereinafter, preferred embodiments of the laminated film for transfer foil and the transfer foil according to the present invention will be described.

The laminated film for transfer foil of the present invention is a laminated film for transfer foil in which a polyolefin film is bonded to at least one surface of a polyester unstretched film, and the polyolefin film contains 0.01 to 0 fatty acid amide as an organic lubricant. .05 contained by weight%, and the range near thickness irregularity of ± 5% of the polyolefin film is, and the thickness of the paste for transfer foil combined film is characterized 200~600μm der Rukoto. By specifying the amount of fatty acid amide contained in the polyolefin film and the thickness unevenness of the polyolefin film, transparency can be maintained, and when coating various types of coatings, uniform thickness coatings can be laminated. It is possible to obtain a transfer foil in which the coating material does not peel off over time and preheating / heating.

  In the laminated film for transfer foil of the present invention, the fatty acid amide added to the polyolefin film is preferably one or a mixture of fatty acid amides having 12 to 24 carbon atoms, such as lauric acid amide, tridecanoic acid amide, myristic acid amide, Pentadecanoic acid amide, valmitic acid amide, heptadecanoic acid amide, stearic acid amide, oleic acid amide, elaidic acid amide, linoleic acid amide, linolenic acid amide, stearolic acid amide, ricinoelaidic acid amide, arachic acid amide, behenic acid amide , Erucic acid amide, brassic acid amide, erucic acid amide, and lignoceric acid amide. Of these, addition of one of stearic acid amide, oleic acid amide, and erucic acid amide or a mixture thereof is preferable from the viewpoint of slippage with a small amount of addition and transparency of the film.

In the laminated film for transfer foil of the present invention, the amount of fatty acid amide added to the polyolefin film needs to be in the range of 0.01 to 0.05 % by weight. It is unpreferable from the point of the blocking property of a film, and the release property of a coating material that it is less than the said range. On the other hand, when the above range is exceeded, when various coating materials for transfer foil are laminated, the coating material peels off due to aging and preheating, and transfer to a molded product causes wrinkles of the coating material, which is not preferable. By setting it as said addition amount range, blocking prevention, the mold release property of a coating material, and the peelability of a coating material can be made compatible.

  In the laminated film for transfer foil of the present invention, the thickness unevenness of the polyolefin film needs to be in the range of ± 5% in order to make the coating thickness of various coating materials uniform. If the thickness unevenness of the film is outside the above range, the coating thickness varies when the coating is applied, and when the coating is transferred to the molded product, thick or thin portions of the coating are produced, This is not preferable because the color becomes worse and the design is inferior. The thickness unevenness of the polyolefin film is more preferably in the range of ± 3%.

  In the laminated film for transfer foil of the present invention, it is preferable that embossing is performed on the polyolefin film surface side, and the average unevenness depth formed by the embossing is 0.02 to 1.0 mm.

  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 preferable 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. When making the embossing workability good, after heating the metal roll temperature above the glass transition temperature of the polyester film and pressurizing it to transfer the embossed pattern, by rapidly cooling and solidifying below the glass transition temperature of the polyester film, The shape of the embossed pattern can be maintained.

  In addition, when a polyolefin film is formed into a sheet by melt extrusion using the T-die method, a cooling drum having an uneven surface is used, and the surface uneven pattern is transferred to the film surface by pressing between the cooling drum and the nip roll. It may be a method.

  Moreover, as other processing methods of embossing, hairline processing, satin processing, sandblasting, etc. are mentioned, but in order to obtain a deep and excellent design, embossing is preferable. Furthermore, 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. If it is less than the range, it tends to be difficult to obtain a deep design property when the surface of the molded product is transferred to the molded product. On the other hand, when the range is exceeded, the average uneven depth is too deep, and film breakage may occur during molding.

  In the laminated film for transfer foil of the present invention, the polyester film 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 viewpoints of heat resistance and productivity, a naphthalenedicarboxylic acid component and / or a terephthalic acid component as a dicarboxylic acid component, one of which is an essential component, one of which is an optional component, a naphthalenedicarboxylic acid component and a terephthalic acid component It is preferable to contain in an amount such that the sum of the components is 90 mol% or more based on the dicarboxylic acid. When other dicarboxylic acid components are contained in an amount exceeding 10 mol%, heat resistance and productivity tend 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 in 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, One of the 4-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%. It is preferable. More preferably, the ethylene glycol component is in the range of 50 to 99.9 mol%, and the sum of 1,3-propanediol component and 1,4-butanediol component, any of which are optional components, is 0.1 to 50 mol % Is preferable. 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 It is preferably in the range of mol%.

  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 tend to be reduced. Become.

  Examples of the polyester that can be preferably used in the present invention include, for example, polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate (PHT), polyethylene naphthalate (PEN), Polycyclohexanedimethylene terephthalate (PCT), polyhydroxybenzoate (PHB), and the like can be mentioned. 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, an alkaline earth metal compound, zinc compound, lead compound, manganese compound, cobalt compound, aluminum compound, antimony compound, titanium compound, etc. 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 film-forming property is particularly deteriorated 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.

  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 due to the polymer. That is, an endothermic curve at the time of crystal melting was determined from a DSC curve when the polymer was 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 the heat resistance, solvent resistance, and printability, and the quality. It is preferable for reducing the variation of the above. 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 one repeating unit (mol) 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 to be added to the polyester is preferably 20 to 1000 mmol%, more preferably 90 to 100% in terms of the phosphorus element amount from the viewpoint of thermal stability, color tone, and the like. It is 900 mmol%, particularly preferably in the range of 120 to 800 mmol%.

  Furthermore, as a method for adding the phosphorus compound, any of a method of adding at the time of polymerization and a method of adding it 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 inferior. 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 laminated film in the present invention according to 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 formed 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 or the like may occur. If 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 tensile measurement, it is preferable that it is a curve from which a yield point is not obtained. 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. Polypropylene obtained by copolymerizing one or more α-olefin monomers in the range of 2 to 15% by weight by the above 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 drying temperature of the coating solvent.

  The polyolefin film in the present invention is preferably an unstretched film particularly from the viewpoint of moldability. The unstretched polyolefin film can have a plane orientation coefficient in the range of 0 to 0.01, preferably in the range of 0 to 0.005. When the plane orientation coefficient exceeds the above range, the followability with the bonded polyester film tends to be deteriorated, so that an undesired tendency that printing distortion and moldability are likely to deteriorate may be caused.

  A thermoplastic elastomer can be added to the polyolefin film constituting the laminated film for transfer foil. Examples of thermoplastic elastomers include ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / vinyl acetate copolymers, hydrogenated block copolymers, and the like. It can be added in the range of 3 to 20 parts by weight from the viewpoint of impact.

  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 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, it is molded by adhering the printed foil surface to a resin plate or steel plate via an adhesive or adhesive film. 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 printing layer are transferred to the surface of the molded product, and the surface is excellent in design with 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, an adhesive such as a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone indene resin 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 in the range of 200 to 600 μm. If it is less than this range, the rigidity, film-forming stability and flatness of the film will deteriorate, and wrinkles will tend to occur during molding. On the other hand, if the above range is exceeded, the handleability and, in some cases, the moldability tends to deteriorate. Furthermore, it is preferable that the ratio of the thickness of a polyester film and the thickness of a polyolefin film is the range of 3-7: 7-3 from the point of a 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 interior / exterior part of an automobile or a makeup for a building material It can be preferably used for transfer foils such as sheets, bathroom panels, home appliance parts, OA product parts, and packaging containers.

  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) Thickness unevenness of polyolefin film The bonded film was immersed in methyl ethyl ketone (MEK) for 12 hours, the polyester film and the polyolefin film were peeled off, and the adhesive adhered to the polyolefin film was removed with MEK. Using this polyolefin film as a measurement sample, an Anritsu film sickness tester KG601A and an electronic micrometer K306C were used to measure the thickness of a film sampled 30 mm wide and 2 m long in any direction of the measurement sample at a measurement interval of 0.2 mm. The maximum value Ta (μm), the minimum value Tb (μm), and the average value Tc (μm) were determined, and thickness spots (%) were determined from the following formula (1) and the following formula (2).
・ Thickness unevenness (plus) = (Ta−Tc) / Tc × 100 (1)
Thickness unevenness (minus) = (Tb−Tc) / Tc × 100 (2).

(6) 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.

(7) 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.

(8) Chemical resistance 3 ml each of toluene, ethyl acetate, and methyl ethyl ketone are dropped on the surface of the laminated film on the polyolefin film side and left at a temperature of 23 ° C. and a humidity of 65% RH for 24 hours, and then clean each solvent with absorbent cotton. The surface condition was visually observed and judged according to the following criteria.
○: Whitening, shrinkage, deformation, no trace of solvent,
Δ: Whitening, shrinkage, deformation is relatively light,
X: Whitening, shrinkage, or deformation is observed.

(9) Formability On the polyolefin film surface side of the bonded 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. UV curable acrylic resin {"LAROMER" LR8983} manufactured by BASF Japan Co., Ltd. with a thickness of 60 μm as the top coat layer, and polyurethane resin gravure ink (“HIRAMIC” manufactured by Dainichi Seika Kogyo Co., Ltd.) as the printing layer 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: Corners of the molded product were slightly rounded, and the thickness after molding was slightly uneven.
X: The thickness after molding was uneven, and wrinkles or tears occurred.

(10) Peelability ABS resin that can be printed from the outer surface by peeling off the laminated film layer on the outer surface using the transfer foil-bonded ABS resin cup-shaped molding obtained by the moldability of (8) above. 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.
○: It is neatly transferred to the molded product and has excellent peelability.
Δ: A part is not transferred to the molded product and the peelability is slightly inferior, but there is no problem in practical use.
X: A part is not transferred to the molded product, the peelability is inferior, and this is a practical problem.

(11) Designability Using the ABS resin cup-shaped molded product obtained with the peelability of (8) above, the surface state of the molded product was visually observed, and the designability was determined according to the following criteria.
○: Surface processability is good, and a deep design can be obtained.
Δ: Slightly insufficient surface processability and slightly inferior design, but no problem in practical use,
X: The surface is glaring and has poor design properties.

(12) Comprehensive evaluation With respect 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 the temperature is raised by a conventional method. Then, a transesterification reaction was performed. Subsequently, 0.020% by weight of an 85% aqueous solution of phosphoric acid was 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.

[Fatty acid amide ethylene-butane-propylene master-A (AB-A)]
Sumitomo Chemical Co., Ltd. ethylene / butane / propylene copolymer (FL6633A, ethylene content = 2.1%, butane content = 5.5%, MI = 6 g / min, melting point = 137 ° C.) 98 parts by weight, fatty acid amide As a result, 2 parts by weight of Nippon Seika Co., Ltd. erucamide (trade name Neutron-S) was supplied to a vent type twin screw extruder (L / D = 36) with two vacuum vents. The supplied resin was melted at 230 ° C., and then extruded into a water tank to produce a master resin of erucamide 2% by weight.

[Fatty acid amide ethylene-butane-propylene master-B (AB-B)]
A master resin of 2% by weight of oleic acid amide was prepared in the same manner as AB-A, except that 2 parts by weight of Nippon Seika Co., Ltd. oleic acid amide (trade name Neutron-P) was used as the fatty acid amide.

[Fatty acid amide ethylene / butane / propylene master-C (AB-C)]
A master resin of 2% by weight of stearic acid amide was prepared in the same manner as AB-A, except that 2 parts by weight of Nippon Seika Co., Ltd. stearic acid amide (trade name Neutron-2) was used as the fatty acid amide.

Example 1
As a polyester film, 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.

  As a 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. As a fatty acid amide, 5% by weight, a mixture of AB-C of 2.5% by weight (fatty acid amide addition amount 0.05% by weight) was used and fed to a vent type 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, and cooled and solidified from a molten state to obtain a polyolefin unstretched film having a thickness of 100 μm.

  Polyurethane adhesive {"Takelac" A610 (concentration 35-45%) manufactured by Mitsui Takeda Chemical Co., Ltd.] / "Takenate" A50 (concentration 20-30%) manufactured by Mitsui Takeda Chemical Co., Ltd. = 9 / 1 (mixed weight ratio), 25 wt% ethyl acetate solution}, the solvent was dried at 100 ° C., and the polyester-based unstretched film was bonded to prepare a bonded film.

  The obtained laminated film was passed through the polyolefin film surface side at a depth of 300 μm heated to 120 ° C. and a size of 0.4 mm between a square engraved roll and a paper roll at a speed of 4 m / min. It was pressed and rapidly cooled to room temperature, embossed with an average unevenness depth of 15 μm, and a laminated film for transfer foil of the present invention was produced.

  Next, a topcoat 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. UV curable acrylic resin {"LAROMER" LR8983} manufactured by BASF Japan Co., Ltd. with a thickness of 60 μm as the top coat layer, and polyurethane resin gravure ink (“HIRAMIC” manufactured by Dainichi Seika Kogyo Co., Ltd.) as the printing layer 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 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 was a molded article having excellent design and deep shape with embossed printing on the surface.

( Comparative Example 7 )
A polyester unstretched film having a thickness of 50 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.

  Sumitomo Chemical Co., Ltd. linear low density polyethylene (FZ202-0, melting point = 118 ° C.) 98.5% by weight as a polyolefin film, AB-A 1.5% by weight (fatty acid amide addition amount) 0.03% by weight of the mixture was fed to a vented 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 mirror casting drum adjusted to a surface temperature of 20 ° C. with 50 MPa compressed air, and cooled and solidified from a molten state to obtain a polyolefin unstretched film having a thickness of 50 μm.

  A polyester unstretched film was bonded to the obtained polyolefin unstretched film by the same method as in Example 1 to obtain a laminated film for transfer foil.

  Next, a top coat layer, a printing layer, and an adhesive layer were sequentially laminated on the polyolefin surface of the obtained transfer foil laminated film by the same method as in Example 1 to prepare a transfer foil. 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.

  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.

(Example 2 )
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 having a thickness of 80 μm was produced by the same method as in Example 1 except that the extrusion temperature was changed to 290 ° C.

  As a polyolefin film, the same method as in Example 1 except that 1% by weight of AB-A (0.02% by weight of fatty acid amide) was added as a fatty acid amide to the ethylene / propylene copolymer used in Example 1. A polypropylene-based unstretched film having a thickness of 125 μm was prepared by the same method as in Example 1 to obtain a laminated film for transfer foil of the present invention.

  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 laminated film for transfer foil having an average unevenness depth of 0.9 μm.

  Next, a top coat layer, a printing layer, and an adhesive layer are laminated on the hairline processed 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.

( Comparative Example 8 )
A polyester non-stretched film was produced in the same manner as in Example 2 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.

  As a polyolefin film, the same method as in Example 1 except that 5% by weight of AB-A (amount of fatty acid amide added: 0.01% by weight) was added as a fatty acid amide to the ethylene / propylene copolymer used in Example 1. A polypropylene-based unstretched film having a thickness of 80 μm was prepared and bonded by the same method as in Example 1 to obtain a bonded film.

  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. Sprayed and sandblasted. A laminated film for transfer foil of the present invention having a sandblast surface with an average unevenness depth of 0.4 μm was prepared.

  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.

( Comparative Example 9 )
The polyester blend was changed as shown in Table 1, and a polyester unstretched film having a thickness of 30 μm was obtained in the same manner as in Example 1. As a polyolefin film, an ethylene / butane / propylene copolymer (FL6633A, ethylene content = 2.1%, butane content = 5.5%, MI = 6 g / min, melting point = 137 ° C.), fatty acid amide, Using a mixture of AB-A 0.25% by weight and AB-C 0.25% by weight (total addition amount of fatty acid amide 0.01% by weight), a bent twin screw extruder (L / D = 36) was used. Supplied. 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, and cooled and solidified from a molten state to obtain a 30 μm thick satin-transfer polyolefin non-stretched film.

  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. A laminated film for transfer foil of the present invention having a satin surface having an average unevenness depth of 0.4 μm was prepared.

  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.

As shown in Table 1, the polyolefin films obtained in Examples 1 and 2 are excellent in transparency and blocking properties by making the addition amount of fatty acid amide and thickness unevenness within a specific range, and are coating agents for transfer foils. Can be applied uniformly, there is no peeling of the coating agent for preheating and heating at the time of molding, and even in molding, by laminating a polyester unstretched film on the polyolefin film, it has excellent moldability and peelability Obtained. The ones in the first embodiment, by performing the roughened polyolefin film surface, printing appearing on the surface of the molded product, respectively embossed pattern, background tone of metal, excellent semi-gloss, the design property with satin tone was gotten.

(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.

  Since the obtained polyolefin film had a fatty acid amide addition amount and thickness spots outside the specific range, the blocking property was poor, the handling property was poor, and the coating property of the coating agent was also poor. Moreover, since the polyester unstretched film was not bonded together, the moldability was inferior in molding and the peelability from the molded product was inferior.

(Comparative Example 2)
A non-stretched 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., a tenter stretch was performed 3.3 times at 115 ° C. in the width direction, then 5% relaxation was performed at 230 ° C. for 5 seconds, and a polyester biaxially stretched film adjusted to a thickness of 50 μm was obtained. Produced. 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, hairline processing was applied to the polyolefin surface in the same manner as in Example 3 to prepare a surface processed film having an average unevenness depth of 0.9 μm. A topcoat layer, a printing layer, and an adhesive layer were laminated on the hairline processed surface in the same manner as in Example 1, and transferred to obtain an ABS copolymer resin molded product.

  Since the obtained polyolefin film was not a fatty acid amide, the blocking property was good, but the transparency was inferior. Further, since the polyester film was a biaxially stretched film in molding, it did not follow the molded product and the moldability was poor.

(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. In addition, 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 having a thickness of 50 μm was obtained by the same method as in Comparative Example 2.

  As a polyolefin film, Sumitomo Chemical Co., Ltd. block type ethylene / propylene copolymer (WF183C, ethylene content = 8%, melting point = 165 ° C.) was used and supplied to a vent type 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 mirror casting drum adjusted to a surface temperature of 20 ° C. with 50 MPa pressure air, and cooled and solidified from a molten state to obtain a polyolefin unstretched film having a thickness of 100 μm.

  In addition, a polyolefin film is bonded to the polyester film by the same method as in Example 1 to obtain a bonded film. The polyester unstretched film surface is embossed by the same method as in Example 1, and the embossed surface is processed in Example 2. A top coat layer, a printing layer, and an adhesive layer were laminated by the same method as described above, and transfer molded to obtain an ABS copolymer resin molded product.

  Since the obtained polyolefin film does not contain fatty acid amide, the blocking property is slightly inferior, the transparency is inferior, the molding does not follow the molded product, the moldability and the peelability are inferior, and the molded product is a coating agent. Wrinkled, and the appearance was inferior.

(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 topcoat layer, a printing layer, and an adhesive layer were laminated on the sandblasted surface in the same manner as in Example 1 and transferred to obtain an ABS copolymer resin molded product.

  The resulting polyolefin film has a fatty acid amide addition amount and thickness unevenness outside the specified range, and the coating property of the coating material is inferior. The coating was wrinkled and the appearance was poor.

(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 was bonded to “Torayfan” 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 was embossed by the same method as in Example 1. The top coat layer, the printing layer, and the adhesive layer were laminated on the embossed surface by the same method as in Example 1, and transfer molded to obtain an ABS copolymer resin molded product.

  Since the polyolefin film was a biaxially stretched film, it did not follow the molded product and was inferior in moldability.

(Comparative Example 6)
As the polyester film, a polyester biaxially stretched film having a thickness adjusted to 100 μm was used by the same method as in Comparative Example 2, and as a polyolefin film by the same method as in Example 1, “Trephan” 2500S (thickness 60 μm) Are bonded together to obtain a bonded film, and the polyolefin film surface is embossed in the same manner as in Example 1, and the embossed surface is coated in the same manner as in Example 1 with the topcoat layer, printing layer, and adhesive layer. Were laminated and transfer molded to obtain an ABS copolymer resin molded product.

  Since the polyester film and the polyolefin film were biaxially stretched films, they did not follow the molded product and had poor moldability.

  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

  Since the laminated film for transfer foil of the present invention is excellent in printability, moldability, releasability and design, it can be preferably used as a film for transfer foil. That is, the laminated film for transfer foil of the present invention can uniformly transfer the transfer foil when various coating agents are applied and the transfer foil is transferred to the molded product, and has an excellent design. Therefore, it can be suitably used for building material decorative sheets, automotive interior / exterior parts, bathroom panels, home appliance parts, packaging containers, and the like.

Claims (7)

A laminated film for transfer foil in which a polyolefin film is bonded to at least one surface of a polyester unstretched film, the polyolefin film containing 0.01 to 0.05 % by weight of a fatty acid amide as an organic lubricant, and the polyolefin film thickness Ri unevenness range near the ± 5%, and the thickness of the paste for transfer foil combined film laminated for transfer foil, characterized in 200~600μm der Rukoto film. The laminated film for transfer foil according to claim 1, wherein the fatty acid amide is at least one selected from oleic amide, stearic acid amide, and erucic acid amide. The lamination for transfer foil according to claim 1 or 2, wherein the polyolefin film surface side is embossed, and the average unevenness depth formed by the embossing is 0.02 to 1.0 mm. the film. The polyester constituting the polyester unstretched film contains 90% by mole or more of naphthalenedicarboxylic acid and / or terephthalic acid as a dicarboxylic acid component, and 20 to 99.9% by mole of an ethylene glycol component as a diol component; The transfer according to any one of claims 1 to 3, which is a polyester having a monomer composition containing 0.1 to 80 mol% of a 3-propanediol component and / or 1,4-butanediol component. Laminated film for foil. The elongation at break of the polyester unstretched film 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. A laminated film for transfer foil as described in 1. The laminated film for transfer foil according to any one of claims 1 to 5, 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 polyolefin film surface side of the transfer foil-bonded film according to claim 1.