JP2011194702A - Laminated film and molding sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film excellent in mold releasability, moldability, and printability, and capable of being manufactured without containing steps such as coating and extrusion-laminating.SOLUTION: The laminated film has at least a layer (layer A) containing a polyester resin as a main component and having a crystal parameter ΔTcg of 35°C or lower, and a layer (layer B) containing polyester as a main component and having a crystal parameter ΔTcg exceeding 35°C. The laminated film has the layer A on at least one of the outermost surface layer, the layer A contains a polyolefin resin, the mass ratio of the polyester contained in the layer A to the polyolefin resin is the polyester resin/polyolefin resin=99.9/0.1-50/50, and stress at 100% elongation at 100°C is 0.5-5 MPa.

Description

  The present invention relates to a laminated film excellent in releasability, moldability, and printability.

  Films having releasability are widely used in various surface protective films, transfer foils, and the like. Surface protective film is used by sticking it on adherends such as resin parts, metal products, glass products, etc. mainly for building materials and optical applications, to prevent scratches or foreign matter from entering during transportation, storage or processing. Playing a role. These surface protective films are required to have an appropriate adhesion to the adherend while being used as a protective film, and an appropriate releasability so that the protective film can be easily removed when the product is used. In the case of protecting a molded body having a three-dimensional shape, the surface protection film is required to have moldability in addition to adhesion and releasability.

  The transfer foil is formed by sequentially laminating an easy-adhesion layer, a release layer / clear layer, a printing layer, an adhesive layer, etc. on one side of a film as a base material (release layer). As a transfer method of these transfer foils, the transfer layer is transferred to a transfer object with a heating roll using a transfer device, or an adhesive layer on the mold of an injection molding machine or blow molding machine. The so-called simultaneous molding transfer method represented by in-mold molding, in which the transfer material is set so as to be in contact with the molding resin, then the molding resin is injected or blown, transferred simultaneously with molding, and the molded product is taken out from the mold after cooling. Etc. are generally known. The in-mold molding method can be molded and transferred at the same time, so it is very useful for applying complex patterns. Plastic used in household appliances, automobile parts, kitchen utensils, cosmetic containers, toys and stationery Widely used in molded products.

As described above, since various surface protection films and films used for transfer foils require moldability and releasability, they can be released into films with good moldability (such as films made of polyester resin). Films imparted with properties are often used.
As a method for imparting releasability, a method of coating a film with a resin having good releasability (Patent Document 1), and extruding a polyolefin resin having good releasability onto a base film such as a polyester film A method of laminating by lamination (Patent Document 2), a method of blending a polyester resin and a polyolefin resin and co-extrusion (Patent Document 3), a method of containing a release agent (wax) in the surface layer of a polyester film (Patent Document) 4) etc. are disclosed, and the improvement of the release property of various films is proposed.

JP 05-138668 A JP 2000-037827 A JP 2009-132806 A JP 2007-76026 A

  However, Patent Document 1 requires a coating process, and Patent Document 2 requires an extrusion laminating process at the time of film production.

  In Patent Document 3, since a film is produced by extrusion molding after dry blending a polyester-based resin and a polyolefin-based resin, the manufacturing cost can be suppressed, but because of the single layer configuration, both moldability and releasability are achieved. It was difficult.

  With respect to Patent Document 4, although the manufacturing cost is suppressed and both moldability and mold release properties are excellent, a mold release agent (wax) contained in the polyester film under some molding conditions (high temperature and long time) ) Bleed out, resulting in a decrease in releasability and poor appearance of the protector and transferred object.

  In view of these problems, the present invention intends to provide a laminated film that is excellent in mold release properties, moldability, and printability, and can be manufactured without including steps such as coating and extrusion lamination.

The present invention employs the following means in order to solve such problems.
1) A layer (A layer) containing a polyester resin as a main component and having a crystallinity parameter ΔTcg of 35 ° C. or lower, and a layer containing a polyester resin as a main component and having a crystallinity parameter ΔTcg of more than 35 ° C. (B layer) A laminated film having at least
The laminated film has an A layer on at least one outermost layer,
The layer A contains a polyolefin resin, and the mass ratio of the polyester resin and the polyolefin resin contained in the layer A is polyester resin / polyolefin resin = 99.9 / 0.1-50 / 50,
A laminated film having a stress at 100% elongation at 100 ° C of 0.5 to 5 MPa.
2) The laminated film according to 1) above, wherein the crystallinity parameter ΔTcg of the A layer is 11 ° C. or less.
3) The laminated film as described in 1) or 2) above, wherein the polyolefin resin comprises a modified polyolefin resin and other polyolefin resins.
4) The mass ratio of the modified polyolefin resin and the other polyolefin resin is modified polyolefin resin / other polyolefin resin = 0.1 / 99.9 to 40/60, in the above 3) The laminated film as described.
5) The sheet | seat for shaping | molding containing the laminated | multilayer film in any one of said 1) -4).

  According to the present invention, a laminated film excellent in releasability, moldability, and printability can be obtained without including steps such as coating and extrusion lamination. More specifically, as for releasability, since it is excellent in releasability from the transfer target, peeling marks are hardly generated in the releasable process. As for formability, since it is excellent in deep drawability, it is possible to follow a complicated surface shape. Regarding printability, various printing inks can be used because of excellent solvent resistance against solvents contained in the printing ink, particularly ethyl acetate and methyl ethyl ketone. The laminated film of the present invention is suitably used as a transfer foil by a decoration method such as in-mold transfer, and is suitably used for applications such as automobile interior / exterior parts, bathroom panels, parts for home appliances, and packaging containers.

The present invention is excellent in releasability, moldability, and printability. Furthermore, as a result of intensive studies on a laminated film that can be produced without including steps such as coating and extrusion lamination, a crystal containing polyester resin as a main component is obtained. A laminated film having at least a layer (A layer) having a property parameter ΔTcg of 35 ° C. or lower and a layer (B layer) having a crystallinity parameter ΔTcg of more than 35 ° C. mainly composed of a polyester resin, The film has an A layer on at least one outermost layer, the A layer contains a polyolefin resin, and the mass ratio of the polyester resin and the polyolefin resin contained in the A layer is polyester resin / polyolefin resin = 99.9. /0.1 to 50/50, and the stress at 100% elongation at 100 ° C. is 0.5 to 5 MPa. It was clarified that this problem can be solved at once.
Hereinafter, the laminated film of the present invention will be specifically described.

(Polyester resin)
The polyester resin which is the main component of the A layer and the B layer of the laminated film of the present invention consists of a polymer basically composed of a dicarboxylic acid component and a glycol component.

  Examples of the dicarboxylic acid component include isophthalic acid, terephthalic acid, diphenyl-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and 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.

  Examples of the glycol component include ethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, aliphatic glycols such as 1,3-propanediol and spiroglycol, alicyclic glycols such as cyclohexanedimethanol, and bisphenol. A glycol component such as aromatic glycol such as -A or bisphenol-S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol-propylene glycol copolymer, or the like can be used.

  Specifically, the polyester resin which is the main component of the A layer and the B layer of the laminated film of the present invention is polyethylene terephthalate (PET), 1,4-cyclohexanedimethanol copolymerized PET (PETG), spiroglycol copolymerized PET. , Polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate (PHT), polyethylene naphthalate (PEN), polypropylene naphthalate (PPN), polybutylene naphthalate (PBN), polycyclohexanedimethylene terephthalate ( PCT), polyhydroxybenzoate (PHB) and the like. Two or more kinds of these polyesters can be used in combination.

(Laminated film)
The laminated film of the present invention includes a layer (A layer) containing a polyester resin as a main component and a crystallinity parameter ΔTcg of 35 ° C. or less, and a layer containing a polyester resin as a main component and a crystallinity parameter ΔTcg exceeding 35 ° C. (B layer) at least, and it is important that it is the structure which has A layer in at least one outermost layer. As will be described later, since the A layer of the present invention is excellent in printability, even when another layer is formed on the A layer when the laminated film of the present invention is used as a molding sheet, the layer hardly deteriorates. There are advantages. Therefore, it is important that the laminated film of the present invention has an A layer on at least one outermost layer.

  Here, the crystallinity parameter ΔTcg is a cold crystallization temperature (Tc) and a glass transition temperature (Tg) observed in a temperature rising process when differential scanning calorimetry (DSC) is performed on a powder obtained by scraping each layer of a laminated film. Is the difference.

  The A layer in the laminated film of the present invention refers to a layer having a polyester resin as a main component and a crystallinity parameter ΔTcg of 35 ° C. or lower. In general, the smaller the value of ΔTcg, the easier it is to crystallize. When the crystallinity parameter ΔTcg of the A layer is 35 ° C. or lower, the printability of the A layer is improved. Therefore, the printability of the laminated film of the present invention having the A layer as at least one outermost layer is improved. Will be. Therefore, even if an organic solvent such as methyl ethyl ketone, toluene, or ethyl acetate comes into contact with the layer A side of the laminated film, it is possible to prevent deterioration of the planarity of the laminated film due to the erosion of the organic solvent. Therefore, even if printing ink containing an organic solvent is printed on the A layer of the laminated film or a clear layer dissolved in the organic solvent is coated on the A layer of the laminated film, the planarity of the laminated film Thus, it is possible to prevent the appearance defect of the protector and the transferred object.

  On the other hand, the B layer in the laminated film of the present invention refers to a layer having a polyester resin as a main component and ΔTcg exceeding 35 ° C. Since the laminated film of the present invention has at least such a B layer, the moldability of the laminated film of the present invention is not deteriorated, and is formed when the laminated film of the present invention is used as a molded body protective film or a transfer foil. High followability to the body and the transfer target is maintained.

  In the laminated film of the present invention, it is important that the ΔTcg of the A layer is 35 ° C. or less. From the viewpoint of improving printability, the ΔTcg of the A layer is more preferably 25 ° C. or less, and further preferably 20 ° C. or less. 11 degrees C or less is especially preferable. When the ΔTcg of the A layer is 11 ° C. or less, the printability is particularly excellent. Therefore, the ΔTcg of the A layer is particularly preferably 11 ° C. or less. Moreover, as a minimum of (DELTA) Tcg, 7 degreeC or more is preferable from a film forming viewpoint, and 10 degreeC or more is more preferable.

  In the laminated film of the present invention, it is important that the ΔTcg of the B layer exceeds 35 ° C., but the ΔTcg of the B layer is more preferably 50 or more, and particularly preferably 70 ° C. or more from the viewpoint of improving moldability. Further, from the viewpoint of the film forming property of ΔTcg, the upper limit is preferably 90 ° C. or less.

  As a method for improving the printability of the laminated film by setting the crystallinity parameter ΔTcg of the A layer of the laminated film of the present invention to 35 ° C. or less, a polyester resin having a high crystallinity is used as the polyester resin as the main component of the A layer. (Hereinafter referred to as a highly crystalline polyester resin), and a method of forming a laminated film without stretching is available. Further, as a method for setting the crystallinity parameter ΔTcg of the B layer to a value exceeding 35 ° C., a polyester resin other than the highly crystalline polyester resin (hereinafter referred to as other polyester resin) is used as the polyester resin as the main component of the B layer. ) Is used. Among them, from the point that the A layer and the B layer can be easily laminated and the moldability of the laminated film becomes good, the laminated film of the present invention is composed of a layer mainly composed of a highly crystalline polyester resin (A layer). It is preferable to obtain a layer (B layer) containing other polyester resin as a main component by coextrusion in a non-stretched state.

  Here, the highly crystalline polyester resin suitable as the polyester resin as the main component of the A layer refers to a resin having a crystallization parameter ΔTcg of 35 ° C. or lower. Specifically, examples of the highly crystalline polyester resin include PPT, PBT, PPN, and PBN. Among these, PBT is most preferable in terms of crystallinity and cost.

  On the other hand, the other polyester resin suitable as the polyester resin as the main component of the B layer refers to a resin having a crystallization parameter ΔTcg exceeding 35 ° C. Specifically, preferred examples of the other polyester resins include PET, 1,4-cyclohexanedimethanol copolymerized PET (PETG), spiroglycol copolymerized PET, and a combination thereof, details of which will be described later. . In the present invention, “resin having a ΔTcg exceeding 35 ° C.” includes a resin in which the crystallization parameter ΔTcg is not observed.

(A layer)
In the laminated film of the present invention, the layer (A layer) containing the polyester resin as a main component and having a crystallinity parameter ΔTcg of 35 ° C. or lower is required to reduce the ΔTcg as a layer to 35 ° C. or lower. A highly crystalline polyester resin is preferred.

  Here, the A layer mainly comprises a polyester resin means that the polyester resin is 50% by mass or more and 99.9% by mass or less with respect to 100% by mass of all the components of the A layer. Therefore, about A layer, Preferably, highly crystalline polyester resin is an aspect of 50 to 99.9 mass% with respect to 100 mass% of all the components of A layer.

  The highly crystalline polyester resin is more preferably contained in an amount of 70 to 99.9% by mass with respect to 100% by mass of all components of the A layer, and 90 to 99.9% by mass. Is particularly preferred. If these highly crystalline polyester resins are less than 50% by mass with respect to 100% by mass of the total components of the layer, ΔTcg of the layer may not be 35 ° C. or lower, and therefore, a laminate having the layer The printability of the film may be insufficient.

(B layer)
In the laminated film of the present invention, a layer (B layer) having a crystallinity parameter ΔTcg of more than 35 ° C., the main component of which is a polyester resin, is used in order to make ΔTcg as a layer larger than 35 ° C. The polyester resin is preferable.

  Here, the B layer having a polyester resin as a main component means an embodiment in which the polyester resin is 50% by mass or more and 100% by mass or less with respect to 100% by mass of all components of the B layer. Therefore, about B layer, Preferably, another polyester resin is an aspect of 50 to 100 mass% with respect to 100 mass% of all the components of B layer.

  The other polyester resin is more preferably contained in an amount of 70 to 100% by mass and particularly preferably 90 to 100% by mass with respect to 100% by mass of all components of the B layer. When these other polyester resins are less than 50% by mass with respect to 100% by mass of the total components of the layer, ΔTcg of the layer may not be able to be a value exceeding 35 ° C. The formability of the laminated film may be insufficient.

  In the present invention, “a layer in which ΔTcg exceeds 35 ° C.” includes a case where ΔTcg of the layer is not observed.

  As other polyester resin suitably used for the B layer of the laminated film of the present invention, as described above, PET, 1,4-cyclohexanedimethanol copolymerized PET (PETG), spiroglycol copolymerized PET, and these are used. A combined state is preferred. The B layer is not particularly limited as long as the polyester resin is the main component and the crystallinity parameter ΔTcg exceeds 35 ° C. Therefore, the B layer may contain a highly crystalline polyester resin. Therefore, the polyester resin that is the main component of the B layer is preferably a combination of another polyester resin and a highly crystalline polyester resin. The B layer is particularly preferably at least one selected from the group consisting of PET, which is another polyester resin, 1,4-cyclohexanedimethanol copolymerized PET (PETG), and spiroglycol copolymerized PET. This is an embodiment containing at least one selected from the group consisting of PPT, PBT, and PPN, which is a highly crystalline polyester resin, containing 1% by mass to less than 50% by mass of the entire B layer.

  As a method of combining two or more kinds of polyester resins in one layer, for example, a method of blending two or more kinds of polymer pellets and supplying them to an extruder and kneading in the extruder to obtain a polyester having an arbitrary component constitution ( (Dry blend method) Obtained by a known method such as a method of obtaining a polyester of an arbitrary component by polymerization using two or more types of monomers (copolymerization method), a method combining a dry blend method and a copolymerization method, etc. be able to. From the viewpoint of polymer production cost, productivity, and heat resistance, it is preferable to use a dry blend method.

(Reaction catalyst during production, anti-coloring agent)
When manufacturing the polyester resin used as the main component of A layer and B layer of the laminated film of this invention, the conventionally used reaction catalyst and coloring inhibitor 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. Preferably, an antimony compound, a germanium compound or a titanium compound is added as a reaction catalyst at any stage before the production of the polyester resin is completed. As a method for adding the reaction catalyst, for example, a method in which the powder of the reaction catalyst is added as it is, a method in which the reaction catalyst is dissolved in a glycol component which is a starting material of the polyester resin, and the like are used. it can.

Although it does not specifically limit as said antimony compound, For example, antimony oxides, such as antimony trioxide, an antimony acetate, etc. can be used.
The titanium compound is not particularly limited, and alkyl titanate compounds such as tetraethyl titanate and tetrabutyl titanate, and composite oxides of titanium and an element selected from silicon, zirconium and aluminum can be preferably used.

  Moreover, as a coloring inhibitor, a phosphorus compound etc. can be used, for example. As a method for containing such a 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, since a polymerization reaction is inhibited when a large amount of a phosphorus compound is added at the time of polymerization, a method of supplying it to an extruder together with a polyester resin is preferable.

(Viscosity of polyester resin)
The intrinsic viscosity of the polyester resin used for the laminated film of the present invention is preferably in the range of 0.6 to 1.3 dl / g. More preferably, it is 0.65-1.2 dl / g, Most preferably, it is the range of 0.7-1.1 dl / g. If the intrinsic viscosity is less than 0.6 dl / g, the moldability of the laminated film may be lowered. Moreover, when intrinsic viscosity exceeds 1.3 dl / g, productivity will fall or the thickness unevenness of a laminated | multilayer film will become remarkable, and as a result, the unevenness of thickness tends to arise also in a laminated | multilayer film.

(Polyolefin resin)
The layer (A layer) in which the crystallinity parameter ΔTcg is 35 ° C. or less in the laminated film of the present invention contains a polyolefin resin, and the mass ratio of the polyester resin and the polyolefin resin contained in the A layer is polyester resin / polyolefin. It is important that the resin = 99.9 / 0.1-50 / 50. The layer A contains a polyolefin resin, and by making the mass ratio of the polyolefin resin of the layer A and the polyester resin within the above range, the release property, moldability, and printability of the laminated film of the present invention can be improved. it can. More preferably, the mass ratio of the polyester resin and the polyolefin resin contained in the A layer is polyester resin / polyolefin resin = 99/1 to 60/40, and particularly preferably polyester resin / polyolefin resin = 95/5. 70/30.

  Part of the polyolefin resin contained in the layer (A layer) having a crystallinity parameter ΔTcg of 35 ° C. or less in the laminated film of the present invention is preferably a modified polyolefin resin. That is, as the polyolefin resin to be contained in the A layer, it is preferable to use a modified polyolefin resin and another polyolefin resin in combination. It is preferable to use a modified polyolefin resin and another polyolefin resin in combination as the polyolefin resin contained in the A layer because compatibility with the polyester resin that is the main component of the A layer is improved.

(Ratio of modified polyolefin resin and other polyolefin resin)
When the modified polyolefin resin and the other polyolefin resin are used in combination as the polyolefin resin contained in the A layer, the mass ratio of the modified polyolefin resin and the other polyolefin resin is modified polyolefin resin / other polyolefin resin = 0. The ratio is preferably 1 / 99.9 to 40/60, more preferably 0.5 / 99.5 to 30/70, and particularly preferably 1/99 to 25/75. If the ratio of the modified polyolefin resin is smaller than the mass ratio of 0.1 / 99.9 (= modified polyolefin resin / other polyolefin resin), the compatibility between the polyolefin resin in the layer A and the polyester resin deteriorates, Transparency may be insufficient. Further, if the ratio of the modified polyolefin resin is larger than the mass ratio of 40/60 (= modified polyolefin resin / other polyolefin resin), the modified polyolefin resin may be decomposed during extrusion or a gelled product may be generated. .

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

  Examples of such modified polyolefin resins include ethylene-vinyl acetate copolymers, ionomer resins, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid. Mention may be made of polyolefin-based copolymer resins containing polar groups such as copolymers. Other modified polyolefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α-olefin copolymer polymerized using a metallocene catalyst, polypropylene, and ethylene-propylene copolymer. Polyolefin resins such as polymers, methylpentene polymers, other random copolymers composed of α-olefin monomers, and block copolymers are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid. Alternatively, a modified polyolefin resin modified by oxidative decomposition of the resin can be used.

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

  These modified polyolefin resins are preferably polyolefin resins modified by unsaturated dicarboxylic acid or modified by oxidative decomposition of the resin, and more preferably modified polyolefin resins modified by unsaturated dicarboxylic acid. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-propylene copolymer, polymethyl A modified polyolefin resin obtained by modifying a polyolefin resin such as pentene and other random copolymers composed of α-olefin monomers and block copolymers with unsaturated dicarboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid. It is preferable from the viewpoint of compatibility with the polyester resin that is the main component of the A layer. As the unsaturated dicarboxylic acid, maleic anhydride is particularly preferable, that is, a modified polyolefin resin obtained by modifying a polyolefin resin with maleic anhydride is particularly preferable.

  Examples of such a modified polyolefin resin with an unsaturated dicarboxylic acid include “Yumex” manufactured by Sanyo Chemical Co., Ltd., “Admer” manufactured by Mitsui Chemicals, Inc., “Modic” manufactured by Mitsubishi Chemical Corporation, and Toyo Kasei Co., Ltd. ) Various resins such as “Toyo Tac” manufactured by the company. Examples of the modified polyolefin resin modified by oxidative decomposition of the resin include “Biscol” and “Sunwax” manufactured by Sanyo Chemical Co., Ltd.

(Acid value of modified polyolefin resin)
When the modified polyolefin resin is contained in the polyolefin resin contained in the A layer in the laminated film of the present invention, the acid value of the modified polyolefin resin is preferably 1 to 80, more preferably 2 to 60, particularly Preferably it is 3-40. If the acid value of the modified polyolefin resin is less than 1, the compatibility between the polyolefin resin and the polyester resin contained in the A layer may be insufficient, and if the acid value of the modified polyolefin resin exceeds 80, The heat resistance of the polyolefin resin becomes insufficient, and the modified polyolefin resin may be decomposed during extrusion or a gel-like material may be generated. The acid value here is a value according to JIS K0070 (1992 formula).

(Molecular weight of modified polyolefin resin)
The number average molecular weight of the modified polyolefin resin is preferably 1,000 to 100,000, more preferably 2,000 to 40,000. If the number average molecular weight is less than 1,000, the heat resistance of the resin is insufficient, and if it is 100,000 or more, the compatibility between the polyolefin resin and the polyester resin contained in the A layer may be insufficient. In addition, the number average molecular weight here can be calculated | required by polystyrene conversion by GPC.

(Melting point of modified polyolefin resin)
The melting point of the modified polyolefin is preferably in the range of 110 to 170 ° C, more preferably 120 to 165 ° C, still more preferably 130 ° C to 160 ° C. When the melting point of the modified polyolefin is lower than 100 ° C, the heat resistance of the laminated film may be insufficient. When the melting point of the modified polyolefin exceeds 170 ° C, the compatibility between the polyolefin resin and the polyester resin contained in the A layer is It may be insufficient.

(Other polyolefin resin)
Other polyolefin resin shall mean polyolefin resin other than modified polyolefin resin. Specific examples of other polyolefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene, and ethylene-propylene. Polyolefin resins such as copolymers and methylpentene polymers can be used.

  Further, as other polyolefin resins, polymers composed of α-olefin monomers such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and the like, α-olefin monomers It is also possible to use a random copolymer comprising, a block copolymer comprising the α-olefin monomer, and the like.

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

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

(MFR and viscosity of other polyolefin resins)
The other polyolefin resin preferably has a melt flow rate (MFR) of 1 to 100 g / 10 minutes measured under conditions of 230 ° C. and a load of 2.16 kg in accordance with JIS-K7210 (1999). 80 g / 10 min is more preferable, and 4 to 60 g / 10 min is further more preferable. Most preferably, it is 10-40 g / 10min. If the MFR of the other polyolefin resin is in the range of 1 to 100 g / 10 min, it has appropriate crystallinity, and the dimensional stability, moisture resistance, and surface smoothness of the laminated film of the present invention are good. In addition, uniform lamination with a layer (B layer) having a crystallinity parameter ΔTcg exceeding 35 ° C. is improved, and a flow mark can be suppressed.

  If the MFR of the other polyolefin resin is smaller than 1 g / 10 minutes, the melt viscosity is too high and the extrudability tends to be lowered. Moreover, when MFR of other polyolefin resin exceeds 100 g / 10min, since crystallinity is too high, film forming property may fall significantly, or the mechanical characteristics of a laminated film may fall significantly. Further, the crystallization of the A layer progresses too much, and there is a risk that the printing accuracy will be lowered by roughening the surface.

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

(Melting points of other polyolefin resins)
Other polyolefin resins preferably have a melting point in the range of 100 to 170 ° C., more preferably 120 to 165 ° C., and still more preferably 130 to 160 ° C. from the viewpoint of heat resistance at the ink drying temperature and moldability. When the melting point of the modified polyolefin is lower than 100 ° C., the heat resistance of the laminated film may be insufficient, and when the melting point of the modified polyolefin exceeds 170 ° C., the extrudability of the laminated film may be lowered.

(Combination of modified polyolefin resin and other polyolefin resin)
When the polyolefin resin constituting the layer A of the laminated film of the present invention is composed of a modified polyolefin resin and other polyolefin resins, the modified polyolefin resin may be polypropylene modified with unsaturated dicarboxylic acid, ethylene-polypropylene copolymer Polymers and polymethylpentene are preferable from the viewpoint of heat resistance and releasability, and among them, polypropylene modified with maleic anhydride, ethylene-propylene copolymer, and polymethylpentene are particularly preferable. Further, as other polyolefin resins, polypropylene, ethylene-propylene copolymer, and polymethylpentene are preferable from the viewpoint of heat resistance and film forming property. Further, the ethylene content of the ethylene-propylene copolymer is preferably 1 to 15% by mass, more preferably 2 to 100% by mass in 100% by mass of the ethylene-propylene copolymer from the viewpoint of heat resistance and film forming property. 10% by mass.

  That is, in the laminated film of the present invention, as a combination of the modified polyolefin resin constituting the B layer and the other polyolefin resin, polypropylene, ethylene-polypropylene copolymer, or polymethylpentene is used as the other polyolefin resin, As the polyolefin resin, an embodiment using a resin obtained by modifying a resin used as another polyolefin resin with maleic anhydride is particularly preferable.

(Thickness of laminated film)
The thickness of the laminated film of the present invention is preferably in the range of 10 to 600 μm, more preferably 20 to 400 μm, and particularly preferably 40 to 300 μm. When the thickness of the laminated film is less than 10 μm, the rigidity, production stability and flatness of the film are lowered, and wrinkles are easily formed during molding, which is not preferable. Moreover, when the thickness of a laminated film exceeds 600 micrometers, a handleability and a moldability may be aggravated.

  In the laminated film of the present invention, the thickness of one layer unit of the layer (A layer) having a crystallinity parameter ΔTcg of 35 ° C. or less is obtained from the point that the printability, transferability and moldability are all good. It is preferably in the range of 0.1% to 30% and 2 μm to 120 μm with respect to the total thickness of 100%, and in the range of 0.2% to 20% and 4 μm to 80 μm with respect to the total thickness of 100% of the laminated film. More preferably it is. If the thickness of the A layer is too thin, chemical resistance and heat resistance may be insufficient, and printability and transferability may be deteriorated. On the other hand, if the thickness of the A layer is too thick, the moldability may be insufficient. The layer (B layer) having a crystallinity parameter ΔTcg exceeding 35 ° C. preferably has a thickness of one layer unit of 70 to 99.9% and 10 μm to 500 μm with respect to 100% of the total thickness of the laminated film. More preferably, they are 80-99.8% and 20 micrometers-400 micrometers. If the thickness of the B layer and other polyester layers is too thin, the moldability may be insufficient, and if the thickness of the B layer is too thick, the heat resistance may decrease and the printability and transferability may be insufficient. .

(surface treatment)
The laminated film of the present invention can improve the coatability of various coating agents, such as a clear layer when the laminated film of the present invention is used as a transfer foil, by performing a surface treatment such as corona discharge treatment. is there. Further, it can be used after being subjected to molding processing such as embossing, printing, or the like, if necessary.

(Contained particles, etc.)
Each layer of the laminated film of the present invention can contain various particles according to the purpose and application. The particles to be contained are not particularly limited as long as they are inert to the polyester resin and polyolefin resin contained in the A layer and the B layer, but are generated in the inorganic system, the organic particles, the crosslinked polymer particles, and the polymerization system. Internal particles can be mentioned. Two or more kinds of these particles may be added. The content of such particles is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, with respect to 100% by mass of all components in each layer.

  When it is a particle-containing purpose to impart easy lubricity to the laminated film of the present invention, it is preferable to contain particles only in the surface layer from the viewpoint of production cost and productivity. In general, the slipperiness is greatly influenced by the shape of the film surface, so that the slipperiness can be obtained by adding particles to the surface layer.

  The kind of the 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, phosphoric acid Various phosphates such as lithium, 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 and the like 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.

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

  In each layer of the laminated film of the present invention, a known additive, for example, a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a plasticizer, a tackifier, or a polysiloxane is used as necessary. An appropriate amount of a defoaming agent such as a coloring agent such as a pigment or a dye can be contained.

(Antistatic agent)
Each layer of the laminated film of the present invention preferably contains an antistatic agent. As such an antistatic agent, various known antistatic agents such as anionic, cationic, nonionic and amphoteric can be used. Among these, it is particularly preferable to use sodium alkylsulfonate or sodium alkylbenzenesulfonate which is an anionic antistatic agent from the viewpoint of heat resistance. 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 such an antioxidant, various known ones such as a phenol-based antioxidant, a phosphite-based antioxidant, and a thioether-based antioxidant can be used. These compounds may be used by mixing a plurality of compounds.

(Elongation at break, stress)
In the laminated film of the present invention, it is important that the stress at 100% elongation at 100 ° C. is 0.5 to 5 MPa. When the laminated film of the present invention is molded at a low temperature of 80 to 120 ° C., foaming due to the decomposition gas of the coating agent can be suppressed when using a coating material such as a UV curing type, or the laminated film of the present invention is used as a transfer foil. In this case, it is preferable from the viewpoint that deformation of the base material resin of the transfer target due to heating during transfer can be suppressed. The laminated film used in the present invention is required to have a stress at 100% elongation at 100 ° C. of 0.5 to 5 MPa in order to give good forming followability as a transfer foil even at a low temperature. Is 0.5-4 MPa, more preferably 0.5-3 MPa. When the stress at 100% elongation at 100 ° C. exceeds 5 MPa, the molding followability may be insufficient when transferred as a transfer foil to a transfer target. When the stress at 100% elongation at 100 ° C. is less than 0.5 MPa, the dimensional stability of the laminated film during heating may be insufficient.

  As a method for making the laminated film of the present invention have a stress at 100% elongation at 100 ° C. in the range of 0.5 to 5 MPa, 1,4-as the polyester resin as the main component of the B layer of the laminated film. Compositions specific to laminated films, including methods that contain cyclohexanedimethanol copolymerized PET (PETG) and methods that blend polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) as the polyester resin that is the main component of layer B The method of giving a structure is mentioned.

  The laminated film of the present invention preferably has a breaking elongation at 100 ° C. of 500% or more, more preferably 700% or more, and further preferably 1,000% or more. When the elongation at break at 100 ° C. is less than 500%, molding followability may be insufficient when transferred to a transfer material as a transfer foil. In addition, although the breaking elongation at 100 degreeC is so good that it is large, 1500% is an upper limit substantially used for various surface protection film and transfer foil use as a value which does not produce a crack in a printing layer or various coating surfaces.

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

  In the coextrusion method, each resin constituting a layer (A layer) having a crystallinity parameter ΔTcg of 35 ° C. or less and a layer (B layer) having a crystallinity parameter ΔTcg exceeding 35 ° C. is transferred from a plurality of extruders to one die. This is a method for producing a laminated film by supplying and simultaneously extruding, and includes a T-die method and an inflation method. The laminated film of the present invention can be produced by either the T-die method or the inflation method, but the T-die method is preferably used from the viewpoint of productivity.

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

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

(Molding sheet)
The laminated film of the present invention is suitably used as a molding sheet. When the laminated film of the present invention is used as a molding sheet such as a transfer foil, a clear layer / printing layer / adhesive layer is further formed on the layer (A layer) surface having a crystallinity parameter ΔTcg of 35 ° C. or lower. It can be used as a molding sheet having an aspect in which layers are provided in this order. Here, the laminated film composed of the clear layer / printing layer / adhesive layer is a laminated structure film for forming a coating film that forms a coating film on a molding resin by transfer.

  The laminated film of the present invention is a laminated film that satisfies both moldability and printability required for a deep drawing transfer foil film, and further, for example, compared with a conventional laminated film such as JP-A-2004-188708. It is a laminated film with excellent cost. For these reasons, the laminated film of the present invention is a sheet for molding, and among them, the surface of parts having complicated shapes, such as automobile interior / exterior parts, building material decorative films, bathroom panels, home appliance parts, OA product parts It can be preferably used as a sheet for transfer foil.

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

  The clear layer forms the surface of the transfer object after the laminated film of the present invention is peeled off when the laminated film of the present invention is used as a transfer foil film that is one embodiment of a molding sheet. A resin that can be heat-cured, ultraviolet-cured, or heat-ray-cured after peeling may be used as the clear layer. Further, in order to improve the weather resistance, an ultraviolet absorber or an ultraviolet reflector may be added to the clear layer.

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

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

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

  Various methods are used as the method for forming the adhesive layer provided for the purpose of imparting adhesiveness to the molded resin. For example, a coating method such as a roll coating method, a gravure coating method, a comma coating method, or a gravure printing method, a screen, etc. Printing methods such as printing are used.

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

  Further, depending on the purpose, a clear layer, a weather resistant layer, a flame retardant layer, an antifouling layer, an antibacterial layer, and the like are formed on the surface of the laminated film A of the present invention by a technique such as coating, coextrusion, thermal lamination, or dry lamination. be able to.

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

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

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

  The measurement was performed five times for each sample and each direction for both stress and breaking elongation, and the average value was evaluated.

(2) Film Thickness and Layer Thickness When measuring the total thickness of the laminated film, the thickness at five arbitrary locations of the sample cut out from the film was measured using a dial gauge, and the average value was obtained.

  When measuring the layer thickness of each layer of the laminated film, use Leica DMLM manufactured by Leica Microsystems Co., Ltd. to photograph the transmitted light on the cross section of the film at a magnification of 100 times, and place it anywhere in the photo. The layer thickness of each layer of the laminated film was measured at five locations, and the average value was determined.

(3) Releasability 1
After producing the transfer foil under the conditions described in each example, the transfer foil was cut into a rectangle of length 100 mm × width 25 mm in the longitudinal direction and width direction to obtain a sample. After part of the interface between the laminated film A layer and the clear layer of the sample was peeled off, the laminated film side and the clear layer side were sandwiched between chucks using a tensile tester (Orientec Tensilon UCT-100). Thereafter, a peel test was performed to determine an average value of the load at the time of peeling. The initial chuck distance was 100 mm, the tensile speed was 300 mm / min, and the temperature was room temperature, and the test was performed in the longitudinal direction and the width direction of the film. Moreover, the measurement was performed 5 times for each sample and each direction, and the average value was evaluated. The evaluation criteria are as follows. A or B is a pass level.
A: Less than 0.5N / 25mm B: 0.5N / 25mm or more, less than 1.0N / 25mm C: 1.0N / 25mm or more (4) Releasability 2
Evaluation was performed in the same manner as (3) except that the sample was heated at 100 ° C. for 10 minutes before the peel test.

(5) Formability For the cup-shaped molded product made of the transfer foil prepared in the example, the moldability was evaluated according to the following criteria. That is, the state of the transfer foil in the cup-shaped molding after molding was visually observed and judged according to the following criteria. A or B is a pass level.
A: The corners are sharply formed.
B: The corner is slightly rounded.
C: The shape is significantly different from the mold shape.

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

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

(7) MFR
According to JIS-K7210 (1999 model), the measurement was performed under conditions of 230 ° C. and a load of 2.16 kg.

(8) 3 ml each of ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and toluene was dropped on the surface of the printable film and left for 6 hours. Then, the solvent was wiped clean, and the surface condition was visually observed and judged according to the following evaluation criteria. did. A and B are acceptable levels. In addition, when an evaluation result differs in each surface of a film, a surface with a better evaluation result on the following evaluation criteria shall be employ | adopted.
A: For all solvents, no whitening, shrinkage, deformation, or trace of solvent is observed.
B: Whitening, shrinkage, or deformation is observed with respect to any one or two kinds of solvents.
C: The one in which whitening, shrinkage, and deformation are observed with respect to any three or more solvents.

(9) Crystallinity parameter ΔTcg of each layer
Each layer is scraped off from the laminated film, and a 5 mg sample is collected for each layer, and a temperature increase rate of 20 ° C./300° C. to −30 ° C. using a differential scanning calorimeter DSCII manufactured by Seiko Instrument Co., Ltd. The peak temperature of the endothermic melting curve when the temperature was raised in minutes was taken as the melting point (Tm). Further, the glass transition temperature (Tg) and the crystallization temperature (Tc) were measured under the same measurement conditions, and the crystallinity parameter (ΔTcg) was calculated from [Equation 2]. Further, when two or more Tg and Tc were observed, the value at which the curve peak (Tc) or the curve change (Tg) was observed to be the largest was adopted.
Crystallinity parameter: ΔTcg = Tc−Tg [Equation 2]
The following raw materials 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 parts by weight of magnesium acetate and 0.03 parts by weight of antimony trioxide are added, and the temperature is raised by a conventional method to perform a transesterification reaction. It was. Next, 0.020 parts by mass of 85% aqueous phosphoric acid solution was added to the transesterification reaction product, and then transferred to a polycondensation reaction tank. Next, the reaction system is gradually depressurized while being heated and heated, and a polycondensation reaction is carried out by a conventional method at 290 ° C. under a reduced pressure of 1 mmHg, and differential scanning calorimetry (in a nitrogen atmosphere, a heating rate of 20 ° C./min) A polyethylene terephthalate resin having a melting point of 257 ° C. and an intrinsic viscosity of 0.65 dl / g was obtained.

[1,4-Cyclohexanedimethanol copolymerized polyethylene terephthalate B (PET-B)]
“6763” (no melting point, intrinsic viscosity 0.72) manufactured by Eastman Chemical Co. was used. The copolymerization ratio (ratio of 1,4-cyclohexanedimethanol) in 100 mol% of diol monomer of 1,4-cyclohexanedimethanol was 30 mol%.

[Polybutylene terephthalate (PBT)]
“Toraycon” (registered trademark) 1200S (melting point: 224 ° C., intrinsic viscosity: 1.26 dl / g) manufactured by Toray Industries, Inc. was used.

[Ethylene-propylene copolymer A (EPC)]
“Y-2045GP” (MFR = 24, containing 4% by mass of ethylene group) manufactured by Prime Polymer Co., Ltd. was used.

[Polypropylene (PP)]
“R101” (MFR = 19) manufactured by Sumitomo Chemical Co., Ltd. was used.

[Polyolefin resin mainly composed of polymethylpentene units (PMP)]
A polyolefin-based resin (melting point: 225 ° C., Vicat softening temperature: 153 ° C.) mainly containing polymethylpentene units was used.

[Maleic anhydride-modified polypropylene (modified PP)]
“Admer QE800” manufactured by Mitsui Chemicals, Inc. was used.

[Polyolefin resin having polymethylpentene unit modified with maleic anhydride (modified PMP)]
A resin (melting point: 210 ° C.) containing 10% by mass of a maleic anhydride group in a polyolefin-based resin (melting point: 225 ° C., Vicat softening temperature: 153 ° C.) mainly containing a polymethylpentene unit was used.

Example 1
After mixing PET-A and PBT at the ratio shown in the table (layer B), supplying to a vent type twin screw extruder (L / D = 36) and melting at 275 ° C., the mixture was passed through two vacuum vents. It was. Next, the resin was passed through a leaf disk filter having a filtration accuracy of 30 μm and then supplied to a multi-manifold die.

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

  After each resin passed through the manifold in the die, two kinds of resins were laminated so as to be A layer / B layer / A layer, and extruded from a slit die into a film shape. Electrostatic application was applied to both ends of the extruded film using a needle-like edge pinning device, and the film was brought into close contact with the casting drum and solidified by cooling. A laminated film of the present invention having a layer thickness of 10 μm per A layer (both A layers have the same thickness) and a total film thickness of 100 μm was obtained.

  A clear layer, a printed layer, and an adhesive layer were formed in this order on one layer A of the obtained laminated film of the present invention, and a molding sheet of the present invention, which was a transfer foil, was obtained.

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

  As a printing layer, using a polyurethane-based resin gravure ink ("Hiramic" (registered trademark) manufactured by Dainichi Seika Kogyo Co., Ltd., main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow / 701R white), A layer having a thickness of 70 μm was formed.

  As the adhesive layer, an acrylonitrile-butadiene-styrene (ABS) copolymer resin film (ABS film “Hiflex” (registered trademark) manufactured by Okamoto Co., Ltd.) was used to form a layer having a thickness of 100 μm.

  Next, a cup-shaped molded body was produced from the obtained transfer foil using a vacuum molding machine with a 50 mm diameter cup concave mold at a temperature of 100 ° C. and a drawing ratio of 1.0. Under the present circumstances, it was set as the cup type molded object that an adhesive layer becomes an innermost outermost layer.

  Subsequently, acrylonitrile-butadiene-styrene (ABS) copolymer resin (ABS resin “Toyolac” (registered trademark) 930 manufactured by Toray Industries, Inc.) heated to 280 ° C. was poured into the cup-shaped molded body. After the ABS is cooled and solidified, the cup-shaped molded product obtained by injecting the ABS copolymer resin into the cup-shaped molded product is taken out from the mold, the laminated film is peeled off, and then the clear layer of the cup-shaped molded product is used with a wavelength of 365 nm. Was cured.

  The release film, moldability, and printability of the laminated film prepared in this example were all good.

(Examples 2-12, 14)
The same procedure as in Example 1 was performed except that the composition of the laminated film was changed as shown in the table. The release properties and moldability of the laminated film prepared in this example were both good.

(Example 13)
The same procedure as in Example 1 was conducted except that the laminated film was composed of two layers of A layer / B layer. The release properties and moldability of the laminated film prepared in this example were both good.

(Comparative Example 1)
Example 1 was repeated except that the film composition was a PET-A (B layer) single layer. Since the laminated film produced in this example did not have the A layer, the releasability and printability were insufficient.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that the composition of the laminated film was changed as shown in the table. The laminated film produced in this example had a large ΔTcg of the A layer, and the moldability was insufficient.

(Comparative Example 3)
The same procedure as in Example 1 was performed except that the composition of the laminated film was changed as shown in the table. The laminated film produced in this example had a small ΔTcg of the B layer and insufficient moldability.

(Comparative Example 4)
The same procedure as in Example 1 was performed except that the composition of the laminated film was changed as shown in the table. Since the laminated film produced in this example did not contain polyolefin resin in the A layer, the releasability was insufficient.

(Comparative Example 5)
The same procedure as in Example 1 was conducted except that carnauba wax was contained in the A layer in an amount of 1% by mass relative to the total mass of the A layer of 100% by mass. The laminated film produced in this example had good release properties, moldability, and printability when not heated, but the release properties after heating at 100 ° C. for 10 minutes were insufficient.

(Comparative Example 6)
PET-A (B layer) was supplied to a vented twin screw extruder (L / D = 36) and melted at 275 ° C., and then passed through two vacuum vent portions. Next, the resin was passed through a leaf disk filter having a filtration accuracy of 30 μm and then supplied to a multi-manifold die.

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

  After each resin passed through the manifold in the die, two kinds of resins were laminated so as to be B layer / A layer / B layer, and extruded from a slit die into a film shape. Electrostatic application was applied to both ends of the extruded film using a needle-like edge pinning device, and the film was brought into close contact with a casting drum whose surface was processed to be cooled and solidified. The surface temperature of the casting drum was adjusted to 55 ° C. A polyester film having a layer thickness of 40 μm per A layer and a total film thickness of 400 μm was obtained.

  Then, before stretching in the longitudinal direction, the film temperature is raised with a heating roll, the preheating temperature is 110 ° C., the stretching temperature is 105 ° C., the stretching is 3.3 times in the longitudinal direction, and the temperature is immediately controlled to 40 ° C. Cooled with a roll. Next, the film was stretched 3.3 times in the width direction at a preheating temperature of 95 ° C. and a stretching temperature of 120 ° C. using a tenter-type transverse stretching machine, and the temperature was maintained at 240 ° C. for 5 seconds while relaxing 4% in the width direction. A heat treatment was performed to obtain a biaxially stretched laminated film having a thickness of 4.0 μm per layer A and a total film thickness of 40 μm.

  After the laminated film was produced, a transfer foil was produced in the same manner as in Example 1, and vacuum forming was performed. The laminated film produced in this example had high stress and insufficient moldability.

  According to the present invention, a laminate film that is excellent in releasability, moldability, and printability and that can be manufactured without including steps such as coating and extrusion lamination can be obtained. It is suitably used as a transfer foil for performing printing transfer processing for in-mold transfer foils, automotive interior / exterior parts, bathroom panels, home appliance parts, packaging containers, and the like.

Claims (5)

At least a layer (A layer) containing a polyester resin as a main component and having a crystallinity parameter ΔTcg of 35 ° C. or less and a layer containing a polyester resin as a main component and having a crystallinity parameter ΔTcg of more than 35 ° C. (B layer) A laminated film having
The laminated film has an A layer on at least one outermost layer,
The layer A contains a polyolefin resin, and the mass ratio of the polyester resin and the polyolefin resin contained in the layer A is polyester resin / polyolefin resin = 99.9 / 0.1-50 / 50,
A laminated film having a stress at 100% elongation at 100 ° C of 0.5 to 5 MPa.   The laminated film according to claim 1, wherein the crystallinity parameter ΔTcg of the A layer is 11 ° C or lower.   The laminated film according to claim 1 or 2, wherein the polyolefin resin comprises a modified polyolefin resin and other polyolefin resins.   The mass ratio of the modified polyolefin resin and the other polyolefin resin is modified polyolefin resin / other polyolefin resin = 0.1 / 99.9 to 40/60, according to claim 3. Laminated film.   The sheet | seat for shaping | molding containing the laminated | multilayer film in any one of Claims 1-4