TW201422432A - Resin film and resin film laminated ornamental panel - Google Patents

Abstract

To provide a resin film using plant-derived raw material as much as possible, and an ornamental panel in which the resin film is laminated on a base panel. A resin film characterized by including at least one of the plant-derived resin layers (A, B, or C) described below. A layer: any of a plant-derived PTT resin, a plant-derived PET resin, a plant-derived olefin-based resin (PP, PE), or a plant-derived PC resin, or a blended composition of two or more of these resins. B layer: any of a plant-derived PTT resin, a plant-derived PET resin, a plant-derived olefin-based resin (PP, PE), or a plant-derived PC resin, or a product obtained by adding a plant-derived compatibilizer and/or a plant-derived elastomer to a blended composition of two or more of these resins. C layer: any of a plant-derived PTT resin, a plant-derived PET resin, a plant-derived olefin-based resin (PP, PE), or a plant-derived PC resin, or a product obtained by adding a plant-derived ionomer to a blended composition of two or more of these resins.

Description

Resin film and decorative sheet laminated with resin film

The present invention relates to a resin film comprising a raw material derived from a plant, and a decorative sheet laminated with a resin film, and more particularly to a resin film having less influence on the global environment for reducing the use of petroleum raw materials as much as possible, and laminating on the substrate A decorative sheet in which a resin film is laminated with the resin film.

Previously, polyethylene terephthalate, polyethylene, polypropylene, and the like have been widely used as a film material widely used in decorative sheets, packaging materials, containers, and the like. These systems use limited resources such as petroleum as raw materials, and are therefore worried about the exhaustion of these. Furthermore, these petroleum and other resources are substances that have been fixed by the long history of carbon on the earth. When the resins obtained from these are discarded, incinerated, etc., a large amount of carbon dioxide is generated, which is worried about an increase in carbon dioxide. The deterioration and warmth of the global environment caused by it.

In addition, as a film material for the purpose of obtaining a biomarker, a film material using polylactic acid (PLA) as a raw material (see Patent Documents 1 and 2) or a decorative film containing polyolefin using a plant-derived material has been proposed. (Refer to Patent Document 3). As a film material using these plant-derived raw materials, various materials have been developed, and it is also relatively easy to obtain, and carbon dioxide is absorbed and fixed during the production process, and it can be recycled or non-depleted resources. Words are superior to petroleum resources.

[First technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-73998 (polylactic acid)

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-207535 (polylactic acid)

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-36341 (polyolefin decorative film)

However, the film materials using the raw materials derived from plants disclosed in Patent Documents 1 to 3 are not considered to have sufficient physical properties of the film for decorative laminate. For example, when a single layer film is laminated to form a double layer film, or when it is laminated on a substrate for use in a decorative material, adhesion, workability, durability, or flame retardancy are required for the film itself, but It is believed that previous membrane materials derived from plants have sufficient characteristics.

An object of the present invention is to provide a high-quality resin film and a decorative sheet using the same as the raw material of the plant, which can reduce the deterioration of the global environment or the use of a limited resource. Another object of the present invention is to provide a decorative sheet in which the resin film is laminated on a substrate such as a metal plate and which is excellent in adhesion or workability. Further, it is still another object of the present invention to provide a resin film using a plant-derived material which raises the biological ratio of the resin film in a manner to satisfy the conditions of the biomarker and imparts the same degree as the resin film of the petroleum-based plastic which was previously used. Performance.

(1) The resin film according to the first embodiment of the present invention comprises one or more of the following resin-derived resin layers (layer A, B or C): layer A: polybutylene terephthalate derived from plants ( Polytrimethylene terephtalate (PTT) resin, plant-derived polyethylene terephthalate (PET) resin, plant-derived olefin resin (polypropylene (PP), polyethylene (PE)), Any one of a polycarbonate (PC) resin derived from a plant, or a blending composition of two or more thereof; a layer B: a polytrimethylene terephthalate (PTT) resin derived from a plant, Plant polyethylene terephthalate (PET) resin, plant-derived olefin resin (polypropylene (PP), polyethylene (PE)), plant-derived polycarbonate (PC) resin, Or a plant-derived compatibilizer and/or a plant-derived elastomer is added to the two or more blending compositions; Layer C: Polypropylene terephthalate (PTT) resin from plants, polyethylene terephthalate (PET) resin from plants, olefin resin (polypropylene (PP), poly Any one of ethylene (PE), a plant-derived polycarbonate (PC) resin, or a plant-derived ionic polymer added to the two or more blend compositions.

(2) The resin film-attached layer according to the second embodiment of the present invention has one or more resin-derived resin layers (A, B or C layers) as claimed in claim 1 and the following D-layer or E-layer as a surface layer. :D layer: containing polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene terephthalate (PET) resin, copolymerization polymerization Any of ethylene terephthalate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, or crystals of the two or more blend compositions Polyester resin; E layer: comprising copolymerized polyethylene terephthalate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, polycarbonate (PC Any one of the resins or a substantially amorphous polyester of the two or more blend compositions.

(3) The resin film-attached layer according to the third embodiment of the present invention has one or more layers of the plant-derived resin layer (layer A, B or C) of the first embodiment as the intermediate layer, and the outermost layer and the most The D layer or the E layer of the second embodiment described above.

(4) The resin film according to the fourth embodiment of the present invention is an alternately laminated layer of the plant-derived resin layer (layer A, B or C) of the first embodiment, and the layer D or layer E of the second embodiment. And the D layer or the E layer is the outermost layer and the lowermost layer.

(5) The resin film of the fifth embodiment of the present invention is a resin film according to any one of the first to fourth embodiments described above, with or without two or more layers.

(6) The resin film according to the sixth embodiment of the present invention is characterized in that a component constituting the D layer (including polybutylene terephthalate (PBT) is blended in the resin layer (A, B or C layer) derived from the plant. Resin, polytrimethylene terephthalate (PTT) resin, polyethylene terephthalate (PET) resin, copolymerized polyethylene terephthalate resin, copolymerized polybutylene terephthalate Any one of an ester resin, a copolymerized polytrimethylene terephthalate resin, or a crystalline polyester of the two or more blending compositions thereof, or a component constituting the E layer (including a copolymerized polyparaphenylene) Ethylene dicarboxylate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, polycarbonate (PC) resin, or two or more of these A substantially amorphous polyester blended with the composition).

(7) The resin film of the present invention is characterized in that a printing layer is provided between any one of the resin films of any one of the above (1) to (6).

(8) The single-layer resin film of the present invention comprises: a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent.

(9) The single-layer resin film of the present invention comprises: polybutylene terephthalate (PBT) resin, plant-derived polytrimethylene terephthalate (PTT) resin, and copolymerized polyethylene terephthalate a blend composition of a diester (PET) resin and a coloring agent; or a polybutylene terephthalate (PTT) resin derived from a plant, a copolymerized polyethylene terephthalate (PET) resin, and a coloring agent. The composition is blended.

(10) The two-layer resin film of the present invention comprises a blending composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, Or a layer of a blending composition of a polybutylene terephthalate (PBT) resin and a coloring agent as a first layer; and as a second layer, a layer comprising polybutadiene phthalate from a plant Blend composition of ester (PTT) resin, polybutylene terephthalate (PBT) resin and color former, or poly pair a layer of a blend composition of a butyl phthalate (PBT) resin and a coloring agent; a layer of at least one layer of the first layer or the second layer of the resin film is blended with a plant-derived polyterephthalic acid Propylene diacrylate (PTT) resin and polybutylene terephthalate (PBT) resin.

(11) The two-layer resin film of the present invention comprises a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, Or a layer of a blending composition of a polybutylene terephthalate (PBT) resin and a coloring agent as a first layer; and a polybutylene terephthalate (PBT) laminated thereon as a second layer a resin, a blended composition of a polyethylene terephthalate (PET) resin and a coloring agent, or a polybutylene terephthalate (PBT) resin, a plant-derived polytrimethylene terephthalate a layer of a blending composition of an ester (PTT) resin, a copolymerized polyethylene terephthalate (PET) resin, and a coloring agent; or a layer of at least one layer of the first layer or the second layer of the resin film It is composed of a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(12) The two-layer resin film of the present invention has a layer containing a copolymerized polyethylene terephthalate (PET) resin as a first layer; and a layer containing a plant-containing aggregate as a second layer thereon a blending composition of a propylene terephthalate (PTT) resin and a coloring agent, or a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from a plant. The blending composition of the coloring agent is further blended with a layer of a resin composition of an antistatic agent.

(13) The two-layer resin film of the present invention has a layer containing a copolymerized polyethylene terephthalate (PET) resin as a first layer; and as a second layer, a layer containing a plant-containing polymer is laminated. A layer of a blend composition of a propylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a color former.

(14) The three-layer resin film of the present invention has the constitution of the two-layer resin film of the above (10) as the first layer and the second layer, and the second layer is laminated with the polyphenylene terephthalate as the third layer. a blend of a butylene dicarboxylate (PBT) resin, a copolymerized polyethylene terephthalate (PET) resin and a color former, or a polybutylene terephthalate (PBT) resin, from a plant a layer of a polytrimethylene terephthalate (PTT) resin, a copolymerized polyethylene terephthalate (PET) resin, and a coloring agent blending composition; in the above first to third resin films At least one or more layers are blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(15) The three-layer resin film of the present invention comprises a layer comprising a copolymerized polyethylene terephthalate (PET) resin as a first layer; and as a second layer, a layer comprising a plant-containing polymer is laminated a blending composition of a propylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, or a polybutylene terephthalate (PBT) resin and a coloring agent. a layer of a composition to be blended thereon; as a third layer, a polybutylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a colorant containing a plant are laminated. And a blending composition of an antistatic agent, or a layer of a blending composition of a polybutylene terephthalate (PBT) resin, a colorant, and an antistatic agent; in the above first to third resin films At least one or more layers are blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(16) The three-layer resin film of the present invention comprises a layer comprising a copolymerized polyethylene terephthalate (PET) resin as a first layer; and as a second layer, a layer comprising a plant-containing polymer is laminated Propylene terephthalate (PTT) a layer of a blending composition of a resin, a polybutylene terephthalate (PBT) resin, and a coloring agent; on the third layer, a polybutylene terephthalate (PBT) resin is laminated as a third layer A layer of a blend composition of colorants.

(17) The three-layer resin film of the present invention comprises a blending composition layer of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent. As the first layer, a printed layer is formed as the second layer, and a biaxial orientation-polyethylene terephthalate resin is laminated as the third layer. Layer.

(18) The four-layer resin film of the present invention has the two layers of the resin film of the above (10) as the first layer and the second layer; and the second layer, the printed layer is formed as the third layer; Further, as the fourth layer, a biaxially stretched polyethylene terephthalate (BO-PET) resin was laminated.

(19) The four-layer resin film of the present invention comprises a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, Or a layer of a blend composition of a polybutylene terephthalate (PBT) resin and a coloring agent as a first layer; a printed layer is formed as a second layer thereon; and a third layer is formed thereon And a laminate comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, or polybutylene terephthalate (PBT) a layer of a resin; further thereon, as a fourth layer, laminated with polytrimethylene terephthalate containing plants a blending composition of (PTT) resin, polybutylene terephthalate (PBT) resin and ultraviolet absorber, or a blend composition of polybutylene terephthalate (PBT) resin and ultraviolet absorber A layer of polybutylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin derived from plants is blended in at least one layer of the resin film other than the above printed layer.

(20) The four-layer resin film of the present invention is laminated with a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a color former. a layer of a blending composition of a polybutylene terephthalate (PBT) resin and a coloring agent as a first layer; a printed layer is formed as a second layer thereon; Layered and laminated with a polyethylene terephthalate (PET) resin layer; further thereon, as a fourth layer, a polyphenyl terephthalate (PTT) resin containing a plant is laminated a blend of a butylene terephthalate (PBT) resin and a UV absorber, or a blend of a polybutylene terephthalate (PBT) resin and a UV absorber; in the above printed layer A layer of at least one layer of the resin film other than the polymer is blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(21) The 5-layer resin film of the present invention comprises a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, Or a layer of a blend composition of a polybutylene terephthalate (PBT) resin and a coloring agent as a first layer; a printed layer is formed as a second layer thereon; and a third layer is formed thereon And a laminate comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, or a polyterephthalic acid a layer of a butylene diester (PBT) resin; as a fourth layer, a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin comprising a plant layer is laminated a blending composition, or a layer of polybutylene terephthalate (PBT) resin; further thereon, as a fifth layer, a polytrimethylene terephthalate (PTT) resin comprising a plant layer is laminated a blend of a polybutylene terephthalate (PBT) resin and a UV absorber, or a blend of a polybutylene terephthalate (PBT) resin and a UV absorber; At least one layer of the resin film other than the printed layer is blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(22) The five-layer resin film of the present invention has the two layers of the resin film of the above (10) as the first layer and the second layer; and the second layer, the printed layer is formed as the third layer; In the above, as a fourth layer, a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, or a polyparaphenylene is laminated. a layer of a butylene formate (PBT) resin; further thereon, as a fifth layer, a polybutylene terephthalate (PTT) resin containing a plant, a polybutylene terephthalate (PBT) a layer of a blended composition of a resin and a UV absorber, or a blend of a polybutylene terephthalate (PBT) resin and a UV absorber; at least one layer of a resin film other than the above printed layer The layer is blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(23) The five-layer resin film of the present invention has the first layer and the second layer of the resin film of the above (10); and the printed layer is formed as the third layer on the second layer; In the above, a copolymerized polyethylene terephthalate (PET) resin layer is laminated as the fourth layer; and further, as a fifth layer, a polytrimethylene terephthalate containing a plant is laminated. a blending composition of (PTT) resin, polybutylene terephthalate (PBT) resin and ultraviolet absorber, or a blend composition of polybutylene terephthalate (PBT) resin and ultraviolet absorber A layer of polybutylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin derived from plants is blended in at least one layer of the resin film other than the above printed layer.

(24) The six-layer resin film of the present invention has the two layers of the resin film of the above (10) as the first layer and the second layer; and the second layer, the printed layer is formed as the third layer; As a fourth layer, a polymerized polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin blend composition, or polyterephthalic acid is laminated. a layer of a butylene diester (PBT) resin; further thereon, as a fifth layer, a polybutylene terephthalate (PTT) resin containing plant-derived material, polybutylene terephthalate (PBT) is laminated as a fifth layer. a resin blending composition, or a layer of polybutylene terephthalate (PBT) resin; further thereon, as a sixth layer, a polyphenylene terephthalate (PTT) containing a plant layer is laminated Blending composition of resin, polybutylene terephthalate (PBT) resin and ultraviolet absorber, or blending composition of polybutylene terephthalate (PBT) resin and ultraviolet absorber A layer of at least one layer of a resin film other than the above-mentioned printing layer is blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin.

(25) The resin film of the present invention is the resin film of any one of the above (9), (11) to (16), (23), and the copolymerized polyethylene terephthalate 2 to 15 mol% of terephthalic acid of the acid component of the ester (PET) resin is substituted with isophthalic acid.

(26) The resin film of the present invention is used in a resin film according to any one of the above (17) and (18), and is replaced by a biaxially-oriented polyethylene terephthalate (BO-PET) resin. And a biaxially-stretched copolymerized polyethylene terephthalate obtained by substituting 2 to 15 mol% of terephthalic acid as an acid component of polyethylene terephthalate with isophthalic acid Ester resin.

(27) The resin film according to any one of the above (1) to (26), wherein a resin layer is contained in any one of the resin layers.

(28) The resin film of the present invention is characterized in that an embossed uneven portion is formed on a layer which is the outermost layer of the resin film according to any one of the above (1) to (27).

(29) The resin film of the present invention is formed with a mirror surface on a layer which is the outermost layer of the resin film according to any one of the above (1) to (27).

(30) The resin film of the present invention is the resin film according to any one of the above (2) to (29), wherein the PTT content of the resin in which PBT and PTT are blended is set to 20 to 80%.

(31) The decorative sheet in which the resin film is laminated in the present invention is a resin film according to any one of the above (1) to (30), at least one area of the substrate, with or without an adhesive.

According to the present invention, it is possible to provide a resin film using a plant-derived raw material which reduces the amount of the petroleum-based resin and uses a plant-derived raw material to satisfy the condition of the biomarker, thereby increasing the biological ratio of the resin film, and imparting the previous Use the same degree of performance of petroleum-based plastic resin film.

Further, the decorative sheet in which the resin film is laminated on the substrate is excellent in adhesion, workability, and durability.

Fig. 1 is a schematic view showing a configuration of a resin film of the first embodiment.

Fig. 2 is a schematic view showing a configuration of a resin film of a second embodiment.

Fig. 3 is a schematic view showing a configuration of a resin film of a third embodiment.

Fig. 4 is a schematic view showing a configuration of a resin film of a fourth embodiment.

Fig. 5 is a schematic view showing a configuration of a resin film of a fifth embodiment.

Figure 6 is a graph showing the change in the modulus of elasticity in the case where a PBT resin is blended with a PBT resin. chart.

Hereinafter, the resin film of the first embodiment of the present invention will be described.

Fig. 1 is a schematic view showing the configuration of a resin film of the first embodiment. Fig. 1(a) shows an example in the case where the resin film is a single layer, (b) shows a configuration in the case where the resin film is two layers, and (c) shows a configuration in the case where the resin film is three layers, (d) A configuration in the case where the resin film is four layers. The resin film contains an A layer, a B layer, or a C layer.

In the case where the resin film is the A layer, it comprises a plant-derived polytrimethylene terephthalate (PTT) resin, a plant-derived polyethylene terephthalate (PET) resin, and a plant-derived olefin resin ( Any one of polypropylene (PP), polyethylene (PE), plant-derived polycarbonate (PC) resin, or two or more of these blend compositions.

In the case where the resin film is the B layer, it is contained in a plant-derived polytrimethylene terephthalate (PTT) resin, a plant-derived polyethylene terephthalate (PET) resin, and a plant-derived olefin resin. (Company (PP), Polyethylene (PE)), Plant-derived Polycarbonate (PC) resin, or a blending agent derived from plants and added to the two or more blending compositions Self-planting elastomers (from plant compatibilizers, plant-derived elastomers can be either). In the case where the resin film is the C layer, it is contained in a plant-derived polytrimethylene terephthalate (PTT) resin, a plant-derived polyethylene terephthalate (PET) resin, and a plant-derived olefin resin. Any one of a polypropylene (PP), a polyethylene (PE), a plant-derived polycarbonate (PC) resin, or a plant-derived ionic polymer added to the two or more blend compositions.

Here, the component derived from a plant means a component which is a starting material of a substance produced by a plant. For example, examples of the plant-derived polytrimethylene terephthalate resin (PTT) which forms the A layer, the B layer, and the C layer include those produced from terephthalic acid and 1,3 propanediol derived from plants.

In addition, as a plant-derived polyethylene terephthalate resin (PET) which forms the A layer, the B layer, and the C layer, terephthalic acid which is a raw material of polyethylene terephthalate ( In the mass ratio of 70%) and monoethylene glycol (mass ratio: 30%), monoethylene glycol is replaced by a raw material derived from sugar cane and the like.

The plant-derived olefin-based resin (polypropylene (PP), polyethylene (PE)) which forms the A layer, the B layer, and the C layer is a low-density polyethylene. Linear low density polyethylene, high density polyethylene, polypropylene, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methyl acrylate copolymer, and copolymers thereof, blenders Or cross-linking, etc.

The polycarbonate-derived polycarbonate (PC) resin which forms the A layer, the B layer, and the C layer includes a polycarbonate containing a sugar alcohol and a polyglycol disclosed in JP-A-2011-241277. Wait.

As the acid-forming resin, a part of the terephthalic acid is replaced by a structure of another dicarboxylic acid, and the other dicarboxylic acid component in this case may, for example, be oxalic acid or malonic acid. Succinic acid, adipic acid, azelaic acid, sebacic acid, pivalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, p-hydroxybenzoic acid, and the like. Further, the other dicarboxylic acid component may be one selected from the above-identified dicarboxylic acid components, or may be a mixture comprising two or more of them. Further, the amount of the other dicarboxylic acid to be substituted may be appropriately selected.

Further, as the alcohol component, for example, one of ethylene glycol may be substituted with another diol component.

Examples of other diol components in this case include propylene glycol, 1,3-propanediol, and 1,4-butane. Alcohol, hexanediol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, neopentyl alcohol, trimethylol, methoxy polyalkylene Glycol and the like. Further, the other diol component may be one selected from the diol components listed above, or may be a mixture comprising two or more combinations. Further, the amount of other diol to be substituted may be appropriately selected.

Further, the resin forming the layers A, B, C, and D may further contain the above-described copolymerization component.

In the laminated resin film formed by the multi-layer structure as described above, the melt viscosity under the shear rate of 10 [1/s] measured according to JIS-K7199 is selected to be 1000 [Pa. In the case where the resin temperature difference is within 30 ° C, preferably within 15 ° C, and more preferably within 5 ° C, any commercially available resin may be selected.

<Compatibilizer>

In the layer B, in order to uniformly mix the blended components, a compatibilizer derived from plants may be mixed. The amount of mixing is appropriately selected depending on the use.

As the compatibilizing agent, a resin such as a vinyl copolymer derived from plants is preferably used.

Examples of the compatibilizing agent for such an ethylene-based copolymer include ethylene-vinyl acetate copolymer derived from plants, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and ethylene-ethyl acrylate copolymer. , ethylene-ethyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-maleic anhydride terpolymer, ethylene-ethyl acrylate - maleic anhydride terpolymer, ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate terpolymer, ethylene-ethyl acrylate-glycidyl methacrylate Ester terpolymer.

Among them, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid can be preferably used. Ethyl ester copolymer.

Further, two or more kinds of compatibilizers may be used in combination.

As a layer B plant-derived elastomer, it can be used to obtain 1,3- from plants. A thermoplastic polyester elastomer or the like which uses propylene glycol as a raw material. Specifically, for example, a product manufactured by DuPont under the trade name Hytrel RS can be cited.

In addition, an environmentally-friendly thermoplastic elastomer composition containing 25% by mass or more of a plant-derived resin disclosed in Japanese Laid-Open Patent Publication No. 2010-254729 or the like can be used.

Examples of the plant-derived ionic polymer as the layer C include an ethylene-methacrylic acid copolymer ionic polymer derived from a plant, an ethylene-acrylic acid copolymer ionic polymer, a propylene-methacrylic acid copolymer ionic polymer, and propylene. -Acrylic copolymer ionic polymer, butene-acrylic acid copolymer ionic polymer, ethylene-vinyl sulfonic acid copolymer ionic polymer, styrene-methacrylic acid copolymer ionic polymer, sulfonated polystyrene ionic polymer , fluorine-based ionic polymer, telechelic polybutadiene acrylic acid ionic polymer, sulfonated ethylene-propylene-diene copolymer ionic polymer, hydrousylated polypentene ionomer, polypentene ionomer, poly( Vinyl pyridinium salt) ionic polymer, poly(vinyltrimethylammonium salt) ionic polymer, poly(vinylbenzyl sulfonium salt) ionic polymer, styrene-butadiene acrylic acid copolymer ionic polymer, poly Amino urethane ionic polymer, sulfonated styrene-2-propenylamine-2-methylpropane sulfonium chloride ion polymer, acid-amine ionic polymer, aliphatic ionic polymer, aromatic ion Thereof and the like.

By blending a compatibilizing agent, an elastomer derived from a plant, or an ionic polymer derived from a plant, a resin film which does not lower the content of a raw material derived from a plant and which has improved workability or adhesion can be obtained.

Further, in FIGS. 1(b) to 1(d), there is a case where a resin layer (layer A, B or C) of the same layer is laminated to form a resin film, but even if it is the same resin layer, it is contained in the layer. The composition of the composition is different. For example, there are cases in which a layer of a compatibilizing agent, an elastomer, and an ionic polymer are separately laminated.

The embodiments described below can also be used in the same manner.

The resin film of the second embodiment of the present invention is shown in Fig. 2 .

Fig. 2(a) shows an example in the case where the resin film is two layers, (b) shows a configuration in the case where the resin film is three layers, and (c) shows a configuration in the case where the resin film is four layers.

The resin film of the second embodiment has one or more resin films of the first embodiment and the following D layer or E layer as a surface layer.

D layer: including polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene terephthalate (PET) resin, copolymerized poly-p-phenylene Any of ethylene glycol formate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, or crystalline polyester of the two or more blending compositions Resin.

E layer: including any of the copolymerized polyethylene terephthalate resin, the copolymerized polybutylene terephthalate resin, the copolymerized polytrimethylene terephthalate resin, and the polycarbonate (PC) resin. One or a substantially amorphous polyester of the two or more blend compositions.

Further, the D layer and the E layer are layers containing the resin component derived from petroleum in the past.

In the resin film of the second embodiment, by forming a multi-layer resin film of a resin film having a composition in which adhesion is improved, it is possible to suppress interlayer peeling of the resin film.

That is, by the layer D layer and the E layer on the resin film derived from the plant, that is, the polybutylene terephthalate (PBT) resin or the polytrimethylene terephthalate (PTT) resin as the previous resin. , polyethylene terephthalate (PET) resin, copolymerized polyethylene terephthalate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin Any one or a crystalline polyester of the two or more blending compositions, or a copolymerized polyethylene terephthalate resin, a copolymerized polybutylene terephthalate resin, a copolymerized poly A layer of a substantially amorphous polyester of either a propylene terephthalate resin or a polycarbonate (PC) resin, or a blend of two or more of the above, can be made into a maintenance product A multilayer resin film of the same surface characteristics.

The resin film of the third embodiment of the present invention is shown in Fig. 3 .

Fig. 3(a) shows an example in the case where the resin film is three layers, (b) shows a configuration in the case where the resin film is four layers, and (c) shows a configuration in the case where the resin film is five layers, (d) A configuration in the case where the resin film is six layers.

The resin film of the third embodiment includes one or more layers of the resin film of the first embodiment as an intermediate layer, and the D layer or the E layer is laminated on the outermost layer and the lowermost layer.

That is, a polybutylene terephthalate (PBT) resin, a polytrimethylene terephthalate (PTT) resin, or a polyparaphenylene phthalate is used as a resin by a resin film from a plant. Ethylene glycol (PET) resin, copolymerized polyethylene terephthalate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, or a crystalline polyester of the two or more blending compositions, or a copolymerized polyethylene terephthalate resin, a copolymerized polybutylene terephthalate resin, a copolymerized polytrimethylene terephthalate A layer of a substantially amorphous polyester of either a diester resin or a polycarbonate (PC) resin or a blend of two or more of the above may be made to maintain the same surface characteristics as the prior product and Adhesive multi-layer resin film.

The resin film of the fourth embodiment of the present invention is shown in Fig. 4 .

Fig. 4(a) shows an example in the case where the resin film is three layers, (b) shows a configuration in the case where the resin film is five layers, and (c) shows a configuration in the case where the resin film is seven layers.

In the resin film of the fourth embodiment, the resin film of the first embodiment and the D layer or the E layer are alternately laminated, and the D layer or the E layer is the outermost layer and the lowermost layer.

That is, by forming a composition in which a resin (D layer or E layer) and a resin derived from plants (A layer, B layer or C layer) are alternately laminated, it is possible to maintain and maintain the content of the raw material from the plant. A multi-layer resin film having the same surface characteristics and adhesion as the previous product.

The resin film of the fifth embodiment of the present invention is shown in Fig. 5 .

Fig. 5(a) shows an example in the case where the resin film is four layers, (b) shows a configuration in the case where the resin film is six layers, and (c) shows a configuration in the case where the resin film is ten layers.

Further, Fig. 5(a) is a laminate of two layers of the resin film of Fig. 2(a), Fig. 5(b) is a laminate of two layers of the resin film of Fig. 3(a), and Fig. 5(c) is a laminate. There are 2 layers of resin film of Figure 4(b). In the resin film of the fifth embodiment, any one of the resin films of the first to fourth embodiments of the first to fourth embodiments is laminated with or without an adhesive, so that the resin film can be produced without reducing the amount of the resin film. A multi-layer resin film having a raw material content ratio and maintaining the same surface characteristics and adhesion as the previous product.

The resin film according to another sixth embodiment of the present invention is characterized in that the layer A, B or C is blended with a component constituting the D layer (D layer: comprising polybutylene terephthalate (PBT) resin, polyparaphenylene) Propylene dicarboxylate (PTT) resin, polyethylene terephthalate (PET) resin, copolymerized polyethylene terephthalate resin, copolymerized polybutylene terephthalate resin, copolymerization polymerization Any of propylene terephthalate resins, or a crystalline polyester resin of the two or more blending compositions thereof, or a component constituting the E layer (including copolymerized polyethylene terephthalate) Resin, total Any one of the polymerized polybutylene terephthalate resin, the copolymerized polytrimethylene terephthalate resin, the polycarbonate (PC) resin, or the two or more of the blended compositions Crystalline polyester).

In other words, by forming a resin film in which the resin is blended to the extent that the content of the raw material from the plant is not reduced, a plant-derived resin film having a composition for improving the adhesion can be obtained, and the interlayer peeling of the resin film can be suppressed or A resin film that improves adhesion.

In particular, the resin film having a multi-layer structure and the film-layered material in which the resin film is laminated on the substrate can reduce the stress concentration to the so-called weak boundary layer (WBL) during processing, thereby improving the suppression of film peeling. effect. Therefore, it can be preferably used for high-processing applications.

Further, in the above resin film, when flame retardancy or durability is required for each resin film, various additives may be blended in order to impart flame retardancy, hydrolysis resistance, or weather resistance.

In addition, for example, an organic or inorganic filler, an anti-blocking agent, a crystallization accelerator, a nucleating agent, a gas adsorbent, an anti-aging agent (ester, guanamine, etc.), an antioxidant, and an anti-odor oxidizing agent may be appropriately formulated. , UV absorber, infrared absorber, light stabilizer, light stabilizer, adhesion imparting agent, plasticizer (such as fatty acid such as stearic acid or oleic acid or such metal salt), softener (mineral oil, wax, paraffin) Classes, etc., stabilizers, heat stabilizers, lubricants, mold release agents, antistatic agents, terminal sealants, polymerization inhibitors, crosslinking agents, denaturants, colorants (including coloring pigments, coloring dyes, etc.) ), coupling agent, preservative, anti-mold agent, flame retardant, flame retardant, anti-caries agent, anti-wear enhancer, matting agent, deodorant, ion exchanger, refractive index modifier and other additives.

Further, embossing can be selectively performed on the surface of the resin film to form an embossed uneven portion, and a high-dimensional design property or a mirror finishing process can be performed.

Further, a gloss adjustment layer may be provided on the surface of the above resin film. The gloss adjustment layer may be colorless and transparent, or may be colored and transparent, and may also be matte transparent, which is provided for adjusting the glossiness of the surface of the resin film, or may be a layer for imparting a protective surface (hard coat layer). The role of the person.

<Bioactivity 25 wt% or more>

Further, in the resin film of the present embodiment, the bioavailability of the entire resin film is preferably 25 wt% or more.

The reason is that the bioavailability of the resin film as a whole is 25 wt% or more, and the Japanese life can be obtained. The bioplastics identification mark recognized by the JBPA can provide the resin film with added value as a commodity material with a small environmental load.

<biomarker>

Here, the biomarkers used in the present invention will be described.

The Japan Society for Organic Resources (JORA), a social corporation, has identified biomarkers for products using biological materials. The purpose of the biomarker is to enable consumers to know the use and utilization of bio-products by giving biomarkers to products produced and utilized by biomaterials, and to promote the use of biomaterials by popularizing such products, and to utilize natural Gifts contribute to the building of a sustainable society.

In addition, regarding the use of biomaterials produced from biological materials such as polylactic acid, the Japan Bioplastics Association (JBPA) has a certain amount or more in view of the viewpoint of preventing global warming and reducing the importance of fossil resource consumption. The bio-plastic product of the organic resource (plant, etc.) as a plastic component has established a bio-plastic identification system, and the product suitable for the benchmark determined by the association is identified as "bioplastic", in order to make it easier for the average consumer. Identify bioplastic products and allow the use of symbolic markers.

In order to carry out the identification of bioplastics, it is necessary to be a plastic product having a bio-plasticity degree in the product (the ratio of the bio-plastic composition in the raw material and the bio-plastic composition of the product to the total amount) of 25 wt% or more. That is, considering the load on the global environment, it is very important to increase the ratio of biomaterials in the resin film as much as possible (minimum of 25 wt% or more). If it is considered that consumers understand it as added value, it is necessary to obtain bioplastics. Identification mark.

The present inventors have considered that the resin film of the present invention is also preferable in order to increase the ratio of the biomaterial as much as possible in view of the above.

<print layer>

The resin film of the present invention can provide a printing layer between any of the layers of the resin film of the present invention.

That is, in the resin film, a printing layer may be formed in order to color or form a pattern. In addition, by partially or completely replacing one of the petroleum-based solvents as a solvent for the ink with a printing ink containing an ester compound obtained from a bio-alcohol or a compound having a hydroxyl group derived from a living organism, it is also possible to use without impairing printing adaptability. The ink which is excellent in the environment and which is excellent in the balance between the evaporative drying property of the ink and the on-machine stability forms a printing layer.

The decorative sheet of the present invention is at least on the substrate with or without an adhesive One area layer has the resin film of the present invention.

The decorative sheet in which the resin film of any of the present invention is laminated on the substrate is excellent in adhesion to a substrate such as a metal plate, and when the decorative sheet is processed, there is no peeling of the resin film or peeling from the substrate, and it can be processed into various molded articles. .

<Binder>

As an adhesive for laminating the resin films or for laminating the resin film and the substrate, since it is fireproof, odorless, and inexpensive, it is preferable to use a usual adhesive such as polyester, acrylic, or vinyl acetate. An emulsion type adhesive such as a resin system, an ethylene-vinyl acetate resin system, a urea resin system, or a urethane resin system.

In addition, an emulsion type adhesive such as a polyester urethane resin or a thermosetting adhesive such as an epoxy-phenol resin or a polyester urethane resin-based adhesive may be used. .

Furthermore, the adhesive is not limited to those exemplified.

Further, as the resin which can be used as a component of the adhesive, a resin having reactivity or affinity to the resin of the A, B, and C layers can be preferably used. The term "reactive or affinity" means a functional group having a functional group having a high affinity with a resin of the A, B, and C layers or a resin capable of reacting with the A, B, and C layers. Examples of the functional group having such a property include an acid anhydride group, a carboxylic acid group, a carboxylate group, a carboxy fluorenyl group, a carboxylic acid oxime group, a carboxy fluorenyl group, a sulfonic acid group, a sulfonate group, A functional group such as a sulfonium chloride group, a sulfonium sulfonate group, a sulfonyl chloride group, an epoxy group, an amine group, a quinone imine group, or a [mouth + hydrazino] oxazoline group.

In the case where the resin films are laminated to each other, the laminate in which the printing layer is located between the resin films can be laminated by using a solvent or the like which has an adhesive property to the printing ink, even if the adhesive layer is not particularly provided. .

<Lubricant>

As the lubricant, an aliphatic hydrocarbon system, a higher aliphatic alcohol, a fatty acid, a fatty acid metal salt, a fatty acid ester or a decylamine derivative, for example, decyl decylamine, oleic acid decylamine, erucic acid amide, mustard can be used. Organic lubricants such as decylamine, decanoate, and acenaphthylamine; or lanthanum, lanthanum citrate, magnesium citrate, etc., zeolite, calcium carbonate, cerium oxide, aluminum oxide, sulfuric acid A commercially available lubricant such as an inorganic lubricant such as hydrazine.

In addition, when the lubricant is kneaded in the resin by the extruder, the lubricant is superior to the amorphous lubricant from the viewpoint of preventing the clogging of the filter in the extruder, but the amorphous lubricant can be remarkably Shows the effect of using a lubricant.

As the lubricant, a fine powder having an average particle diameter of 0.5 to 10 μm, preferably 1 to 5 μm is used. The fine powder is contained in the resin layer of the decorative film in an amount of 0.05 to 3% by mass, preferably 0.1 to 0.3% by mass. By containing a fine powder having a particle diameter of the above-described appropriate range in a suitable range of the resin, the wound shape of the film can be improved and the effect of preventing wrinkles can be obtained without impairing the excellent design properties.

However, it is not limited to those described above.

Further, in addition to the lubricant as described above, a light stabilizer, a radical scavenger, an antioxidant, a process stabilizer, a metal inerting agent, or the like may be added in order to improve the heat resistance and weather resistance of the resin. Or processing additives, and other additives that are usually added to improve the processability of the resin.

<antistatic agent>

As the antistatic agent, a nonionic antistatic agent, a cationic antistatic agent, an amphoteric antistatic agent, or the like can be used, and in particular, a cationic one can be preferably used. In the case of a cationic system, in particular, the antistatic effect of the coating layer provided on the surface of the film can be exerted until the decorative sheet is formed. In terms of the surface, it is excellent, and this effect can be achieved highly. Among the cationic antistatic agents, a polymer having a pyridine ring in the main chain is preferably used, and specific examples thereof include polydiallyldimethylammonium chloride and poly(diallyldimethyl). Ammonium chloride / dimethyl ammonium chloride / N-methylol acrylamide).

However, it is not limited to those described above.

<UV absorber>

As the ultraviolet absorber, a triazine type, a benzophenone type, a benzotriazole type, a benzoate type, a cyanoacrylate type, a salicylate type, or the like can be preferably used.

Further, by containing a hindered amine light stabilizer, a heat stabilizer, and an antioxidant, the ultraviolet deterioration preventing effect can be further enhanced.

However, it is not limited to those described above.

In the manufacture of the resin film, the resin composition constituting each resin film can be mixed. It is used by melt kneading. mixing. As the kneading machine, a melt kneader which is usually used can be used, and since a resin film can be formed while kneading, it is preferable to use a biaxial extruder. Alternatively, a twin-screw extruder can be used for mixing. It is extruded into a rope shape and used for granulation. The obtained resin film can be made thinner and higher in strength by extending in the uniaxial direction or the biaxial direction.

In addition, the shrinkage rate can also be adjusted by adjusting the heat setting temperature after the extension. The extension can be carried out by a usual method such as stretching between rolls, tenter stretching, tube stretching, tenter stretching, and simultaneous biaxial stretching.

These laminated films can be produced by a generally known method. For example, the first layer and the second layer may be dry laminated by an adhesive to laminate.

Further, a lamination method in which a layered resin film is formed by pressing the second layer on the resin film of the first layer may be employed.

Alternatively, it can be produced by a co-extrusion method in which three or more extruders are simultaneously extruded and laminated in a feed module or a nozzle.

Among them, the co-extrusion method is best because it can be produced by one extrusion and the efficiency is also high. The co-extrusion method can use a T-die method or a circular head method.

Further, the obtained film can also have tensile strength and impact strength by performing uniaxial stretching and biaxial stretching.

In addition, as a film forming method in which a resin film is laminated to a stratified layer, a commercially available film may be used and laminated by a pressure roller or the like, and the Japanese Patent Laid-Open No. Hei 11-42744, Japanese Patent Laid-Open No. Hei-2006- A film forming method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei.

(PPT resin blending effect)

Fig. 6 is a graph showing changes in the modulus of elasticity when PTT resin is blended in a PBT resin. It is understood that in any case of a monomer, the higher the temperature, the smaller the elastic modulus of the PBT resin and the PTT resin.

However, the Tg (glass transition temperature) of the PBT resin and the PTT resin was about 45 ° C. From Fig. 6, it was found that the elastic modulus of the PBT/PTT blended resin in the temperature region showed particularly excellent values.

That is, when the content of the PTT resin is 20 to 80%, the modulus at 45 ° C shows an extremely small value.

Therefore, it is understood that the workability in the vicinity of Tg is good when the PTT resin content is 20 to 80%, preferably 30 to 70%, more preferably 40 to 60%, as a result of the results shown in FIG. .

Usually, when forming in a temperature range higher than Tg, it is easy to cause work. In order to ensure the workability, it is necessary to increase the processing temperature and lower the modulus of elasticity. Therefore, it is necessary to set the temperature so as to achieve the balance.

However, as described above, in the PBT/PTT blended resin, the PTT content is optimized, whereby the modulus of elasticity can be lowered even in the temperature region near the Tg, and as a result, a resin having good processability can be obtained. Floor.

Further, it is known that the effect of improving the workability by using such a PBT/PTT blended resin is not only the film of the single layer of the resin but also at least one of the layers of the resin film formed of the multilayer layer. Obtained. Although the details of the mechanism are not clear, it is presumed that the reason is that the stress dispersion effect at the time of processing is obtained by providing a layer having a low modulus of elasticity, so that the workability of the entire film is improved.

Further, the modulus of elasticity is determined in the following manner based on JIS K 7161 (test method for plastic-tensile properties).

First, the polyester resin film was cut into a tensile test piece having a width of 5 mm and a length of 50 to 60 mm.

Using a tensile tester (Tensilon) that maintains the measurement environment at a specific set temperature, the nominal stress-elongation curve is measured on the tensile test piece under the conditions of a stroke of 20 mm and a tensile speed of 200 mm/min. Find the nominal stress σ 0 and the elongation El.

The elongation El can be obtained by the following formula.

El=100×(L-L0)/L0

Here, L0 is the length of the sample before stretching, and L is the length of the sample after stretching.

On the obtained nominal stress-elongation curve, the elastic modulus E was obtained from the slope of the range of the linearity in the vicinity of the elongation of 2 to 4% by the least square method.

E=△σ 0/△El×100

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples.

<Example 1>

The layer structure of the resin film is a two-layer structure of D layer (PBT resin) / A layer (PTT from plant) from top to bottom as shown in Fig. 2 (a), and is set to D layer thickness: 50 μm. Thickness of /A layer: 150 μm.

Next, the two-layer resin film is laminated via an adhesive in the form of an A-layer contact substrate (galvanized steel sheet).

Then, the bending process was performed at a processing temperature of 45 ° C using a plate bending machine, and as a result, a good molded article free from peeling of the resin film was obtained, and the possibility of being used as a decorative sheet was confirmed.

<Example 2>

The layer structure of the resin film is set to be E layer (copolymerized PET resin) / B layer (PC from plant) / D layer (blend of PBT and PET) from top to bottom as shown in Fig. 3 (a) The three-layer structure was manufactured to have a thickness of E layer: 50 μm/B layer thickness: 150 μm/D layer thickness: 50 μm. Then, the bending process was performed at a processing temperature of 45 ° C using a plate bending machine, and as a result, a good molded article free from peeling of the resin film was obtained, and the possibility of being used as a decorative sheet was confirmed.

<Example 3>

The resin film of Example 3 is a single layer film formed to contain a blend of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, and a coloring agent derived from plants. A resin film of the composition.

Examples of the plant-derived polytrimethylene terephthalate resin (PTT) include those produced from terephthalic acid and 1,3 propanediol derived from plants.

As the polybutylene terephthalate (PBT) resin, the prior resin can be used to the extent that the content of the raw material derived from the plant is not lowered.

Thereby, the adhesion can be improved. It can be made into a resin film that improves adhesion.

Further, examples of the colorant include film coloring materials such as coloring pigments and coloring dyes.

The resin film of Example 3 is a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a colorant (pigment 15 mass) which is heated and melted by an extruder. The blended composition of %) and lubricant (0.15 mass%) was extruded from a T-die onto a casting roll to form a monolayer film having a thickness of 100 μm.

As a lubricant, 3% by mass of a masterbatch (including 5 mass% of an amorphous lubricant having an average particle diameter of 5 μm) manufactured by DIC Co., Ltd. was kneaded, and the resin was adjusted so as to contain 0.15 mass% of the lubricant.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 51% by mass).

<Example 4>

The resin film of Example 4 was set as a single layer film to prepare a polybutylene terephthalate (PBT) resin, a plant-derived polytrimethylene terephthalate (PTT) resin, and a copolymerized polyparaphenylene. A resin film of a blend composition of a diethylene glycol diester (PET) resin and a color former.

Alternatively, a resin film comprising a blended composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a copolymerized polyethylene terephthalate (PET) resin, and a color former is prepared.

The resin film of Example 4 is a plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, which is heated and melted by an extruder, and is used as an acid component between benzene. A blending composition of 15 mol% of a copolymerized polyethylene terephthalate (PET) resin and a coloring agent (pig 4% by mass) of a dicarboxylic acid was extruded from a T-die onto a casting roll to have a thickness of 90 μm. Single Layer film.

Further, the blending mass ratio of PTT, PBT and PET was set to 3:1:1 (PTT content = 57.6 mass%).

<Example 5>

The resin film of Example 5 is a two-layer film formed of a resin film containing plant-derived polytrimethylene terephthalate (PTT) resin or polybutylene terephthalate (PBT) resin. A layer of a blending composition of a coloring agent or a blending composition of a polybutylene terephthalate (PBT) resin and a coloring agent is used as the first layer, and the layer is laminated as a second layer. a plant polybutylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin and a coloring agent blending composition, or a polybutylene terephthalate (PBT) resin and A layer of a blend composition of colorants.

Further, a layer of polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin derived from plants is contained in at least one layer of the first or second resin film. Resin.

The resin film of Example 5 is a plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and a color former which are heated and melted by an extruder by co-extrusion. a blend composition of (pigment 15% by mass), a blend composition with a polybutylene terephthalate (PBT) resin, a colorant (pigment 15% by mass), and a lubricant (0.15 mass%) in a thickness ratio 4:1 was extruded from a T-die onto a casting roll to form a 2-layer film having a thickness of 100 μm.

The lubricant was the same as in Example 3.

Further, the blending ratio of PTT to PBT was 2: 2 (PTT content = 51% by mass) and 9: 1 (PTT content = 765 % by mass).

<Example 6>

The resin film of Example 6 was set as a two-layer film, and was formed into a resin film which would contain a plant-derived polytrimethylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin. And a blending composition layer of a coloring agent as a first layer, on which a polybutylene terephthalate (PBT) resin and a copolymerized polyethylene terephthalate are laminated as a second layer ( PET) blending composition of resin and color former, or polybutylene terephthalate (PBT) resin, plant-derived polytrimethylene terephthalate (PTT) resin, copolymerized polyethylene terephthalate A layer of a blend composition of a diester (PET) resin and a color former.

Further, at least one layer of the first layer or the second layer of the resin film contains a blend of a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin. Resin.

The resin film of Example 6 is a plant-derived polytrimethylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin which is heated and melted by an extruder by co-extrusion. a blending composition of a polyethylene terephthalate (PET) resin copolymerized with 15 mol% of phthalic acid and a coloring agent (40% by mass of pigment), and a polyethylene terephthalate derived from plants a blend composition of an ester (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment 40% by mass), and a lubricant (0.15 mass%) in a thickness ratio of 1:2 from a T-die The head was extruded on a casting roll to form a two-layer film having a thickness of 90 μm.

The lubricant was the same as in Example 3.

Furthermore, the blending mass ratio of PTT, PBT and PET is set to 2:1:2 (PTT content = 24% by mass), and the blending mass ratio of PTT to PBT is set to 1:1 (PTT content = 30% by mass).

<Example 7>

The resin film of Example 7 is a two-layer film, and is formed as a resin film which has a layer containing a copolymerized polyethylene terephthalate (PET) resin as a first layer, and as a second layer thereon Layered and laminated with a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin and a coloring agent, or a polytrimethylene terephthalate (PTT) resin derived from plants, polyparaphenylene The blended composition of the butylene dicarboxylate (PBT) resin and the coloring agent is further blended with a layer of the resin composition of the antistatic agent.

As an antistatic agent, 10% by mass of Pelestat NC6321 manufactured by Sanyo Chemical Industry Co., Ltd. was used.

The resin film of Example 7 is a plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, and antistatic, which are heated and melted by an extruder by co-extrusion. a blending composition of an electric agent (10% by mass), a coloring agent (pigment: 30% by mass), and a polyethylene terephthalate (PET) resin copolymerizing 15 mol% of phthalic acid as an acid component A blending composition of a lubricant (0.15 mass%) was extruded from a T-die at a thickness ratio of 4:1 onto a casting roll to prepare a two-layer film having a thickness of 40 μm.

The lubricant was the same as in Example 3.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 36% by mass).

<Example 8>

The resin film of Example 8 was a two-layer film, and a layer containing a copolymerized polyethylene terephthalate (PET) resin was used as the first layer, and a layer containing the plant was contained as a second layer. A layer of a blend composition of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, and color former.

The resin film of Example 8 is a plant-derived polymer which is heated and melted by an extruder by co-extrusion. a blend composition of a propylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a color former (pigment 20% by mass), and 15 mol of phthalic acid as an acid component The % copolymerized polyethylene terephthalate (PET) resin was extruded from a T-die onto a casting roll at a thickness ratio of 4:1 to form a two-layer film having a thickness of 70 μm.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 48% by mass).

<Example 9>

The resin film of the ninth embodiment is a three-layer film, and is formed into a resin film in which the two-layer resin film described in Example 10 is used as the first layer and the second layer, and the second layer is used as the first layer. a three-layer laminated product comprising a polybutylene terephthalate (PBT) resin, a copolymerized polyethylene terephthalate (PET) resin, and a coloring agent, or a polybutylene terephthalate A layer of an ester (PBT) resin, a plant-derived polytrimethylene terephthalate (PTT) resin, a copolymerized polyethylene terephthalate (PET) resin, and a blending composition of a color former.

Further, at least one layer of the first to third resin films contains a blend of poly(trimethylene terephthalate) (PTT) resin and polybutylene terephthalate (PBT) resin derived from plants. Resin.

The resin film of Example 9 is a polybutylene terephthalate (PBT) resin which is heated and melted by an extruder by co-extrusion, and a polyparaphenylene copolymer which is 15 mol% of phthalic acid as an acid component. Blended composition of ethylene formate (PET) resin and color former (pig 4% by mass), plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) Blending combination of resin and coloring agent (pig 4% by mass), blending with polybutylene terephthalate (PBT) resin, colorant (pig 4% by mass), and lubricant (0.15 mass%) The material was extruded from a T-die onto a casting roll at a thickness ratio of 2:3:1 to form a three-layer film having a thickness of 90 μm.

The lubricant was the same as in Example 3.

Furthermore, the blending ratio of PBT to PET is set to 1:1, and the blending ratio of PTT to PBT is set to 3:2 (PTT content = 57.6 mass%), and 4:1 (PTT content rate). 2 types of = 76.8 mass%).

<Example 10>

The resin film of Example 10 is a three-layer film, and is formed into a resin film which is a layer containing a copolymerized polyethylene terephthalate (PET) resin as a first layer, and as a second layer thereon Layered and laminated with a blending composition comprising plant polybutylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and color former, or polybutylene terephthalate a layer of a blending composition of an ester (PBT) resin and a coloring agent, on which a polytrimethylene terephthalate (PTT) resin or polybutylene terephthalate containing a plant is laminated as a third layer A blend of a diester (PBT) resin, a colorant and an antistatic agent, or a blend of a polybutylene terephthalate (PBT) resin, a colorant, and an antistatic agent.

Further, at least one layer of the first to third resin films contains a blend of plant-derived polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin. Resin.

The resin film of Example 10 was produced in the following manner.

a blending composition of a polybutylene terephthalate (PBT) resin, an antistatic agent (10% by mass), and a coloring agent (pigment of 30% by mass) which are heated and melted by an extruder by co-extrusion, a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a color former (pigment of 30% by mass), and an acid component 15 mol% copolymerized polyethylene terephthalate (PET) resin and lubricant (0.15 mass%) The blended composition was extruded from a T-die onto a casting roll at a thickness ratio of 1:2:1 to form a three-layer film having a thickness of 40 μm.

The lubricant was the same as in Example 3. The same antistatic agent was used as in Example 7.

Further, the blending mass ratio of PTT to PBT was set to 1:1 (PTT content = 35 mass%).

<Example 11>

The resin film of Example 11 is a three-layer film, and is formed into a resin film which is a layer containing a copolymerized polyethylene terephthalate (PET) resin as a first layer, and as a second layer thereon Layered and laminated with a blend of resin derived from plant polybutylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin, or polybutylene terephthalate (PBT) A layer of a blending composition of a resin and a coloring agent, on which a layer comprising a blending composition of a polybutylene terephthalate (PBT) resin and a coloring agent is laminated as a third layer.

The resin film of Example 11 is a blended composition of a polybutylene terephthalate (PBT) resin heated by an extruder and a coloring agent (pigment 20% by mass) by co-extrusion, and a plant-derived composition. a blending composition of a polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent (pigment 20% by mass), and a phthalic acid as an acid component 15 mol% of a copolymerized polyethylene terephthalate (PET) resin was extruded from a T-die at a thickness ratio of 2:2:1 onto a casting roll to form a 3-layer film having a thickness of 70 μm.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 48% by mass).

<Example 12>

The resin film of Example 12 was set as a 3-layer film, and was formed into a resin film which would contain a plant-derived polytrimethylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin. And a blending composition layer of a coloring agent as a first layer, on which a printed layer is formed as a second layer A brush layer on which a layer containing biaxially-oriented polyethylene terephthalate (BO-PET) resin is laminated as a third layer.

The resin film of Example 12 is a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a colorant (pigment 15 mass) which is heated and melted by an extruder. The blended composition of %) and lubricant (0.15 mass%) was extruded from a T-die onto a casting roll to form a film having a thickness of 50 μm. Printing a solid printed layer and a pattern printed layer on a lower surface of a commercially available biaxially stretched polyethylene terephthalate (BO-PET) film having a thickness of 25 μm so that the printed layer overlaps with the colored resin layer The two films are heated and pressure-bonded and laminated to form a laminated resin film under the conditions of a heating temperature of 120 ° C for the pressure-bonding roller, a feed rate of the resin film of 20 m/min, and a pressing pressure of 2.45 MPa. .

The lubricant was the same as in Example 3.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 51% by mass).

<Example 13>

The resin film of the embodiment 13 is a four-layer film, and is formed into a resin film in which the two layers of the resin film described in the tenth embodiment are the first layer and the second layer, and the second layer is used as the first layer. A printed layer was formed in three layers, and a biaxially stretched polyethylene terephthalate (BO-PET) resin was laminated as a fourth layer thereon.

The resin film of Example 13 is a plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and a color former which are heated and melted by an extruder by co-extrusion. a blending composition of (pigment 15% by mass), a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a colorant (pigment 15% by mass) And a blending composition of a lubricant (0.15 mass%), extruded at a thickness ratio of 4:1 from a T-die to the casting A two-layer film having a thickness of 60 μm was formed on the roll.

Thereafter, the solid printed layer and the pattern printed layer were printed on the lower surface of a commercially available biaxially stretched polyethylene terephthalate (BO-PET) film having a thickness of 25 μm to make the printed layer and the above-mentioned lubricating layer The side of the colored resin layer which does not enter the agent overlaps, and the two films are heated under the conditions of a heating temperature of the pressure roller 120 ° C, a feed rate of the resin film: 20 m/min, and a pressure for press bonding: 2.45 MPa. A laminated resin film is formed by laminating.

The lubricant was the same as in Example 3.

In addition, the blending ratio of PTT and PBT was 2:2 (PTT content = 51% by mass) and 1:3 (PTT content = 21.3% by mass).

<Example 14>

The resin film of Example 14 was set as a 4-layer film, and was formed into a resin film which would contain a plant-derived polytrimethylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin. A layer of a blending composition of a coloring agent is used as a first layer, and a printed layer is formed as a second layer thereon, and a polyethylene terephthalate containing plant-derived material is laminated as a third layer thereon. a layer of an ester (PTT) resin, a blend of polybutylene terephthalate (PBT) resin, or a layer of polybutylene terephthalate (PBT) resin, and further thereon, as a fourth layer a laminate comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a UV absorber, or polybutylene terephthalate A layer of a blend composition of a (PBT) resin and a UV absorber.

Further, a layer of a polybutylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin derived from a plant is contained in at least one layer of the resin film other than the printed layer.

Here, as a UV absorber, 10% by mass of a benzotriazole-based ultraviolet absorber masterbatch (including 20% by mass of Adekastab LA-31 manufactured by ADEKA Co., Ltd.) manufactured by DIC Co., Ltd. is kneaded. The resin was adjusted so as to contain 2.0% by mass of the ultraviolet absorber.

The resin film of Example 14 was a mixture of a polybutylene terephthalate (PBT) resin heated by an extruder and a UV absorber (5 mass%) and a lubricant (0.15 mass%) by co-extrusion. Composition, blended composition with plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, and lubricant (0.15 mass%) in thickness ratio 1:8 was extruded from a T-die onto a casting roll to form a two-layer film having a thickness of 45 μm. The solid printed layer and the pattern printed layer were printed by a gravure rim machine on the surface of the layer of the two-layer film which did not contain the ultraviolet absorber.

Thereafter, a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment 15% by mass), and a lubricant (0.15 mass%) were additionally used. The film formed by extrusion of the blended composition is superposed on the printed layer side of the printed film, and the heating temperature of the pressure-bonding roll is 120 ° C, the feed rate of the resin film is 20 m/min, and the pressure-bonding is rolled. Under pressure: 2.45 MPa, the two films were heat-compressed and laminated to form a laminated resin film.

The lubricant was the same as in Example 3.

Further, the blending mass ratio of PTT and PBT was set to 3:2 (PTT content = 60% by mass and 51% by mass), and both were set to 4:1 (PTT content = 80% by mass and 68 mass) 4 kinds of %).

<Example 15>

The resin film of Example 15 was set as a 4-layer film, and was formed as a resin film which would contain from Plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and coloring agent blending composition, or polybutylene terephthalate (PBT) resin A layer of a blending composition of a coloring agent is used as a first layer, and a printing layer is formed as a second layer thereon, and a copolymerized polyethylene terephthalate is laminated as a third layer thereon. a (PET) resin layer, and further, as a fourth layer, a polyphenylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and an ultraviolet absorbing material containing a plant are laminated. A blending composition of the agent, or a layer of a blend composition of a polybutylene terephthalate (PBT) resin and a UV absorber.

Further, at least one or more layers of the resin film other than the printed layer include a blended resin of a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from a plant.

The resin film of Example 15 was a polybutylene terephthalate (PBT) resin and a UV absorber (5 mass%) and a lubricant (0.15 wt%) which were heated and melted by an extruder by co-extrusion. The composition is blended with a polyethylene terephthalate (PET) resin copolymerized with 15 mol% of phthalic acid as an acid component, and extruded from a T-die at a thickness ratio of 1:3 to a casting roll. A two-layer film having a thickness of 40 μm was formed. The solid printed layer and the patterned printed layer were printed on the surface of the copolymerized PET layer of the two-layer film by a gravure rim machine.

Thereafter, a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment 15% by mass), and a lubricant (0.15 mass%) were additionally used. The film formed by extrusion of the blended composition is superposed on the printed layer side of the printed film, and the heating temperature of the pressure-bonding roll is 120 ° C, the feed rate of the resin film is 20 m/min, and the pressure-bonding is rolled. Under pressure: 2.45 MPa, the two films were heat-compressed and laminated to form a laminated resin film.

The lubricant was the same as in Example 3. The same procedure as in Example 14 was used for the ultraviolet absorber.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 51% by mass).

<Example 16>

The resin film of Example 16 was set as a 5-layer film, and was formed into a resin film which would contain a plant-derived polytrimethylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin. A layer of a blending composition of a coloring agent is used as a first layer, and a printed layer is formed as a second layer thereon, and a polyethylene terephthalate containing plant-derived material is laminated as a third layer thereon. a layer of an ester (PTT) resin, a blend of polybutylene terephthalate (PBT) resin, or a layer of polybutylene terephthalate (PBT) resin, on which a layer is laminated as a fourth layer There are blending compositions comprising plant polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, or polybutylene terephthalate (PBT) resin. a layer, and further, as a fifth layer, a laminate comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a UV absorber A layer of a composition, or a blend composition of a polybutylene terephthalate (PBT) resin and a UV absorber.

Further, a layer of a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from a plant is contained in at least one layer of the resin film other than the printed layer.

The resin film of Example 16 was a mixture of a polybutylene terephthalate (PBT) resin heated by an extruder and a UV absorber (5 mass%) and a lubricant (0.15 mass%) by co-extrusion. Composition, plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blend composition, and plant-derived polytrimethylene terephthalate (PTT) A blended composition of a resin, a polybutylene terephthalate (PBT) resin, and a lubricant (0.15 mass%) is extruded from a T-die onto a casting roll at a thickness ratio of 1:6:2. A three-layer film having a thickness of 45 μm. The solid printed layer and the pattern printed layer were printed by a gravure rim machine on the surface of the layer of the three-layer film which did not contain the ultraviolet absorber.

Thereafter, a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment 15% by mass), and a lubricant (0.15 mass%) were additionally used. The film formed by extrusion of the blended composition is superposed on the printed layer side of the printed film, and the heating temperature of the pressure-bonding roll is 120 ° C, the feed rate of the resin film is 20 m/min, and the pressure-bonding is rolled. Under pressure: 2.45 MPa, the two films were heat-compressed and laminated to form a laminated resin film.

The lubricant was the same as in Example 3. The same procedure as in Example 14 was used for the ultraviolet absorber.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 60% by mass and 51% by mass).

<Example 17>

The resin film of the embodiment 17 is a five-layer film, and is formed into a resin film in which the two-layer resin film described in the tenth embodiment is used as the first layer and the second layer, and the second layer is used as the first layer. 3 layers are formed with a printed layer on which a layer of polybutylene terephthalate (PTT) resin or polybutylene terephthalate (PBT) resin containing plants is laminated as a fourth layer. a composition, or a layer of polybutylene terephthalate (PBT) resin, and further thereon, as a fifth layer, a polytrimethylene terephthalate (PTT) resin containing a plant, and a poly layer A blend of a butylene terephthalate (PBT) resin and a UV absorber, or a blend of a polybutylene terephthalate (PBT) resin and a UV absorber.

Further, at least one or more layers of the resin film other than the printed layer include a blended resin of a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from a plant.

The resin film of Example 17 was a mixture of a polybutylene terephthalate (PBT) resin heated by an extruder and a UV absorber (5 mass%) and a lubricant (0.15 mass%) by co-extrusion. Composition, blended composition with plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, and lubricant (0.15 mass%) in thickness ratio 1:8 was extruded from a T-die onto a casting roll to form a two-layer film having a thickness of 45 μm. The solid printed layer and the pattern printed layer were printed by a gravure rim machine on the surface of the layer of the two-layer film which did not contain the ultraviolet absorber.

Thereafter, in addition, a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment) which is heated and melted by an extruder by co-extrusion 15% by mass of the blended composition, blended composition with polybutylene terephthalate (PBT) resin, colorant (pigment 15% by mass), and lubricant (0.15 wt%) in thickness ratio 4:1 was extruded from a T-die onto a casting roll to form a two-layer film having a thickness of 80 μm, so that the lubricant-free layer of the two films coincided with the printed layer side of the printed film, and was crimped. The film was heated and pressure-bonded under the conditions of a heating temperature of the roll of 120 ° C, a feed rate of the resin film: 20 m/min, and a press pressure for press bonding: 2.45 MPa, and laminated to form a laminated resin film.

The lubricant was the same as in Example 3. The same procedure as in Example 14 was used for the ultraviolet absorber.

Further, the blending mass ratio of PTT to PBT is set to be 3:2 (PTT content = 60% by mass and 51% by mass), and both are 4:1 (PTT content = 80 mass) % And 4 kinds of 68% by mass).

<Example 18>

The resin film of the embodiment 18 is a five-layer film, and is formed into a resin film in which the two layers of the resin film described in the tenth embodiment are the first layer and the second layer, and the second layer is used as the first layer. A printed layer is formed on three layers, and a copolymerized polyethylene terephthalate (PET) resin layer is laminated as a fourth layer thereon, and a layer is included as a fifth layer. a blend of polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and ultraviolet absorber, or polybutylene terephthalate (PBT) resin and A layer of a blend composition of UV absorbers.

Further, at least one or more layers of the resin film other than the printed layer include a blended resin of a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from a plant.

The resin film of Example 18 was a mixture of a polybutylene terephthalate (PBT) resin heated by an extruder and a UV absorber (5 mass%) and a lubricant (0.15 mass%) by co-extrusion. The composition and the polyethylene terephthalate (PET) resin copolymerized with 15 mol% of phthalic acid as an acid component are extruded from a T-die onto a casting roll at a thickness ratio of 1:3. A two-layer film having a thickness of 40 μm was formed. The solid printed layer and the patterned printed layer were printed on the surface of the copolymerized PET layer of the two-layer film by a gravure rim machine.

Thereafter, in addition, a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment) which is heated and melted by an extruder by co-extrusion 15% by mass of the blended composition, blended composition with polybutylene terephthalate (PBT) resin, colorant (pigment 15% by mass), and lubricant (0.15 mass%) to a thickness ratio of 4 : 1 is extruded from a T-die onto a casting roll to form a two-layer film having a thickness of 100 μm, so that the lubricant-free layer of the two layers overlaps the printed layer side of the printed film, and the pressure-bonding roll is used. The film was heated and pressure-bonded at a heating temperature of 120 ° C, a resin film feed rate of 20 m/min, and a pressure for press-bonding: 2.45 MPa, and laminated to form a laminated resin film.

The lubricant was the same as in Example 3. The same procedure as in Example 14 was used for the ultraviolet absorber.

In addition, the blending ratio of PTT and PBT was 2:2 (PTT content = 51% by mass) and 1:2 (PTT content = 28.3% by mass).

<Example 19>

The resin film of the example 19 is a resin film which is formed into a resin film in which the two layers of the resin film described in the tenth embodiment are the first layer and the second layer, and the second layer is used as the second layer. A third layer is formed with a printed layer on which a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from plants is laminated as a fourth layer. a blending composition, or a layer containing a lubricant in a polybutylene terephthalate (PBT) resin, and further comprising, as a fifth layer, a polytrimethylene terephthalate comprising a plant ( a PTT) resin, a blend of polybutylene terephthalate (PBT) resin, or a layer of polybutylene terephthalate (PBT) resin, and further thereon, as a sixth layer a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a UV absorber, or polybutylene terephthalate (PBT) a layer of a blended composition of a resin and a UV absorber.

Further, at least one layer of the resin film other than the printed layer contains a blend of a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin. Resin.

The resin film of Example 19 was a mixture of a polybutylene terephthalate (PBT) resin heated by an extruder and a UV absorber (5 mass%) and a lubricant (0.15 mass%) by co-extrusion. Composition, plant-derived polytrimethylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin blend composition, and plant-derived polytrimethylene terephthalate a blending composition of (PTT) resin, polybutylene terephthalate (PBT) resin and lubricant (0.15 mass%), extruded from a T-die at a thickness ratio of 1:6:2 to a casting roll A three-layer film having a thickness of 45 μm was formed. The solid printed layer and the pattern printed layer were printed by a gravure rim machine on the surface of the layer of the three-layer film which did not contain the ultraviolet absorber.

Thereafter, in addition, a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant (pigment) which is heated and melted by an extruder by co-extrusion 15% by mass of the blended composition, blended composition with polybutylene terephthalate (PBT) resin, colorant (pigment 15% by mass), and lubricant (0.15 mass%) to a thickness ratio of 4 :1 is extruded from a T-die onto a casting roll to form a two-layer film having a thickness of 80 μm, so that the lubricant-free layer of the two layers overlaps the printed layer side of the printed film, and is used for crimping. The film was heated and pressure-bonded under the conditions of a heating temperature of 120 ° C of a roll, a feed rate of a resin film: 20 m/min, and a nip pressure of 2.45 MPa, and laminated to form a laminated resin film.

The same procedure as in Example 14 was used for the ultraviolet absorber.

Further, the blending mass ratio of PTT to PBT was set to 3:2 (PTT content = 60% by mass and 51% by mass).

<Example 20>

The resin film of Example 20 was formed as in any of the above Examples 4, 6 to 11, and 18. In the resin film, 2 to 15 mol% of terephthalic acid as an acid component of the copolymerized polyethylene terephthalate (PET) resin to be formed is substituted with isophthalic acid.

Here, the reason why it is 2 to 15 mol% is that the crystal or the melting point is lowered and the flexibility is increased by substituting terephthalic acid with isophthalic acid, and if it is less than 2%, the effect is weak. More than 15% by mole, the melting point is excessively lowered and excessively softened.

<Example 21>

The resin film of the embodiment 21 is formed in the resin film according to any one of the above embodiments 12 and 13, and is replaced by the biaxially-oriented polyethylene terephthalate (BO-PET) resin. A biaxially-stretched copolymerized polyethylene terephthalate resin obtained by substituting 2 to 15 mol% of terephthalic acid as an acid component of polyethylene terephthalate with isophthalic acid By.

Here, the reason for setting it as 2 to 15 mol% is the same as that in the case of the embodiment 20.

<Example 22>

In the resin film of any one of the above-mentioned Examples 1 to 21, the resin film of any one of the above-mentioned one or more layers is contained in the resin film.

The lubricant was the same as in Example 3.

<Example 23>

The resin film of the embodiment 23 is formed into a layer which is the outermost layer of the resin film as in any one of the embodiments 1 to 22 (the layer of the last layer), and the embossed uneven portion is formed by roll processing and given a solid High sense of design.

The resin film of Example 23 was formed by heating processing on the outermost surface of the resin film formed in advance at an embossing roll temperature of 120 ° C, a resin film feed rate of 20 m/min, and an embossing pressure of 2.45 MPa. Embossed bumps.

<Example 24>

The resin film of Example 24 was formed on the layer which is the outermost layer of the resin film of any one of Examples 1 to 22 (the layer of the last layer), and the mirror surface was formed by roll processing to give a mirror finish. Designer.

The resin film of Example 24 was subjected to a mirror surface processing on the outermost surface of the resin film formed in advance at a mirror roll temperature of 120 ° C, a resin film feed rate of 20 m/min, and a processing pressure of 1 MPa.

<Example 25>

In the resin film of any one of Examples 1 to 24, the PTT content of the resin in which PBT and PTT are blended is set to 20 to 80%.

Further, the PTT content is preferably set to 30 to 70%, and more preferably 40 to 60%.

That is, according to Fig. 6, when the content of the PTT resin is 20 to 80%, the modulus at 45 °C shows an extremely small value because the PTT resin content is 20 to 80%, preferably. When it is 30 to 70%, and more preferably 40 to 60%, the workability in the vicinity of Tg is good.

As a result, by optimizing the PTT content of the PBT/PTT blended resin, the modulus of elasticity can be lowered even in the temperature region near the Tg, and a resin layer having good workability can be obtained.

<Example 26>

The resin film of Example 26 was formed by laminating a resin film as in any one of Examples 1 to 25 on one surface of a substrate to form a decorative sheet in which a resin film was laminated.

Here, as the adhesive, a polyester urethane resin-based adhesive is used.

That is, at a heating temperature of 210 ° C, a pressure of 1.47 MPa, and a pressure bonding time of 5 seconds, the polyester urethane was coated on a zinc alloy plated steel plate having a thickness of 0.5 mm at a coating amount of 10 g/m ² . The base material of the ethyl ester resin-based adhesive was heat-compressed, and the resin films described in Examples 1 to 25 were laminated to prepare a test piece. The test piece was bent at a processing temperature of 45 ° C using a bending machine. As a result, a good molded article without peeling off the resin film was obtained, and the possibility of being used as a decorative sheet was confirmed.

[Industrial Availability]

The resin film of the present invention can be used as a resin film using a plant-derived raw material, which uses a plant-derived raw material to increase the biological ratio of the resin film in a manner to satisfy the conditions of the biomarker, and imparts a resin film using the petroleum-based plastic. The same level of performance.

Further, since the decorative sheet in which the resin film is laminated on the substrate is excellent in adhesion, workability, and durability, the industrial applicability is extremely high.

Claims (31)

A resin film comprising one or more layers of the following resin-derived resin layer (layer A, B or C): layer A: a polytrimethylene terephtalate (PTT) resin derived from a plant, Plant-derived polyethylene terephthalate (PET) resin, plant-derived olefin resin (polypropylene (PP), polyethylene (PE)), plant-derived polycarbonate ( Any of polycarbonate, PC) resins, or two or more blending compositions; layer B: polyphenyl terephthalate (PTT) resin from plants, polyterephthalic acid from plants Ethylene glycol (PET) resin, plant-derived olefin resin (polypropylene (PP), polyethylene (PE)), plant-derived polycarbonate (PC) resin, or two or more of these Adding plant-derived compatibilizer and/or plant-derived elastomer to the blending composition; layer C: from plant polybutylene terephthalate (PTT) resin, plant-derived polyterephthalic acid Ethylene glycol (PET) resin, plant-derived olefin resin (polypropylene (PP), polyethylene (PE)) Any one of plant-derived polycarbonate (PC) resins or a plant-derived ionic polymer added to the two or more blend compositions. A resin film characterized in that one or more layers of the resin-derived resin layer (layer A, B or C) described in claim 1 and the following layer D or layer E as a surface layer are laminated: D layer : Polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene terephthalate (PET) resin, copolymerized poly(p-phenylene terephthalate) Ethylene formate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, or crystal of the two or more blending compositions Polyester resin; E layer: comprising copolymerized polyethylene terephthalate resin, copolymerized polybutylene terephthalate resin, copolymerized polytrimethylene terephthalate resin, polycarbonate (PC) A substantially amorphous polyester of either of the resins or the two or more of the blended compositions. A resin film characterized by laminating a resin-derived resin layer (layer A, B or C) according to item 1 of the above-mentioned application of the intermediate layer as an intermediate layer; and as the outermost layer and the lowermost layer as requested Item 2, layer D or layer E. A resin film characterized by alternately laminating a resin-derived resin layer (layer A, B or C) according to claim 1 and a layer D or layer E of claim 2, and The above D layer or E layer is the outermost layer and the lowermost layer. A resin film characterized by laminating two or more layers of the resin film according to any one of claims 1 to 4, with or without an adhesive. The resin film according to any one of claims 1 to 5, wherein a component constituting the D layer (including polyterephthalic acid) is blended in the above-mentioned resin-derived resin layer (layer A, B or C) Butadiene ester (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene terephthalate (PET) resin, copolymerized polyethylene terephthalate resin, copolymerized polypair Any one of a butyl phthalate resin, a copolymerized poly(trimethylene terephthalate resin), or a crystalline polyester of the two or more types of blended compositions, or a component constituting the E layer (including Any one of a copolymerized polyethylene terephthalate resin, a copolymerized polybutylene terephthalate resin, a copolymerized polytrimethylene terephthalate resin, or a polycarbonate (PC) resin, or A substantially amorphous polyester of two or more blending compositions. A resin film characterized by any one of claims 1 to 6 A printed layer is provided between any of the layers of the resin film. A single-layer resin film characterized by comprising a blend composition of a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a color former. A single-layer resin film comprising: polybutylene terephthalate (PBT) resin, plant-derived polytrimethylene terephthalate (PTT) resin, copolymerized polyethylene terephthalate a blending composition of (PET) resin and coloring agent; or a blend of poly(trimethylene terephthalate) (PTT) resin, copolymerized polyethylene terephthalate (PET) resin and coloring agent from plants combination. A two-layer resin film comprising a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, or A layer of a blend composition of polybutylene terephthalate (PBT) resin and a coloring agent is used as the first layer; and as a second layer, a polytrimethylene terephthalate containing a plant is laminated a layer of a (PTT) resin, a blend of a polybutylene terephthalate (PBT) resin and a color former, or a blend of a polybutylene terephthalate (PBT) resin and a coloring agent; A plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin are blended in at least one layer of the first layer or the second layer of the resin film. A two-layer resin film comprising a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, or A layer of a blend composition of a polybutylene terephthalate (PBT) resin and a coloring agent is used as the first layer; and as a second layer, a polybutylene terephthalate (PBT) is laminated as a second layer. Resin, copolymerization a blending composition of a polyethylene terephthalate (PET) resin and a coloring agent, or a polybutylene terephthalate (PBT) resin, a plant-derived polytrimethylene terephthalate (PTT) a layer of a resin, a copolymerized composition of a polyethylene terephthalate (PET) resin and a coloring agent; and a layer derived from at least one layer of the first layer or the second layer of the resin film Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin. A two-layer resin film comprising a layer comprising a copolymerized polyethylene terephthalate (PET) resin as a first layer; and a layer comprising a plant-containing layer as a second layer a blending composition of a propylene terephthalate (PTT) resin and a coloring agent, or a polybutylene terephthalate (PTT) resin derived from plants, a polybutylene terephthalate (PBT) resin, and The blending composition of the colorant is further a layer of a resin composition in which an antistatic agent is blended. A two-layer resin film comprising a layer comprising a copolymerized polyethylene terephthalate (PET) resin as a first layer; and a layer comprising a plant-containing layer as a second layer A layer of a blend composition of propylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin, and color former. A three-layer resin film comprising, as a first layer and a second layer, a structure of a two-layer resin film according to claim 10; and a layer of the second layer as a third layer a polybutylene terephthalate (PBT) resin, a blended composition of a copolymerized polyethylene terephthalate (PET) resin and a coloring agent, or a polybutylene terephthalate (PBT) resin, a layer of a blending composition of a plant polybutylene terephthalate (PTT) resin, a copolymerized polyethylene terephthalate (PET) resin, and a coloring agent; in the above first layer to the third layer At least one layer of the resin film is blended with a plant-derived polymer Propylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin. A three-layer resin film comprising a layer comprising a copolymerized polyethylene terephthalate (PET) resin as a first layer; and a layer comprising a plant-containing layer as a second layer Blending composition of propylene terephthalate (PTT) resin, polybutylene terephthalate (PBT) resin and color former, or polybutylene terephthalate (PBT) resin and coloring agent a layer of a composition; as a third layer, a laminate comprising a polybutylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, a colorant, and a blending composition of an antistatic agent, or a layer of a blending composition of a polybutylene terephthalate (PBT) resin, a colorant, and an antistatic agent; in the above first to third resin film At least one or more layers are blended with a plant-derived polytrimethylene terephthalate (PTT) resin and a polybutylene terephthalate (PBT) resin. A three-layer resin film comprising a layer comprising a copolymerized polyethylene terephthalate (PET) resin as a first layer; and a layer comprising a plant-containing layer as a second layer a layer of a blend composition of a propylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent; thereon, as a third layer, a layer comprising a polyparaphenylene A layer of a blend composition of a butylene formate (PBT) resin and a color former. A three-layer resin film characterized in that a blend composition layer comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent is used as a first layer; on the second layer, a printed layer is formed; On top of this, as the third layer, a layer containing a biaxial orientation-polyethylene terephthalate resin is laminated. A four-layer resin film comprising, as a first layer and a second layer, a composition of a two-layer resin film according to claim 10; and printing on the second layer as a third layer A layer on which a biaxially-oriented polyethylene terephthalate (BO-PET) resin is laminated as a fourth layer. A four-layer resin film comprising a blend composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a color former, or A layer of a blend composition of a polybutylene terephthalate (PBT) resin and a coloring agent is used as a first layer; a printed layer is formed as a second layer thereon; and as a third layer a laminate comprising a polybutylene terephthalate (PTT) resin derived from a plant, a polybutylene terephthalate (PBT) resin, or a polybutylene terephthalate (PBT) resin a layer of a polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a UV absorber incorporated from a plant as a fourth layer. a composition, or a layer of a blending composition of a polybutylene terephthalate (PBT) resin and an ultraviolet absorber; and a layer derived from at least one layer of the resin film other than the printed layer Polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin. A 4-layer resin film characterized in that it comprises a plant-derived polytrimethylene terephthalate a layer of a (PTT) resin, a blend of a polybutylene terephthalate (PBT) resin and a color former, or a blend of a polybutylene terephthalate (PBT) resin and a coloring agent as a layer a first layer; a printed layer is formed as the second layer; and a polyethylene terephthalate (PET) resin layer is laminated as a third layer; and further thereon As a fourth layer, a laminate comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a UV absorber, or polyparaphenylene is laminated. a layer of a blend composition of a butylene dicarboxylate (PBT) resin and a UV absorber; a polytrimethylene terephthalate derived from a plant is blended in at least one layer of the resin film other than the above printed layer (PTT) resin and polybutylene terephthalate (PBT) resin. A five-layer resin film comprising a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and a coloring agent, or A layer of a blend composition of a polybutylene terephthalate (PBT) resin and a coloring agent is used as a first layer; a printed layer is formed as a second layer thereon; and as a third layer a laminate comprising a polybutylene terephthalate (PTT) resin derived from a plant, a polybutylene terephthalate (PBT) resin, or a polybutylene terephthalate (PBT) resin a layer on which a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin is laminated as a fourth layer, or a layer of polybutylene terephthalate (PBT) resin; Further, as a fifth layer, a blend composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and an ultraviolet absorber is laminated. Or a layer of a blending composition of a polybutylene terephthalate (PBT) resin and a UV absorber; a layer of at least one layer of a resin film other than the above printed layer is blended with a polyphenylene derived from a plant Propylene dicarboxylate (PTT) resin and polybutylene terephthalate (PBT) resin. A five-layer resin film comprising, as a first layer and a second layer, a composition of a two-layer resin film according to claim 10; and printing on the second layer as a third layer a layer on which a blending composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, or a poly layer is laminated as a fourth layer a layer of a butylene terephthalate (PBT) resin; further thereon, as a fifth layer, a polybutylene terephthalate (PTT) resin containing a plant, a polybutylene terephthalate a blending composition of an ester (PBT) resin and a UV absorber, or a layer of a blend composition of a polybutylene terephthalate (PBT) resin and a UV absorber; at least a resin film other than the above printed layer More than one layer is blended with plant-derived polytrimethylene terephthalate (PTT) resin and polybutylene terephthalate (PBT) resin. A five-layer resin film comprising, as a first layer and a second layer, a composition of a two-layer resin film according to claim 10; and printing on the second layer as a third layer a layer on which a polyethylene terephthalate (PET) resin layer is laminated as a fourth layer; Further, as a fifth layer, a blend composition comprising a plant-derived polytrimethylene terephthalate (PTT) resin, a polybutylene terephthalate (PBT) resin, and an ultraviolet absorber is laminated. Or a layer of a blending composition of a polybutylene terephthalate (PBT) resin and a UV absorber; a layer of at least one layer of a resin film other than the above printed layer is blended with a polyphenylene derived from a plant Propylene dicarboxylate (PTT) resin and polybutylene terephthalate (PBT) resin. A six-layer resin film comprising, as a first layer and a second layer, a composition of a two-layer resin film according to claim 10; and printing on the second layer as a third layer a layer on which a blending composition of a polybutylene terephthalate (PTT) resin or a polybutylene terephthalate (PBT) resin derived from a plant or a poly-pair is laminated as a fourth layer a layer of butyl phthalate (PBT) resin; further thereon, as a fifth layer, a polybutylene terephthalate (PTT) resin or polybutylene terephthalate containing a plant is laminated a blending composition of (PBT) resin or a layer of polybutylene terephthalate (PBT) resin; further thereon, as a sixth layer, laminated with polytrimethylene terephthalate containing plants a blending composition of (PTT) resin, polybutylene terephthalate (PBT) resin and ultraviolet absorber, or a blend composition of polybutylene terephthalate (PBT) resin and ultraviolet absorber a layer of poly(trimethylene terephthalate) derived from plants in a layer of at least one or more layers of the resin film other than the above-mentioned printing layer TT) resin and polybutylene terephthalate (PBT) resin. The resin film according to any one of claims 9, 11 to 16, and 23, which is obtained by copolymerization 2 to 15 mol% of terephthalic acid of the acid component of the polyethylene terephthalate (PET) resin is substituted with isophthalic acid. The resin film according to any one of claims 17 to 18, wherein the biaxially-extending polyethylene terephthalate (BO-PET) resin is replaced by a polyethylene terephthalate. A biaxially-stretched copolymerized polyethylene terephthalate resin in which 2 to 15 mol% of terephthalic acid of an ester acid component is substituted with isophthalic acid. The resin film according to any one of claims 1 to 26, wherein a lubricant is contained in any one of the resin layers constituting one or more layers. A resin film obtained by forming an embossed uneven portion on a layer which is the outermost layer of the resin film according to any one of claims 1 to 27. A resin film characterized in that a mirror surface is formed on a layer which is the outermost layer of the resin film according to any one of claims 1 to 27. The resin film according to any one of claims 2 to 29, wherein the PTT content of the resin in which PBT and PTT are blended is set to 20 to 80%. A decorative sheet laminated with a resin film, characterized in that the resin film of any one of claims 1 to 30 is provided on at least one area of the substrate with or without an adhesive.