JP2008110566A - Plastic molded object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic molded object excellent in surface smoothness or decorative properties, reduced in the occurrence of mold strain at the time of molding and excellent in workability at the time of molding. <P>SOLUTION: The plastic molded object is constituted by laminating a thermoplastic resin layer, a decorative layer, a rubber layer, and a resin molded layer in this order. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a plastic molded body, and more particularly, to a plastic molded body that is excellent in surface smoothness and decorativeness and that hardly causes molding distortion during molding.

  Plastic moldings have been used in a wide range of fields. In particular, molded products using fiber-reinforced composite materials are thin, lightweight, high-rigidity, excellent in productivity, economical efficiency, electrical / electronic equipment parts, automotive equipment parts, personal computers, OA equipment, AV equipment, mobile phones, telephones It is frequently used for parts and casings of electrical and electronic equipment such as facsimiles, home appliances, and toy supplies, and is expected to grow rapidly.

  For example, in a molded body using a fiber reinforced composite material, a fiber reinforced resin sheet for thermoforming is molded into molded bodies of various shapes by press molding, drawing molding, vacuum molding, or the like.

  As a method for producing the above-mentioned fiber reinforced resin sheet for thermoforming, there is known a method in which thermoplastic resin sheets are laminated on the upper and lower sides of a fiber reinforced mat, and the fiber reinforced mat is impregnated with resin by heating and pressing the sheet. When a molded product is molded using the thermoformed fiber-reinforced resin sheet obtained by such a method, the reinforcing fibers float on the surface of the molded product, resulting in poor appearance. In addition, if reinforcing fibers emerge on the surface of the molded product, it also becomes an obstacle when the surface is painted or plated.

  Further, a method is known in which a fiber reinforced mat is impregnated with an uncured thermosetting resin, and the thermosetting resin is cured simultaneously with molding by a press molding machine or the like. This method also has the same problem as described above.

  If the molded body is molded by such a method, the reinforcing fibers may float on the surface of the molded body, resulting in poor appearance. In addition, if reinforcing fibers emerge on the surface of the molded product, it also becomes an obstacle when the surface is painted or plated. Therefore, it is required to have a smooth surface for displaying a map.

As a method of solving such a problem, for example, a method of forming a thermoplastic resin skin layer having a melting point higher than that of the matric resin of the sheet on the surface of a fiber reinforced thermoplastic resin sheet (see Patent Document 1), A method of laminating a thermoplastic resin layer that does not contain a fiber mat on the surface layer of a fiber reinforced thermoplastic resin sheet made of fiber mat (see Patent Document 2), and a crosslinking agent on at least one side of a core layer made of a fiber reinforced thermoplastic resin sheet A method of laminating a surface layer made of a thermoplastic resin sheet and heating and pressurizing the surface layer to thermally fuse the core layer and the surface layer, and crosslinking the surface thermoplastic resin layer with a crosslinking agent (see Patent Document 3) ) Elasto such as ethylene-propylene rubber or acrylonitrile-butadiene rubber on at least one side of the core layer made of fiber reinforced thermoplastic resin sheet The tensile elastic modulus is 1000 via a method of laminating a surface layer made of a mar sheet by thermal fusion (see Patent Document 4) and a low elastic modulus layer having a tensile elastic modulus of 0.1 to 500 MPa on at least one surface of the fiber reinforced plastic layer. A method of disposing a high elastic modulus layer of ˜30000 MPa (see Patent Document 5) is disclosed.
JP 58-188649 A JP 63-214444 A JP-A-5-84737 Japanese Patent Laid-Open No. 5-154922 Japanese Patent Laid-Open No. 2006-51813

  Surface smoothness is improved by the method disclosed in the above patent document, and in some applications it can meet market requirements, but in applications where a highly smooth surface is required, such as a projected image. It may not be possible to meet market demands.

  Further, in the methods disclosed in Patent Documents 1 to 3, since the low elastic modulus layer is not included in the constituent layer of the molded body, there is no layer that relieves strain generated when molding into the molded body. Therefore, the dimensional accuracy and dimensional stability of the molded body may be a problem.

  Moreover, since the method of patent document 4 and 5 has arrange | positioned the low elastic modulus layer in the structure layer of a molded object, the said subject is improved, However, In these methods, the low elastic modulus with a bad handleability is improved. Since the method of incorporating the layers into the molded body independently is employed, the operability of the cage for manufacturing the molded body may be inferior, or the frequency of occurrence of defective products may increase.

  Furthermore, none of the methods disclosed in the above-mentioned patent documents give consideration to decorating the surface of the molded body or disposing a functional layer on the surface.

  As described above, each of the conventional methods has problems.

  The object of the present invention is made in the background of the above-mentioned problems of the prior art, is excellent in surface smoothness and decorativeness, is less likely to cause molding distortion during molding, and is excellent in workability during molding. The object is to provide a plastic molding.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, this invention consists of the following structures.

  1. A plastic molded body comprising a thermoplastic resin layer, a decorative layer, a rubber layer, and a resin molded body layer laminated in this order.

  2. 2. The plastic molding according to 1 above, wherein the decorative layer is at least a printed layer and / or a metal thin film layer.

  3. 3. The plastic molded body according to 1 or 2 above, wherein the resin molded body layer is a fiber-reinforced plastic layer.

  4). 4. The plastic molding according to any one of 1 to 3, wherein the thermoplastic resin layer is an unstretched film or sheet.

  5. 4. The plastic molded article according to any one of 1 to 3, wherein the thermoplastic resin layer is a biaxially stretched polyester film having a degree of plane orientation of 0.005 to 0.15.

  6). The plastic molded body according to any one of 1 to 5 above, wherein a polymer film layer made of at least one selected from polyester, polyurethane and acrylic polymer is disposed between the rubber layer and the decorative layer.

  7. 7. The plastic molded article according to 6 above, wherein a polymer film is disposed on the surface side of the thermoplastic resin layer that contacts the decorative layer.

  8). 8. The molded product according to any one of 1 to 7 above, wherein the plastic molded product is a sheet.

  9. 9. The plastic molded article according to 8 above, wherein the plastic molded article has a curved portion.

  The plastic molded body of the present invention is formed by laminating a thermoplastic resin laminate comprising at least a thermoplastic resin layer / decorative layer / rubber layer on the surface of the resin molded body layer so that the thermoplastic resin layer side is a surface layer. Further, it has an advantage that extremely high surface smoothness can be obtained by the surface smoothness of the thermoplastic resin layer and the print-through effect by the rubber layer.

  In addition, since the strain that occurs during molding of the molded body can be reduced by utilizing the elasticity of rubber, for example, the surface state of the molded body can be improved as described above, and the distortion that occurs during molding can be reduced. Furthermore, the external force applied to the molded body in the use of the molded body can be relaxed by the elasticity of the rubber. For example, the durability of the plastic molded body can be improved. Can be granted.

  In addition, the thermoplastic resin laminate is provided with a decorative layer and has excellent surface characteristics as described above, and thus has an advantage that a molded body having high gloss and high decorativeness and design can be obtained.

  Further, as described above, the plastic molded body of the present invention is incorporated into the plastic molded body as a laminated body in which the thermoplastic resin layer is integrated as described above. Compared to the method of incorporating the molded product into the slab, there are advantages that the workability at the time of producing the molded body can be improved and the frequency of occurrence of defective products can be reduced.

  The plastic molded body of the present invention is a resin molded body layer comprising a thermoplastic resin laminate comprising at least a thermoplastic resin layer / decorative layer / rubber layer (hereinafter also referred to as a decorative molding thermoplastic resin laminate). It is preferable to laminate on the surface so that the thermoplastic resin layer side becomes a surface layer.

(1) Thermoplastic resin layer The type of resin that forms the thermoplastic resin layer, which is a constituent layer of the above-mentioned decorative molding thermoplastic resin laminate, is the type of resin that is used for the base material in the market demand or plastic molding. The selection may be made as appropriate. Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polyamide, polyamideimide, polycarbonate, polysulfone, polyacetal, polyphenylene ether, polyphenylene sulfide, poly Examples include arylate, polyetherimide, polyethersulfone and polyetherketone, and blends and alloy compositions thereof.

  The thermoplastic resin layer is preferably made of an unstretched film or sheet. The unstretched film or sheet is preferable because of excellent moldability. The thickness of the unstretched film or sheet is preferably 50 to 500 μm, more preferably 100 to 400 μm, and still more preferably 200 to 400 μm. By setting the thickness of the unstretched film or sheet to 50 μm or more, sufficient rigidity can be obtained, and recesses are hardly generated due to shrinkage stress. Further, by making the thickness of the unstretched film or sheet 500 μm or less, the characteristics of the plastic molded body that is lightweight can be utilized.

  In the present invention, it is preferable to use a biaxially stretched polyester film having a plane orientation degree of 0.005 to 0.15 as the thermoplastic resin layer. The biaxially stretched polyester film has a good balance of economy, heat resistance, solvent resistance, dimensional stability, surface smoothness, thickness accuracy, mechanical properties, etc. Sex can be imparted.

  Hereinafter, the case where said biaxially-stretched polyester film is used for a thermoplastic resin layer is explained in full detail as a representative example.

  The upper limit of the degree of plane orientation of the film is more preferably 0.14, and 0.13 is preferable when high moldability is required. The degree of plane orientation is a physical property related to moldability. The higher the degree of plane orientation, the more the molecular chains are arranged in the plane direction and the moldability is lowered. Accordingly, the smaller the degree of plane orientation, the better the moldability. However, the strength of the film decreases, flatness such as thickness unevenness tends to deteriorate, and the solvent resistance tends to decrease. From such a viewpoint, the lower limit of the degree of plane orientation is more preferably 0.01, and even more preferably 0.04.

  As a manufacturing method of said biaxially stretched polyester film, after drying polyester as needed, for example, it supplies to a well-known melt extruder, it extrudes from a slit-shaped die | dye to a sheet form, By the system of electrostatic application etc. The unstretched sheet is stretched after being brought into close contact with the casting drum, cooled and solidified to obtain an unstretched sheet. Such a stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching. In short, the unstretched sheet is stretched and heat-treated in the longitudinal direction and the width direction of the film to obtain a film having a desired degree of plane orientation. The method is adopted.

  In the above-mentioned biaxially stretched polyester film, the method for bringing the degree of plane orientation to the above range is, for example, a method by optimizing the stretch ratio and heat setting temperature using a homopolyester resin such as polyethylene terephthalate or polyethylene naphthalate as a raw material. And a polyester resin, a method of reducing the degree of plane orientation by using a copolyester resin or a compounded resin in which the copolyester resin and the homopolyester resin are blended, a method combining the above methods, and the like. .

  For example, in the method of reducing the degree of plane orientation under stretching conditions, the stretching ratio of biaxial stretching is 1.6 to 4.2 times in each direction, and preferably 1.7 to 4.0 times. In particular, 1.8 to 3.2 times is preferable. In this case, either of the stretching ratios in the longitudinal direction and the width direction may be increased or the same. The stretching speed is desirably 1000% / min to 200000% / min, and the stretching temperature can be any temperature as long as it is not less than the glass transition temperature of the polyester and not less than the glass transition temperature + 100 ° C., preferably It is good to extend | stretch in the range of 80-170 degreeC.

 Further, the film is heat-treated after biaxial stretching, and this heat treatment can be performed by any conventionally known method such as in an oven or on a heated roll. The heat treatment temperature is preferably in the range of 120 ° C. or higher and 245 ° C. or lower, more preferably 150 to 220 ° C. The heat treatment temperature has an appropriate range depending on the resin used as a raw material, and may be appropriately set within the temperature range so as to obtain the required physical properties. The heat treatment time is preferably 1 to 60 seconds. The heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Furthermore, re-stretching may be performed once or more in each direction, and then heat treatment may be performed. Here, the heat treatment temperature can be confirmed by the peak temperature of the crystal melting sub-peak caused by the heat treatment observed by DSC.

  In the present invention, the method exemplified below is preferably used when applied to applications requiring high moldability.

As a polyester film having a high moldability (hereinafter also referred to simply as a polyester film for molding), the 100% elongation stress (F100 ₂₅ ) at 25 ° C. in the longitudinal direction and the width direction of the film are both 30. A polyester film of ~ 300 MPa is preferred.

F100 ₂₅ in the longitudinal direction and the width direction of the film is 40 to 300 MPa, and the lower limit is preferably 50 MPa, more preferably 60 MPa. The upper limit is preferably 250 MPa, more preferably 200 MPa, and still more preferably 180 MPa. When F100 ₂₅ is less than 40 MPa, when the roll-shaped film is pulled and unwound, the film is stretched or torn, resulting in poor workability. On the other hand, when F100 ₂₅ exceeds 300 MPa, the moldability becomes poor. In particular, when molding is performed using a mold having irregularities and depressions, a film before molding may be followed by lightly following those molds in advance. In such a case, it is difficult to mold the film, and the finished product may have poor design properties.

Moreover, as for this polyester film for shaping | molding, it is more preferable that the stress at the time of 100% expansion | extension (F100100) at ₁₀₀ degreeC in the longitudinal direction and the width direction of a film is all 1-100 Mpa.

The upper limit of F100 ₁₀₀ in the longitudinal direction and the width direction of the film is preferably 90 MPa, more preferably 80 MPa, and particularly preferably 70 MPa from the viewpoint of moldability. On the other hand, the lower limit of F100 ₁₀₀ is preferably 5 MPa, more preferably 10 MPa, and particularly preferably 20 MPa from the viewpoint of elasticity and shape stability when using a molded product.

  In the molding polyester film, the thermal shrinkage in the longitudinal direction and the width direction at 150 ° C. is preferably 0.01 to 5.0%. The lower limit value of the heat shrinkage rate at 150 ° C. is more preferably 0.1%, still more preferably 0.5%. On the other hand, the upper limit value of the thermal shrinkage rate at 150 ° C. is more preferably 4.5%, further preferably 4.1%, and particularly preferably 3.2%. Even if the thermal shrinkage rate of the film in the longitudinal direction and the width direction at 150 ° C. is less than 0.01%, there is no significant difference in practical effect, and the productivity is greatly reduced. There is no necessity to make the shrinkage rate less than 0.01%. On the other hand, when the thermal shrinkage ratio of the film in the longitudinal direction and the width direction at 150 ° C. exceeds 5.0%, the film is likely to be deformed in the post-processing step that takes heat, and the appearance and design properties of the post-processed film Becomes defective.

  The haze of the molding polyester film is preferably 0.1 to 3.0%. The lower limit of haze is more preferably 0.3%, still more preferably 0.5%. On the other hand, the upper limit of haze is more preferably 2.5%, still more preferably 2.0%. It is difficult to produce a film having a haze of less than 0.1% on an industrial scale with high normal productivity. On the other hand, when the haze of the film exceeds 3.0%, when the vapor deposition or sputtering surface of the metal or the printed surface is viewed from the back surface of the film, the metal or the printed surface looks dull, resulting in poor design. In addition, it is difficult to obtain a film having a haze of 2.0% or less by a method for forming irregularities on the film surface by incorporating particles in the film, which is generally performed for improving handling properties in the film. . This characteristic is an important characteristic when the polyester laminate for rubber composite of the present invention is used as an outermost layer of a molded product and used for decoration.

  Moreover, when using the polyester laminated body for rubber composites of this invention as an outermost layer of a molded object, it is preferable that the surface roughness (Ra) of the film of at least one side is 0.005-0.030 micrometer. The lower limit value of Ra is more preferably 0.006 μm, still more preferably 0.007 μm. On the other hand, the upper limit of Ra is more preferably 0.025 μm, and still more preferably 0.015 μm. As the Ra of at least one side of the film becomes smaller, it becomes difficult to wind the film, and the frequency of occurrence of blocking or breaking of the film increases when the film once wound up in a roll shape is unwound. On the other hand, when Ra exceeds 0.03 μm, the protrusion becomes a defect in a post-processing step such as vapor deposition, sputtering, or printing, and the design property is deteriorated.

  Although the manufacturing method of the polyester film for shaping | molding which has the said characteristic is not limited, Implementing with the method illustrated below is a preferable embodiment.

  It is preferable to use a copolymer polyester containing 5 to 50 mol% of a copolymer component as a raw material. A polyester film obtained by using a copolymer polyester containing 5 to 50 mol% of a copolymer component as a raw material has a lower crystallization rate and lower crystallinity than a polyethylene terephthalate film or the like. In addition, in order to reduce the degree of surface orientation and the thermal shrinkage at 150 ° C., when a method of heat treatment at a higher temperature than usual is used, the heat treatment is rapidly performed at a high temperature after the end of stretching. The mobility of the molecules that make up the lower material is increased. Therefore, the surface protrusions formed by the bulging of the particles (particles in the biaxially oriented film or particles in the coating layer) in the stretching process are buried again in the heat treatment zone, so that the surface roughness is sufficient. Can't get. Therefore, avoiding the problem of haze reduction when the amount of added particles is increased more than necessary in order to suppress the blocking and tearing when winding the film neatly and unwinding the film wound into a roll. can do.

  In order to solve the above-mentioned problem, it is preferable that the heat treatment zone has two stages (or more) and the first stage heat treatment temperature TS1 and the second stage heat treatment temperature TS2 are controlled within a specific range.

  As a result, the crystallization of the film is promoted to some extent before the particles are buried inside the film in the first heat treatment zone, and the temperature is further increased in the second heat treatment zone. The mobility of the molecules is sufficiently lowered, and the film having a low thermal shrinkage rate can be obtained by further promoting the crystallinity while forming the protrusions on the surface. Moreover, it is not necessary to contain particles more than necessary from the viewpoint of transparency.

  The copolymer polyester used for the molding polyester film having the above characteristics is composed of (a) an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol. A copolymer polyester or (b) a copolymer polyester composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol is preferred. Moreover, it is preferable from the point which further improves the moldability that the polyester which comprises a biaxially-oriented polyester film further contains a 1, 3- propanediol unit or a 1, 4- butanediol unit as a glycol component.

  Any method of the above copolyester alone, one or more homopolyesters or a blend of copolyesters, or a combination of homopolyesters and copolyesters is possible. Among these, the blending method is preferable from the viewpoint of suppressing the lowering of the melting point.

  As the above-mentioned copolymer polyester, when using a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol, as the aromatic dicarboxylic acid component, Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more, Particularly preferred is 95 mol% or more, and particularly preferred is 100 mol%.

  Examples of branched aliphatic glycols include neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and the like. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.

  Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable. Furthermore, it is a more preferable embodiment that 1,3-propanediol or 1,4-butanediol is used as a copolymerization component in addition to the glycol component. Use of these glycols as a copolymerization component is suitable for imparting the above-mentioned properties, and is also excellent in transparency and heat resistance, and from the viewpoint of improving the adhesion with the adhesion modified layer. Is also preferable.

  Further, when a copolymer polyester composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol is used as the copolymer polyester, the amount of ethylene glycol is 70 with respect to the total glycol component. It is at least mol%, preferably at least 85 mol%, particularly preferably at least 95 mol%, particularly preferably at least 100 mol%. As the glycol component other than ethylene glycol, the above-mentioned branched aliphatic glycol, alicyclic glycol, or diethylene glycol is preferable.

  Examples of the catalyst used for producing the copolymer polyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, titanium / silicon composite oxides, and germanium compounds. . Of these, titanium compounds, antimony compounds, germanium compounds, and aluminum compounds are preferred from the viewpoint of catalytic activity.

  When manufacturing the said copolyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.

  The above copolyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, and particularly preferably from the viewpoint of moldability, adhesion, and film-forming stability. 60 dl / g or more. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.

  By using one or more homopolyesters or copolymerized polyesters as the polyester raw material and blending them to form a film, transparency is maintained while maintaining the same flexibility as when only the copolymerized polyester is used. And a high melting point (heat resistance) can be realized. In addition, when only a high melting point homopolyester (for example, polyethylene terephthalate) is used, it is possible to realize a melting point (heat resistance) having no flexibility and practical problem while maintaining high transparency.

  In addition, it is more preferable from the viewpoint of moldability to blend the above copolyester and at least one homopolyester other than polyethylene terephthalate (for example, polytetramethylene terephthalate or polybutylene terephthalate) as a raw material. .

  The melting point of the molding polyester film having the above characteristics is preferably 200 to 245 ° C. from the viewpoint of heat resistance and moldability. By controlling the type and composition of the polymer to be used and the film forming conditions within the range of the melting point, a balance between moldability and finish can be achieved, and a high-quality molded product can be produced economically. Here, the melting point is an endothermic peak temperature at the time of melting, which is detected at the time of primary temperature rise in so-called differential scanning calorimetry (DSC). The melting point was determined by measuring using a differential scanning calorimeter (manufactured by Mac Science, DSC3100S) at a heating rate of 20 ° C./min. The lower limit of the melting point is more preferably 210 ° C, particularly preferably 230 ° C. If the melting point is less than 200 ° C, the heat resistance tends to deteriorate. Therefore, it may become a problem when exposed to high temperature during molding or use of a molded product. Further, when the rubber layer is crosslinked by thermal crosslinking, distortion may occur in the polyester film laminate, which is not preferable.

  Further, the molding polyester film preferably has a light transmittance at a wavelength of 370 nm of 50% or less, more preferably 40% or less, and particularly preferably 30% or less. By controlling the light transmittance of the polyester film for molding at a wavelength of 370 nm to 50% or less, the weather resistance of the molded body is improved particularly when the rubber composite polyester laminate of the present invention is used as the outermost layer of the molded body. Can be made.

  As a method of controlling the light transmittance at a wavelength of 370 nm to 50% or less, a method of blending an ultraviolet absorber in any of the constituent layers of the molding polyester film is used. The ultraviolet absorber may be either inorganic or organic as long as it can impart the above characteristics. Examples of organic ultraviolet absorbers include benzotoazole, benzophenone, cyclic imino ester, and combinations thereof. From the viewpoint of heat resistance, benzotoazole and cyclic imino ester are preferred. When two or more kinds of ultraviolet absorbers are used in combination, ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.

  Examples of the benzotriazole ultraviolet absorber include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyhexyl) phenyl ] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert -Butyl-3 '-(methacryloyloxyethyl) phenyl] -2 -Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-( Methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. However, it is not particularly limited to these.

  Examples of the cyclic imino ester ultraviolet absorber include 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazine. -4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1- Benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl -3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2- o-methoxy Enyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one) 2,2'-bis (3,1-benzoxazin-4-one), 2, 2'-ethylenebis (3,1-benzoxazin-4-one), 2,2'-tetramethylenebis (3,1-benzoxazin-4-one), 2,2'-decamethylenebis (3 1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine-4 -On), 2,2 '-(4,4 '-Diphenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2,6- or 1,5-naphthalene) bis (3,1-benzoxazin-4-one), 2 , 2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene) bis (3,1-benzoxazine- 4-one), 2,2 '-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene) bis (3 1-benzoxazin-4-one) 1,3,5-tri (3,1-benzoxazin-4-on-2-yl) benzene, 1,3,5-tri (3,1-benzoxazine-4 -On-2-yl) naphthalene and 2,4,6-tri (3,1- Zooxazin-4-on-2-yl) naphthalene, 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,6 -Dione, 2,7-dimethyl-4H, 9H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,9-dione, 2,8-diphenyl- 4H, 8H-benzo (1,2-d; 5,4-d ′) bis- (1,3) -oxazine-4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2 -D; 5,4-d ') bis- (1,3) -oxazine-4,6-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one) 6,6'-bis (2-ethyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-phenyl- 4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-phenyl- 4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-ethylenebis (2- Phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-butylenebis (2- Phenyl-4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6′-oxybis (2- Phenyl-4H, 3,1-benzoo Sazine-4-one), 6,6'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-sulfonylbis (2-phenyl-4H, 3,1) -Benzoxazin-4-one), 6,6'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 7,7′-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-methylenebis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), 7,7′-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7′-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one) 7,7'-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one) 7,7'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-methyl-4H, 3,1-benzoxazin-4-one) ), 6,7'-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,7'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one) ), And 6,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one).

  When blending the above-mentioned organic ultraviolet absorber into a film, it is exposed to a high temperature in the extrusion process. Therefore, it is necessary to use an ultraviolet absorber having a decomposition start temperature of 290 ° C. or higher as a process contamination during film formation. It is preferable in order to reduce it. If an ultraviolet absorber having a decomposition start temperature of 290 ° C. or lower is used, the decomposed product of the ultraviolet absorber adheres to the roll group of the manufacturing apparatus during film formation, and may reattach to the film or be damaged. Since it becomes an optical fault, it is not preferable.

  Examples of inorganic ultraviolet absorbers include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.

  The upper limit of the melting point is preferably higher from the viewpoint of heat resistance, but when the polyethylene terephthalate unit is the main component, the film having a melting point exceeding 250 ° C. tends to deteriorate moldability. In addition, transparency tends to deteriorate. Furthermore, in order to obtain high moldability and transparency, it is preferable to control the upper limit of the melting point to 245 ° C.

  Moreover, in order to improve handling properties, such as the slipperiness and winding property of a film, it is preferable to form an unevenness | corrugation on the film surface. As a method for forming irregularities on the film surface, a method of incorporating particles in the film is generally used.

  Examples of the particles include internal particles having an average particle size of 0.01 to 10 μm, external particles such as inorganic particles and / or organic particles. When particles having an average particle diameter exceeding 10 μm are used, defects in the film are liable to occur, and the design and transparency tend to deteriorate. On the other hand, in the case of particles having an average particle diameter of less than 0.01 μm, handling properties such as film slipperiness and winding property tend to be lowered. The lower limit of the average particle diameter of the particles is more preferably 0.10 μm, particularly preferably 0.50 μm, from the viewpoint of handling properties such as slipping property and winding property. On the other hand, the average particle diameter of the particles is more preferably 5 μm, particularly preferably 2 μm, from the viewpoint of transparency and reduction of film defects due to coarse protrusions.

  The average particle size of the particles is taken by taking a plurality of photographs of at least 200 particles by electron microscopy, tracing the outline of the particles on an OHP film, and converting the trace image to an equivalent circle diameter with an image analyzer. To calculate.

  Examples of the external particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxyapatite and the like, and styrene, silicone, acrylic Organic particles or the like containing acids as constituent components can be used. Among these, inorganic particles such as dry, wet and dry colloidal silica and alumina and organic particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components are preferably used. Two or more of these internal particles, inorganic particles and / or organic particles may be used in combination as long as the characteristics defined in the present invention are not impaired.

  Furthermore, the content of the particles in the film is preferably in the range of 0.001 to 10% by mass. When the amount is less than 0.001% by mass, the handling property is likely to be deteriorated, for example, the slipperiness of the film is deteriorated or winding becomes difficult. On the other hand, if it exceeds 10% by mass, it tends to cause formation of coarse protrusions, deterioration of film forming property and transparency.

Moreover, since the particle | grains contained in a film generally differ in refractive index from polyester, it becomes a factor which reduces the transparency of a film.
In many cases, the molded product is printed on the surface of the film before the film is molded in order to improve the design. Since such a printing layer is often applied to the back side of a molding film, it is desired that the transparency of the film is high from the viewpoint of printing clarity.

  Therefore, in order to obtain a high degree of transparency while maintaining the handleability of the film, the particles are not substantially contained in the base film of the main layer, and the particles are only in the surface layer having a thickness of 0.01 to 5 μm. It is effective to use a laminated film having a laminated structure containing. The upper limit of the thickness of the surface layer is preferably 3 μm, particularly preferably 1 μm. In this case, the particles exemplified above can be used.

    In order to make the haze of the above-mentioned film 0.1 to 3.0%, the particles are not substantially contained in the film, and the particles are contained only in the surface layer having a thickness of 0.01 to 5 μm. It is preferable to have a laminated structure. In addition, it is difficult to obtain a film having a haze of 3.0% or less only by incorporating particles in the film while maintaining handling properties.

  Note that “substantially no particles are contained in the base film” as used above means, for example, in the case of inorganic particles, the content that is below the detection limit when inorganic elements are quantified by fluorescent X-ray analysis. means. This is because contaminants derived from foreign substances may be mixed without intentionally adding particles to the base film.

  The thin surface layer can be formed by a coating method or a coextrusion method. Especially, in the case of the coating method, since the adhesiveness with a printing layer can also be improved by using the composition which consists of adhesiveness modification resin containing particle | grains as an application layer, it is a preferable method. As said adhesive property modification resin, resin which consists of at least 1 sort (s) chosen from polyester, a polyurethane, an acrylic polymer, and / or those copolymers is preferable.

  As the particles to be contained in the surface layer, the same particles as those described above can be used. Among the particles, silica particles, glass fillers, and silica-alumina composite oxide particles are particularly suitable from the viewpoint of transparency because the refractive index is relatively close to that of polyester.

  Furthermore, the particle content in the surface layer is preferably in the range of 0.01 to 25% by mass. When the content is less than 0.01% by mass, handling properties are likely to deteriorate, for example, the slipperiness of the film is deteriorated or winding becomes difficult. On the other hand, when it exceeds 25 mass%, transparency and applicability tend to deteriorate.

  In order to impart other functions, the molding polyester film can be made into a laminated structure by a known method using different types of polyester. The form of the laminated film is not particularly limited. For example, the laminated film has an A / B two-kind two-layer structure, a B / A / B two-kind three-layer structure, and a C / A / B three-kind three-layer structure. The form is mentioned

  It is important that the molding polyester film is a biaxially stretched film. By molecular orientation by biaxial stretching, the thermal deformation rate of the film under a micro tension (initial load 49 mN) can be controlled within a preferable range, and solvent resistance and dimensional stability, which are disadvantages of the unstretched sheet. Is improved. The correspondence can improve the solvent resistance and heat resistance, which are disadvantages of the unstretched sheet, while maintaining the good formability of the unstretched sheet.

  The method for producing the biaxially oriented polyester film is not particularly limited. For example, after drying the polyester resin as necessary, the polyester resin is supplied to a known melt extruder, extruded from a slit-shaped die into a sheet, and electrostatically applied. The method of sticking to a casting drum by this method, cooling and solidifying to obtain an unstretched sheet, and then biaxially stretching the unstretched sheet is exemplified.

  As the biaxial stretching method, a method is employed in which an unstretched sheet is stretched and heat-treated in the longitudinal direction (MD) and width direction (TD) of the film to obtain a biaxially stretched film having a desired in-plane orientation degree. . Among these methods, in terms of film quality, the MD / TD method in which the film is stretched in the longitudinal direction and then stretched in the width direction, or the TD / MD method in which the film is stretched in the width direction and then stretched in the longitudinal direction. An axial stretching method and a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched almost simultaneously are desirable. In the case of the simultaneous biaxial stretching method, a tenter driven by a linear motor may be used. Furthermore, if necessary, a multistage stretching method in which stretching in the same direction is performed in multiple stages may be used.

  The film stretching ratio when biaxially stretching is preferably 1.6 to 4.2 times in the longitudinal direction and the width direction, particularly preferably 1.7 to 4.0 times. In this case, the stretching ratio in the longitudinal direction and the width direction may be either larger or the same ratio. More preferably, the stretching ratio in the longitudinal direction is 2.8 to 4.0 times, and the stretching ratio in the width direction is 3.0 to 4.5 times.

  As the stretching conditions for producing the molding polyester film, it is preferable to select, for example, the following conditions.

  In the longitudinal stretching, it is more preferable that the stretching temperature is 50 to 110 ° C. and the stretching ratio is 1.6 to 4.0 times so that the subsequent lateral stretching can be performed smoothly.

  Usually, when stretching the polyethylene terephthalate, if the stretching temperature is lower than the appropriate conditions, the yield stress increases rapidly at the beginning of the lateral stretching, and therefore stretching cannot be performed. Moreover, even if it can extend | stretch, since thickness and a draw ratio become easy to become nonuniform, it is unpreferable.

  In addition, when the stretching temperature is higher than appropriate conditions, the initial stress is low, but the stress does not increase even when the stretch ratio is high. Therefore, the film has a small stress at 100% elongation at 25 ° C. Therefore, by taking the optimum stretching temperature, a highly oriented film can be obtained while ensuring stretchability.

  However, when the copolymerized polyester contains 1 to 40 mol% of a copolymer component, the stretching stress rapidly decreases as the stretching temperature is increased so as to eliminate the yield stress. In particular, since the stress does not increase even in the latter half of the stretching, the orientation does not increase and the stress at 100% elongation at 25 ° C. decreases.

  Such a phenomenon is likely to occur when the thickness of the film is 60 to 500 μm, and is particularly noticeable in a film having a thickness of 100 to 300 μm. Therefore, in the case of a film using the copolymerized polyester of the present invention, the stretching temperature in the transverse direction is preferably set as follows.

First, preheating temperature is performed in the range of +10 degreeC-+50 degreeC of the glass transition temperature at the time of measuring the mixture after extruding film material with an extruder in DSC. Next, in the first half of the transverse stretching, the stretching temperature is preferably −20 ° C. to + 15 ° C. with respect to the preheating temperature. In the latter half of the transverse stretching, the stretching temperature is preferably 0 ° C. to −30 ° C., particularly preferably −10 ° C. to −20 ° C. with respect to the stretching temperature of the first half. By adopting such conditions, the first half of the transverse stretching is easy to stretch because the yield stress is small, and the second half is easily oriented. In addition, it is preferable that the draw ratio of a horizontal direction shall be 2.5 to 5.0 times. As a result, it is possible to obtain a film that satisfies F100 ₂₅ and F100 ₁₀₀ defined in the present invention.

  Further, the film is heat-treated after biaxial stretching. This heat treatment condition is an important condition for achieving both haze and surface roughness, that is, slipperiness of the film. The stretched film is subsequently heat-treated in the tenter. In this case, it is important to perform the heat treatment in two or more stages. The first stage heat treatment temperature (TS1) is −5 ° C. to −30 ° C. of the second stage heat treatment temperature (TS2), the lower limit is preferably −10 ° C., and the upper limit is preferably −25 ° C. The second stage heat treatment temperature (TS2) is carried out in the range of −5 ° C. to −35 ° C. of the melting point when the mixture obtained by extruding the film material with an extruder is measured by DSC. The lower limit is preferably −10 ° C., and the upper limit is preferably −30 ° C. An intermediate heat treatment zone can be provided between TS1 and TS2, and a heat treatment zone can be provided after TS2. In these cases, TS2 shows the highest heat treatment temperature. By taking such conditions, a film having a low haze and good sliding properties can be obtained.

  The reason is considered as follows. A polyester film containing about 5 to 50 mol% of a copolymer component as in the present invention has a lower crystallization speed and lower crystallinity than a polyethylene terephthalate film. Therefore, when heat treatment is performed rapidly at a high temperature after the end of stretching, the mobility of molecules constituting the material having low crystallinity is increased in the heat treatment zone. Therefore, the surface protrusions formed by the bulging of the particles (particles in the film and / or particles of the coating layer) in the stretching process are buried again in the heat treatment zone, so that sufficient surface roughness is obtained. I can't. Therefore, in order to wind up the film neatly, the content of the particles is increased more than necessary, which causes a decrease in haze. On the other hand, if the temperature of TS2 is lower than a predetermined temperature, a film having a sufficiently low thermal shrinkage at 150 ° C. cannot be obtained.

  Therefore, taking the method of the present invention in which the heat treatment zone has two stages (or more) is that the crystallization of the film is promoted to some extent before the particles are buried in the TS1 and the TS2 zone is sufficient. Even when the temperature is increased, the molecular mobility is sufficiently lowered as compared with the state of the previous paragraph, and the film is further promoted in crystallinity with the surface protrusions formed, and a film having a low thermal shrinkage rate can be obtained. Moreover, the addition of more than necessary particles can be prevented.

  In general, as a means for lowering the degree of plane orientation, a method of lowering the draw ratio and a method of increasing the blending amount of the copolymer component are known, but the former method deteriorates the thickness unevenness of the film. This is not preferable because the melting point is lowered and the heat resistance is deteriorated. In the present invention, in order to reduce the plane orientation degree of the biaxially oriented polyester film and the thermal shrinkage at 150 ° C., heat setting is performed at a higher temperature than usual.

  Further, in the present invention, it is necessary to use a copolymer polyester as a biaxially oriented polyester film, and since the melting point is lower than that of a uniform polymer, if the heat setting temperature is increased, the clip that holds the film in the transverse stretching step is used. The film is difficult to peel off. Therefore, it is important to sufficiently cool the vicinity of the clip when the clip releases the film at the tenter outlet. Specifically, in order to make it easy to peel the film and the clip, (1) a method of providing a heat shielding wall on the clip portion so that the clip is hardly heated, and (2) a method of adding a clip cooling mechanism to the tenter. (3) A method in which the cooling section after heat setting is set long in order to enhance the cooling capacity, and the entire film is sufficiently cooled. (4) The cooling efficiency is increased by increasing the length of the cooling section and the number of sections. It is preferable to employ a method of increasing the clip, and (5) a method of enhancing the cooling of the clip by using a type in which the return portion of the clip travels outside the furnace.

The polyester for rubber composite of the present invention is preferably formed by laminating a crosslinked polymer layer having a thickness of 0.01 to 5 μm on at least one side of the polyester film. The thickness of the crosslinked polymer layer is more preferably 0.03 to 3 μm, and further preferably 0.05 to 1 μm. If the thickness of the crosslinked polymer layer is less than 0.01 μm, the effect of improving the adhesion between the polyester film and the rubber layer is lowered, which is not preferable. On the other hand, if it exceeds 5 μm, the effect of improving the adhesion between the polyester film and the rubber layer is saturated, which is disadvantageous economically. Also,
The stress at 10% elongation (25 ° C.) in the longitudinal direction and the width direction of the film described later is increased, which may cause deterioration in moldability and decrease in durability of delamination strength between the rubber layer and the polyester film. Therefore, it is not preferable.

  The thickness of the biaxially stretched polyester film is preferably 50 to 500 μm, more preferably 100 to 400 μm, and even more preferably 200 to 400 μm, like the unstretched film or sheet. If it is smaller than 50 μm, the rigidity becomes insufficient, and a recess may be formed due to the stress caused by the shrinkage. When the thickness is larger than 500 μm, the weight increases, and as a result, the weight of the plastic molded body increases, and the characteristic of the plastic molded body that is lightweight may be impaired.

(2) Decorative layer The decorative layer, which is a constituent layer of the thermoplastic molding laminate for decorative molding, has a function of improving decorativeness and design, and the decoration is made at least by printing and / or a metal thin film. It is preferable that

  As a printing method for forming the decorative layer, a known printing method such as gravure printing, flat printing, flexographic printing, dry offset printing, pad printing, or screen printing may be used according to the product shape or printing application. Can do. In particular, offset printing and gravure printing are suitable for multicolor printing and gradation expression.

  Furthermore, the decorative layer may be not only a printed layer but also a metal or metal oxide thin film layer, and may be a combination of a printed layer and a metal or metal oxide thin film layer. Examples of methods for forming a metal or metal oxide thin film layer include vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.

  Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method can be used. Among these, the vapor deposition method and the plating method are preferable for forming the metal layer, and the vapor deposition method is preferable for forming the metal oxide layer. The vapor deposition method and the plating method can be used in combination.

  As the metal for the vapor deposition method, aluminum, chromium, silver, gold, and a combination thereof are used. In the present invention, the thermoplastic resin laminate for decorative molding is used by being incorporated in a plastic molded body as a constituent material of the plastic molded body, and may be molded into a complicated shape. Therefore, it is preferable that the metal forming the metal layer has excellent spreadability. For example, in the case of aluminum metal, the one containing a metal such as indium is preferable.

  In the case of using a decoration method in which a thin film layer of metal or metal oxide is partially used, after a solvent-soluble resin layer is formed on a portion that does not require the thin film layer, a thin film layer is formed on the entire surface thereof. There is a method of removing the unnecessary metal thin film together with the solvent-soluble resin layer by forming a film and performing solvent cleaning. The solvent often used in this case is water or an aqueous solution. As another decoration method, a method of forming such a thin film on the entire surface, then forming a resist layer on a portion where the thin film is to be left, etching with acid or alkali, and removing the resist layer Is mentioned.

  The spreadability is a characteristic required even when the printing ink is used. Therefore, it is preferable to use a flexible resin such as a polyurethane resin as a main component as the binder resin constituting the printing ink.

(3) Intermediate layer (between the thermoplastic resin layer and the decorative layer)
In the thermoplastic resin laminate for decorative molding, an intermediate layer made of at least one selected from polyester, polyurethane, or acrylic polymer is disposed between the thermoplastic resin layer and the decorative layer. Is preferred.

  Each of the above polymers may be used alone, or two or three different types may be used in combination.

  The polyester has an ester bond in the main chain or side chain, and is obtained by polycondensation of a dicarboxylic acid and a diol.

  As the carboxylic acid component constituting the polyester, aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2 -Bisphenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid, etc. can be used. From the viewpoint of the strength and heat resistance of the laminated film, these aromatic dicarboxylic acids are preferably polyesters that occupy 30 mol% or more, more preferably 35 mol% or more, and most preferably 40 mol% or more of the total dicarboxylic acid component. It is preferable to use it.

  Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.

  As the glycol component of the polyester resin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3- Diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2 , 4-Trimethyl-1,6-hexanediol, 1,2-si Rhohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A 4,4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidene Phenol, 4,4′-isopropylidene bin diol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and the like can be used.

  In addition, when using polyester as an aqueous solution as a coating solution, in order to facilitate water-solubilization or water-dispersion of the polyester, a compound containing a sulfonate group, a compound containing a phosphonate group, and a carboxylate group are included. It is preferred to copolymerize the compound.

  Examples of the compound containing a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2, 3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3 , 6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellitate, 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, etc., or alkali metal salts, alkaline earth metal salts, ammonium salts thereof. However, it is not limited to these.

  Examples of the compound containing a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo -1,4-bis (hydroxyethoxy) benzene or the like, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof can be used, but are not limited thereto.

  Examples of the compound containing a phosphonate group include phosphoterephthalic acid, 5-phosphosophthalic acid, 4-phosphoisophthalic acid, 4-phosphonaphthalene-2,7-dicarboxylic acid, phospho-p-xylylene glycol, 2-phospho- 1,4-bis (hydroxyethoxy) benzene or the like, or an alkali metal salt, alkaline earth metal salt, or ammonium salt thereof can be used, but is not limited thereto.

  In the present invention, for example, a modified polyester copolymer such as a block copolymer or a graft copolymer modified with acrylic, urethane, epoxy, or the like can be used.

  Preferred polyesters include a copolymer having an acid component selected from terephthalic acid, isophthalic acid, sebacic acid, and 5-sodium sulfoisophthalic acid, and a glycol component selected from ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol. Examples include coalescence. When water resistance is required, a copolymer having trimellitic acid as its copolymer component can be suitably used instead of 5-sodium sulfoisophthalic acid.

The polyester can be produced by the following production method.
For example, a polyester resin composed of terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid as a dicarboxylic acid component, and ethylene glycol or neopentyl glycol as a glycol component will be described.
First, terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and ethylene glycol, neopentyl glycol are directly esterified, or terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and ethylene glycol, neopentyl glycol Can be produced by a first-stage esterification step or transesterification step in which a transesterification reaction is carried out and a second-stage polycondensation step in which a reaction product of this first step is subjected to a polycondensation reaction.

  At this time, as the reaction catalyst, for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used.

  Further, as a method for obtaining a polyester resin having a large amount of carboxylic acid at the terminal and / or side chain, JP-A-54-46294, JP-A-60-209073, JP-A-62-240318, JP-A-53-26828, JP-A-53-26829, JP-A-53-98336, JP-A-56-116718, JP-A-61-124684, JP-A-62-240318 Although it can be produced from a resin obtained by copolymerization of a trivalent or higher polyvalent carboxylic acid described in Japanese Patent Publication No. Gazette, etc., other methods may be used.

  The intrinsic viscosity of the polyester is not particularly limited, but is preferably 0.3 dl / g or more, more preferably 0.35 dl / g or more, and most preferably 0.4 dl / g or more in terms of adhesiveness. It is to be. The glass transition point (hereinafter sometimes abbreviated as Tg) of the polyester is preferably 0 to 130 ° C, more preferably 10 to 85 ° C. When Tg is less than 0 ° C., for example, heat-resistant adhesiveness is inferior, or a blocking phenomenon occurs in which laminated films adhere to each other. On the contrary, when it exceeds 130 ° C., the stability and water dispersibility of polyester may be inferior. Therefore, it is not preferable.

  The polyurethane urethane is not particularly limited as long as it has a urethane bond, and the main component is obtained by polymerizing a polyol compound and a polyisocyanate compound.

  As the polyurethane, a urethane resin whose affinity for water is enhanced by introducing a carboxylate group, a sulfonate group, or a sulfuric acid half ester base can be used. The content of a carboxylate group, a sulfonate group, or a sulfuric acid half ester base is preferably 0.5 to 15% by mass.

  Examples of the polyol compound include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaprolactone. Polyhexamethylene adipate, polytetramethylene adipate, trimethylolpropane, trimethylolethane, glycerin, acrylic polyol, and the like can be used.

  Examples of the polyisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, and the like. it can.

  Here, the main structural components of the urethane resin may contain a chain extender, a crosslinking agent, and the like in addition to the polyol compound and the polyisocyanate compound.

  As the chain extender or crosslinking agent, ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine, or the like can be used.

  The polyurethane having an anionic group is, for example, a method of using a compound having an anionic group for polyol, polyisocyanate, chain extender, etc., or a method of reacting an unreacted isocyanate group of the produced polyurethane with a compound having an anionic group. Alternatively, it can be produced by a method of reacting a specific compound with a group having active hydrogen of polyurethane, but is not particularly limited.

  The anionic group in the polyurethane is preferably used as a sulfonic acid group, a carboxylic acid group, and an ammonium salt, lithium salt, sodium salt, potassium salt or magnesium salt thereof, and particularly preferably a sulfonic acid group.

  The amount of the anionic group in the polyurethane is preferably 0.05% by mass to 8% by mass. If it is less than 0.05% by mass, the water dispersibility of the polyurethane tends to be poor, and if it exceeds 8% by mass, the water resistance and blocking resistance tend to be inferior.

  Examples of the monomer component constituting the acrylic polymer include, for example, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. 2-ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Hydroxyl group-containing monomers such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N- Amide group-containing monomers such as methylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide and N-phenylacrylamide, amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate, glycidyl Epoxy group-containing monomers such as acrylate and glycidyl methacrylate, monomers containing carboxyl groups such as acrylic acid, methacrylic acid and salts thereof (lithium salt, sodium salt, potassium salt, etc.) or salts thereof can be used. Are copolymerized using one or more of them. Furthermore, these can be used in combination with other types of monomers.

  Examples of other types of monomers include epoxy group-containing monomers such as allyl glycidyl ether, sulfonic acids such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.). Monomers containing a carboxylic group such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.) or a salt thereof, Monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumar Acid monoester, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, etc. can be used vinyl chloride.

  Moreover, as said acrylic polymer, a modified acrylic polymer, for example, a block copolymer modified with polyester, urethane, epoxy, etc., a graft copolymer, etc. can be used.

  The Tg of the acrylic polymer is not particularly limited, but is preferably −10 to 90 ° C., more preferably 0 to 50 ° C., and most preferably 10 to 40 ° C. When an acrylic resin having a low Tg is used, the heat resistant adhesiveness tends to be inferior and blocking tends to occur. On the other hand, when the acrylic resin is too high, the adhesiveness may deteriorate and the film forming property may be inferior. The molecular weight of the acrylic polymer is preferably 50,000 or more, more preferably 300,000 or more from the viewpoint of adhesiveness.

  Examples of the acrylic polymer include a copolymer selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and acrylic acid.

  The acrylic polymer is preferably dissolved, emulsified or suspended in water and used as an aqueous liquid from the viewpoint of environmental pollution and explosion-proof properties during coating. Such water-based acrylic polymers are copolymerized with monomers having a hydrophilic group (acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and salts thereof, etc.) and emulsion polymerization using reactive emulsifiers and surfactants, It can be prepared by a method such as suspension polymerization or soap-free polymerization.

  In the present invention, the polyester, polyurethane, or acrylic polymer is preferably crosslinked.

  Examples of the crosslinking method include a method of crosslinking the polymer using a crosslinking agent.

  The crosslinking agent in the method of crosslinking using the above-mentioned crosslinking agent is not particularly limited, but functional groups present in the above-described polymer, such as carboxyl group, hydroxyl group, methylol group, amide group, etc. Any melamine-based crosslinking agent, oxazoline-based crosslinking agent, isocyanate-based crosslinking agent, aziridine-based crosslinking agent, epoxy-based crosslinking agent, methylolized or alkylolized urea-based, acrylamide-based Polyamide resins, amide epoxy compounds, various silane coupling agents, various titanate coupling agents, and the like can be used. In particular, a melamine-based crosslinking agent and an oxazoline-based crosslinking agent can be suitably used from the viewpoint of compatibility with a polymer, adhesiveness, and the like.

  For example, the melamine-based crosslinking agent is not particularly limited, but a melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting a methylolated melamine with a lower alcohol, or These mixtures can be used. Moreover, as a melamine type crosslinking agent, a monomer, the condensate which consists of a multimer more than a dimer, or a mixture thereof can be used. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used. The functional group has an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and an imino group type methylated melamine resin, a methylol group type melamine resin, or a methylol group type. Examples include methylated melamine resins and fully alkyl type methylated melamine resins. Among these, an imino group type melamine resin and a methylolated melamine resin are preferable, and an imino group type melamine resin is most preferable. Furthermore, an acidic catalyst such as p-toluenesulfonic acid may be used in order to promote thermal curing of the melamine-based crosslinking agent.

  The oxazoline-based crosslinking agent is not particularly limited as long as it has an oxazoline group as a functional group in the compound, but includes at least one monomer containing an oxazoline group, and at least one kind What consists of an oxazoline group containing copolymer obtained by copolymerizing other monomers is preferable.

  Monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be used, and one or a mixture of two or more thereof can also be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

  In the oxazoline-based cross-linking agent, the at least one other monomer used for the monomer containing the oxazoline group is not particularly limited as long as it is a monomer copolymerizable with the monomer containing the oxazoline group. Acrylates or methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylate-2-ethylhexyl, methacrylate-2-ethylhexyl, etc. Unsaturated carboxylic acids such as acid, methacrylic acid, itaconic acid and maleic acid, unsaturated nitriles such as acrylonitrile and methacrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide, N-methylol methacrylate Contains unsaturated amides such as amides, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, vinyl chloride, vinylidene chloride and vinyl fluoride. Halogen- [alpha], [beta] -unsaturated monomers, [alpha], [beta] -unsaturated aromatic monomers such as styrene and [alpha] -methylstyrene can be used, and these should be used alone or in a mixture of two or more. You can also.

  The isocyanate-based crosslinking agent is not particularly limited as long as it has an isocyanate group as a functional group in the compound, but use of a polyfunctional isocyanate compound containing two or more isocyanate groups in one molecule. Is preferred.

  As the polyfunctional isocyanate compound, a low-molecular or high-molecular aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate can be used. Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and trimers of these isocyanate compounds. Furthermore, an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly The terminal isocyanate group containing compound obtained by making it react with polymer active hydrogen compounds, such as ether polyols and polyamides, can be mentioned.

  In addition, when using an isocyanate compound as a crosslinking agent, it is also possible to use a block type isocyanate compound.

  The blocked isocyanate can be prepared by subjecting the above isocyanate compound and blocking agent to an addition reaction by a conventionally known appropriate method. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methyl etiketooxime, and cyclohexanone oxime. Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol ; Lactams such as ε-caprolactam, δ-valerolactam, ν-butyrolactam, β-propyllactam; aromatic amines; imides; acetylacetone, acetoacetate Active methylene compounds such as malonic acid ethyl ester; mercaptans; imines; ureas; diaryl compounds; and sodium bisulfite and the like.

  Epoxy-based crosslinking agent There is no particular limitation as long as the compound has an epoxy group as a functional group in the compound, but it is preferable to use a polyfunctional epoxy compound containing two or more epoxy groups in one molecule.

  Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A and oligomer thereof, diglycidyl ether of hydrogenated bisphenol A and oligomer thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and Polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl Examples include ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

  Examples of the cross-linking agent include phenol formaldehyde resins of condensates with formaldehyde such as alkylated phenols and cresols; adducts of urea, melamine, benzoguanamine, and the like with formaldehyde, and the adducts having 1 to 1 carbon atoms. And amino resins such as alkyl ether compounds composed of 6 alcohols.

  Examples of the phenol formaldehyde resin include alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amylphenol, 4,4′-sec-butylidenephenol, p-tert-butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl o-cresol, p-phenylphenol, xylenol, etc. Mention may be made of condensates of phenols and formaldehyde.

  Examples of amino resins include methoxylated methylol urea, methoxylated methylol N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. Are preferably methoxylated methylol melamine, butoxylated methylol melamine, methylolated benzoguanamine, and the like.

  The polymer and the cross-linking agent can be mixed and used at an arbitrary ratio. However, in order to express the effects of the present invention more remarkably, the cross-linking agent is 2 parts by mass with respect to 100 parts by mass of the polymer. It is preferable to add more than 50 parts by weight, more preferably 3-25 parts by weight. When the addition amount of the cross-linking agent is less than 2 parts by mass, the effect of addition is small, and when it exceeds 50 parts by mass, the adhesiveness tends to decrease.

  In the present invention, in addition to the above method, for example, a crosslinked polymer layer may be formed using a self-crosslinking type polymer in which a crosslinkable functional group is introduced into the above-described polymer. The crosslinking method in the case of this method is not limited. For example, thermal crosslinking may be used, and crosslinking using high-energy active rays such as ultraviolet rays, electron beams, and γ rays may be used.

  Further, various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, and the like within the range in which the effects of the present invention are not impaired in the crosslinked polymer layer, Pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents and the like may be blended.

  In particular, the addition of inorganic particles in the crosslinked polymer layer further improves the slipperiness and blocking resistance of the thermoplastic resin layer in the method of forming a crosslinked polymer layer on the thermoplastic resin layer. preferable. In this case, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, or the like can be used as the inorganic particles to be added. Inorganic particles used preferably have an average particle size of 0.005 to 5 μm, more preferably 0.01 to 3 μm, and most preferably 0.05 to 2 μm, although the mixing ratio to the resin in the laminated film is not particularly limited. The solid content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

  As the method for forming the crosslinked polymer layer, for example, a so-called coating method is applied in which a solution for forming the crosslinked polymer layer is applied to the surface of a film or sheet for forming the thermoplastic resin layer and dried. The method is preferred. When the thermoplastic resin layer is a biaxially stretched film, the step of applying the coating liquid in the method includes a method of coating the unstretched film and then stretching in at least one direction, a method of coating after longitudinal stretching Any method such as a method of applying to the film surface after the orientation treatment is possible. Especially, when using the polyester film which is a preferred embodiment, when producing the polyester film, the polyester film is applied before the completion of the crystal orientation of the film, and after stretching in at least one direction, the crystal orientation of the polyester film is changed. The so-called in-line coating method, which is completed, is a preferable method capable of exhibiting the effects of the present invention more remarkably.

  Various coating methods such as reverse coating method, gravure coating method, rod coating method, bar coating method, Mayer bar coating method, die coating method, spray coating method and the like can be used as the coating method of the coating liquid.

(4) Rubber layer The type of rubber used in the rubber layer constituting the thermoplastic resin laminate for decorative molding is appropriately selected depending on market requirements, the type of resin used for the base material of the plastic molded body, and the like. For example, natural rubber (NR), silicone rubber (Q), ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), acrylic rubber (ACM), fluoro rubber (FKM), etc. Or a mixture thereof.

  For the rubber layer, reinforcing fillers, pigments, dyes, anti-aging agents, antioxidants, mold release agents, flame retardants, thixotropic agents, dispersants for fillers, cross-linking agents, cross-linking aids as necessary And a crosslinking initiator etc. can be mix | blended.

  The rubber layer may be a single layer or multiple layers.

  The rubber layer preferably has a crosslinked structure in the end, but may be uncrosslinked in the state of the decorative molding thermoplastic resin laminate. For example, an uncrosslinked rubber laminate may be used as a molded body member and subjected to crosslinking treatment at the time of molding or after molding.

  In the thermoplastic resin laminate for decorative molding, as a method for laminating the rubber layer, for example, the thermoplastic resin layer and the rubber layer on which the decorative layer is laminated may be bonded with an adhesive, or an adhesive is used. Alternatively, a thermoplastic resin layer in which a rubber layer and a decorative layer are laminated may be directly laminated and bonded. In particular, the latter method is economically advantageous because the use of an adhesive for bonding a thermoplastic resin layer in which a rubber layer and a decorative layer are laminated and the bonding step can be omitted. Moreover, since a fall of a moldability can be suppressed with an adhesive bond layer, it is a preferable embodiment.

  In the thermoplastic resin laminate, the delamination strength between the rubber layer and the decorative layer is preferably 9 N / 20 mm or more. 10 N / 20 mm or more is more preferable, and 11 N / 20 mm or more is more preferable. Most preferably, even if a cut is made at the interface between the rubber layer and the decorative layer with a knife, the interface cannot be formed.

  When the delamination strength is less than 9 N / 20 mm, for example, when a molding process or a molded body is used, interface peeling between the rubber layer and the thermoplastic resin layer may occur.

  In the present invention, as a method for imparting the above-mentioned delamination strength, for example, a method of blending an adhesion improver into the rubber layer is preferable.

  As the adhesion improver, it is preferable to use a compound containing a reactive group active against radical reaction. Examples of this compound include acrylic acid derivatives, methacrylic acid derivatives, and allyl derivatives. Among them, derivatives having 2 or more, particularly 3 or more unsaturated bonds are preferable. These compounds are widely used as rubber co-crosslinking agents, and examples thereof include acrylic acid esters and methacrylic acid esters of polyhydric alcohols, allyl esters of polycarboxylic acids, triallyl isocyanurate, triallyl cyanurate, and the like. .

  The polyhydric alcohol acrylic ester or methacrylic ester is an ester compound obtained by esterifying two or more alcoholic hydroxyl groups of a polyhydric alcohol having two or more alcoholic hydroxyl groups with acrylic acid or methacrylic acid. Glycol diacrylate, ethylene glycol dimethacrylate, 1,3 butanediol diacrylate, 1,3 butanediol dimethacrylate, 1,4 butanediol acrylate, 1,4 butanediol methacrylate, 1,6 hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2,2'bis (4-acryloxydiethoxyphenyl) propane, 2,2'bis (4-methacrylate) Roxydiethoxyphenyl) prone, glycerol dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, tetramethylol methane diacrylate, tetramethylol methane dimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol tetraacrylate, tetramethylol tetramethacrylate, dimer diol diacrylate, da Merging all dimethacrylate and the like, particularly compounds containing three or more allyl esters or methacrylic esters are preferred. In addition, although said compound illustrated each single ester compound of acrylic acid and phthalacrylic acid, the form of mixed ester of acrylic acid and methacrylic acid may be sufficient.

  Examples of the allyl ester of polyvalent carboxylic acid include phthalic acid diarylate, trimellitic acid diarylate, and pyromellitic acid tetraarylate.

  Any one of the rubber film adhesion improvers may be used alone, or two or more may be used in combination. Further, the adhesion improver used in the present invention is not limited to the above exemplary compounds.

  The compounding amount of the adhesive property improving agent is 0.2 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total rubber component. On the contrary, when the amount exceeds 20 parts by mass, the effect of improving the adhesive strength reaches saturation, and the physical properties of the rubber decrease.

  Moreover, in order to accelerate | stimulate the expression of the adhesive improvement effect by an above described adhesive improvement agent, it is a preferable embodiment to mix | blend a peroxide compound with respect to a rubber layer. By the correspondence, the delamination strength between the rubber and the polyester film for rubber composite is further improved.

  The peroxide compound may be either acyl-based or alkyl-based, such as benzoyl peroxide, monochlorobenzoyl peroxide, 2,4 dichlorobenzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5. Bis (t-butylperoxy) hexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-bis-t-butylperoxy-3,3,5-trimethyl Examples include cyclohexane, di-t-butyl peroxide, t-butyl cumyl peroxide and the like.

  The compounding amount of the peroxide compound is preferably 0.05 to 10 parts by mass, particularly 1 to 8 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount is less than 0.05 parts by mass, the expression of the adhesion improving effect is not promoted, and when it exceeds 10 parts by mass, the above promoting effect is saturated and the physical properties of the rubber film are lowered.

When rubber other than silicone rubber is used, it is preferable to blend uncrosslinked silicone rubber in the rubber layer. The uncrosslinked silicone rubber is an organopolysiloxane represented by an average unit formula: RaSiO _{(4-a) / 2} . In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group, such as an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, vinyl group, allyl group, butenyl. Group, alkenyl group such as pentenyl group and hexenyl group, aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aralkyl group such as benzyl group and phenethyl group, 3 -Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group, etc. are mentioned, and preferred are methyl group, vinyl group, phenyl group and 3,3,3-trifluoropropyl group. In the above formula, a is a number in the range of 1.9 to 2.1. The silicone rubber component is represented by the above average unit formula. Specific siloxane units constituting the silicone rubber component are, for example, R ₃ SiO _1/2 units, R ₂ (HO) SiO _1/2 units, R ₂ SiO _2/2 units, RSiO _3/2 units and SiO _4/2 units.

The main component of the silicone rubber component is a linear polymer essentially comprising R ₂ SiO _2/2 units and R ₃ SiO _1/2 units or R ₂ (HO) SiO _1/2 units, and in some cases a small amount The RSiO _3/2 unit and / or the R ₃ SiO _1/2 unit can be partially branched. Moreover, a resinous polymer composed of R ₃ SiO _1/2 units and SiO _4/2 units can be blended as a part of the silicone rubber component. As described above, the silicone rubber component may be a mixture of two or more polymers.

  In addition, the molecular structure of the uncrosslinked silicone rubber component is not particularly limited, and examples thereof include a straight chain, a partially branched straight chain, a branched chain, and a resin. Is a linear polymer or a mixture containing a linear polymer as a main component.

Examples of the silicone rubber component include, for example, molecular chain both ends trimethylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylphenylpolysiloxane, molecule Trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, both ends of the chain trimethylsiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-capped dimethylsiloxane / methyl (3,3) 3,3-trifluoropropyl) siloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, both ends of molecular chain dimethyl Nylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylphenylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane Copolymer, dimethylvinylsiloxy group-capped dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group, dimethylvinylsiloxy group-capped dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer Dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, silanol group-blocked dimethylpolysiloxane, molecular chain Silanol group-blocked methylvinylpolysiloxane, molecular chain both-end silanol-blocked methylphenylpolysiloxane, molecular chain both-end silanol-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both-end silanol-blocked dimethylsiloxane / methylphenyl Siloxane copolymer, silanol group-capped dimethylsiloxane / methyl (3,3,3-trifluoropropyl) siloxane copolymer, both chain end-capped dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane Polymer, molecular chain both ends trimethoxysiloxy-blocked dimethylpolysiloxane, molecular chain both ends trimethoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethoxysiloxane Si-group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, trimethoxysiloxy-group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, R ₃ SiO _1/2 unit and SiO _4/2 unit comprising organopolysiloxane _copolymers, R 2 _{Si O 2/2} units and _RSiO consisting _3/2 units organopolysiloxane _copolymer, R 3 _{Si O 1/2} units and _R 2 _{SiO 2/2} units and RSiO _{3 /} Organopolysiloxane copolymer comprising ₂ units, and a mixture of two or more of these. The viscosity of the silicone rubber component at 25 ° C. is not particularly limited, but is practically preferably 100 centistokes or more, particularly 1,000 centistokes or more.

  The blending amount of the uncrosslinked silicone rubber is preferably 5 to 100 parts by mass, particularly 10 to 70 parts by mass with respect to 100 parts by mass of the ethylene propylene rubber. When the blending amount is less than 5 parts by mass, the improvement of the adhesion improving effect is not promoted. On the contrary, when the blending amount exceeds 100 parts by mass, the above promoting effect reaches saturation and is not economical. In addition, the heat resistance of rubber | gum may improve by mix | blending silicone rubber.

  Further, instead of blending uncrosslinked silicone rubber into the rubber layer, an uncrosslinked silicone rubber composition layer in which an adhesion improver is blended as an intermediate layer is interposed between the polyester for rubber composite and the rubber layer. The delamination strength between the rubber composite polyester and the rubber layer may be improved. In this case, the uncrosslinked silicone rubber can be the same as described above, and the adhesion improver can be the same as that blended in the rubber layer. And the compounding quantity of the adhesive improvement agent with respect to silicone rubber is 0.5-30 mass parts with respect to 100 mass parts of silicone rubbers in the case of the said methacrylic acid ester, Especially 1-20 mass parts is preferable, 0.5 mass part If it is less than 30%, the adhesive strength with the substrate film becomes insufficient, and if it exceeds 30 parts by mass, the strength is saturated, which is economically disadvantageous.

  The thickness of the uncrosslinked silicone rubber layer is preferably 0.0005 to 0.05 mm.

  If necessary, reinforcing fillers, pigments, dyes, antioxidants, antioxidants, mold release agents, flame retardants, thixotropic agents, filler dispersants, and the like can be blended. Moreover, a peroxide can be mix | blended as an adhesive improvement promoter for promoting the adhesive improvement effect by said adhesive improvement agent.

  As a method of blending the above compounding agent with rubber, for example, a method of using a rubber kneader such as a two-roll roll, a Banbury mixer, or a dough mixer (kneader) when producing a rubber compound is preferable. Moreover, when melt | dissolving rubber | gum in a solvent and forming into a film by the casting method, you may add and mix | blend at any stage after melt | dissolving a rubber compound in a solvent and producing a solution.

  The thermoplastic resin laminate for decorative molding of the present invention preferably has a delamination strength of 8 N / 20 mm or more between the rubber layer and the decorative layer after immersion in toluene (at 25 ° C. for 72 hours). 9N / 20mm or more is more preferable, and 10N / 20mm or more is more preferable. By setting the delamination strength between the rubber layer and the decorative layer to 8 N / 20 mm or more, the reliability with respect to the durability of the molded body is improved.

  The method for imparting the above properties is not limited, but it is preferable to arrange a layer made of at least one selected from polyester, polyurethane, or acrylic polymer between the rubber layer and the decorative layer.

  In the present invention, the polyester, polyurethane, or acrylic polymer preferably has a crosslinked structure.

  Examples of the crosslinking method include a method of crosslinking the polymer using a crosslinking agent.

  The polyester, polyurethane, or acrylic polymer or crosslinking agent may be the same as the intermediate layer provided between the thermoplastic resin layer and the decorative layer. The components in both layers may be the same or different.

  The intermediate layer made of at least one selected from the polyester, polyurethane, or acrylic polymer is preferably formed by the same method as described above.

  In addition, when providing the intermediate layer which consists of at least 1 sort (s) chosen from polyester, a polyurethane, or an acryl-type polymer between a decorating layer and a rubber layer as mentioned above, delamination strength is a rubber layer and bridge | crosslinking. The delamination strength means either the delamination strength between the polymer layer or the delamination strength between the crosslinked polymer layer and the decorative layer.

  In the present invention, as a method for producing the thermoplastic resin laminate for decorative molding, for example, an uncrosslinked rubber layer is laminated on the surface of the decorative layer, and the rubber layer is subsequently crosslinked to produce. The method is preferred. In the method, it is a more preferable embodiment that the rubber layer is blended with the above-mentioned adhesion improver.

  By the above method, a thermoplastic resin laminate for decorative molding that satisfies the above-mentioned delamination strength without using an adhesive economically can be produced.

  As a method of laminating a rubber layer on a thermoplastic resin layer in which a decorative layer is arranged, for example, a solution obtained by dissolving a rubber composition in a solvent is applied to a film or sheet made of a thermoplastic resin and dried to form a rubber layer. Examples thereof include a forming method, a method of forming a rubber layer by extruding a rubber composition under high pressure on a film or sheet made of a thermoplastic resin, and a calendar method. When liquid rubber such as liquid silicone rubber is used, it can be applied without dilution with a solvent.

  In the above production method, the crosslinking method may be, for example, thermal crosslinking, or may be crosslinking with a high energy active ray such as an electron beam or γ ray. In particular, the method using actinic radiation does not require the addition of additives for radical generation such as peroxides, so there is no deterioration in rubber properties due to residues of these additives, and it can be crosslinked efficiently and produced. It is suitable because of its high properties.

  In the present invention, it may be desired to change the surface roughness of the rubber film as appropriate. In such a case, as a means for controlling the surface roughness of the rubber film, for example, a cover sheet made of a film or fabric having a different surface roughness is stacked on the surface of the uncrosslinked rubber film so that the surface form of the cover sheet is made of rubber. It is known to transfer to the film surface. Specifically, as a means for imparting fine irregularities to the surface of a general rubber sheet, a polyethylene film or vinyl chloride film subjected to matting or embossing, or a filament fabric such as nylon taffeta or polyester taffeta is used as a cover sheet. The basis weight used is widely used.

  The above cover sheet is superimposed on the surface of the rubber layer at the time of crosslinking and is peeled off after the crosslinking is completed. As described above, in order to improve the delamination strength between the polyester film and the rubber layer, when an adhesion improver or the like is blended, the rubber layer and the cover sheet can be peeled off even if the cover sheet is peeled off after crosslinking. Since the peel strength between them is also improved, it is difficult to peel off the cover sheet. On the other hand, if the cover sheet is peeled before the crosslinking treatment, there is a problem that the rubber of the rubber film is chipped and adheres to the cover sheet.

  Therefore, when the surface roughness of the rubber layer is controlled by the cover sheet, it is preferable to perform a surface treatment for improving the peelability of the cover sheet. Moreover, you may use the film | membrane which consists of a raw material with low adhesive force with respect to a rubber layer, for example, a poly-4-methylpentene-1 or an ethylene methylmethacrylate copolymer, as a cover sheet. Moreover, a rubber film can be multilayered and the compounding quantity of an adhesive improvement agent can be decreased on the cover sheet side rather than the polyester side. Moreover, when performing bridge | crosslinking by electron beam irradiation, it is also a suitable method to perform the irradiation from the polyester film side. This method is preferable because the interlayer adhesion between the rubber layer and the polyester film is also improved.

(5) Resin molded body layer (base material)
The resin used for the base material of the plastic molded body of the present invention is appropriately selected according to market demands, and for example, any of a thermoplastic resin and a cured product of a thermosetting resin can be used.

  Examples of the thermoplastic resin include the same resins as those forming the thermoplastic resin layer that is a constituent layer of the thermoplastic resin laminate. The resin may be the same or different.

  Specific examples of the thermosetting resin include, but are not limited to, unsaturated polyester resins, vinyl ester resins, epoxy resins, and phenol resins.

  Among these, since the balance between heat resistance and mechanical properties is excellent, it is preferable to use a cured product of a thermosetting resin. Especially, the balance between heat resistance and mechanical properties is particularly excellent, and the cure shrinkage is small. It is more preferable to use an epoxy resin because of its characteristics.

  In the present invention, the base material of the plastic molded body is preferably a fiber reinforced plastic in which a resin selected from the above resins and fibers are combined. The fiber-reinforced plastic can increase the strength and elastic modulus of the molded body due to the reinforcing effect of the fibers, and can lead to weight reduction.

  Specific examples of the reinforcing fiber include glass fiber, carbon fiber, aramid fiber, alumina fiber, and boron fiber. Among these, carbon fibers are preferably used because they have excellent characteristics of high strength and high elastic modulus while being lightweight.

  As the reinforcing fibers, both short fibers and long fibers can be used. When emphasizing mechanical properties, it is preferable to use reinforcing fibers having a length of 10 cm or more because fiber-reinforced plastics having excellent properties of high strength and high elastic modulus can be obtained while being lightweight. . When emphasizing moldability, it is preferable to use reinforcing fibers having a length of 10 cm or less.

  Specific examples of the reinforcing fiber array structure include a single direction, two directions, and a random direction. Specific examples of the form of the reinforcing fiber include a mat, a woven fabric, and a knitted fabric. Among them, it is preferable to use a single-directional array structure because a fiber-reinforced plastic molded body having excellent properties of high strength and high elastic modulus can be obtained while being lightweight. Moreover, since it is excellent in handleability, it is preferable to use the thing of the form of a textile fabric or a knitting.

(6) Plastic molded body The plastic molded body of the present invention is preferably in the form of a sheet. Furthermore, the plastic molded body preferably has a curved portion. By taking advantage of the feature that it is possible to deal with complex shapes and is lightweight, this correspondence makes it possible to use electrical / electronic equipment parts, automotive equipment parts, personal computers, OA equipment, AV equipment, mobile phones, telephones, facsimiles, home appliances, toy supplies. It can be suitably used in various applications such as parts and casings of electrical / electronic devices.

  The molding method of the plastic molded body of the present invention may be appropriately selected depending on the constituent material of the molded body, the shape of the molded body, and the like, and examples thereof include press molding, draw molding, and vacuum molding.

  As a method for forming a plastic molded body of the present invention, for example, a thermoplastic resin laminate and a resin molded body (base material) may be combined and integrally molded, or after both are molded separately, You may bond together with an adhesive agent or an adhesive. When the former method is used and a thermosetting resin is used as the resin molding, the thermosetting resin may be cured in the molding process. A pre- or post-curing treatment may be performed before or after molding. Further, the rubber layer of the thermoplastic resin laminate may be molded in an un- or semi-crosslinked state and crosslinked after the molding step or after molding. Further, the thermoplastic resin laminate and the resin molded body may be directly bonded, or an adhesion improving layer may be formed between them.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, but may be implemented with appropriate modifications within a scope that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

  The measurement and evaluation methods employed in this specification are as follows.

1. Plane orientation degree (ΔP)
Using a sodium D line (wavelength 589 nm) as a light source and using an Abbe refractometer, the refractive index (Nz) in the longitudinal direction of the film, the refractive index (Ny) in the width direction, and the refractive index (Nz) in the thickness direction are measured. The degree of plane orientation (ΔP) was calculated from the equation.
ΔP = ((Nx + Ny) / 2) −Nz

2. Stress at 10% elongation A sample was cut with a single-blade razor into strips having a length of 180 mm and a width of 10 mm, respectively, in the longitudinal direction and the width direction of the polyester film having a crosslinked polymer layer. Next, the strip sample was pulled using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the 10% elongation stress (MPa) and elongation at break (%) in each direction were determined from the obtained load-strain curve. .

  The measurement was performed in an atmosphere of 25 ° C. under the conditions of an initial length of 40 mm, a distance between chucks of 100 mm, a crosshead speed of 100 mm / min, a recorder chart speed of 200 mm / min, and a load cell of 25 kgf. In addition, this measurement was performed 10 times and the average value was used.

3. Interlaminar peel strength Insert a knife at the interface between the rubber layer of the polyester film laminate and the polyester film (or anchor coat layer if there is an anchor coat layer on the polyester film surface), and apply stress to the part to generate interfacial debonding. The peel strength was measured by a T-type peel method according to JIS K6854.

4). Adhesive Durability After immersing the polyester film laminate in toluene adjusted to 25 ° C. for 72 hours, the sample was taken out, wiped off with toluene, and the delamination strength was measured by the above method.

5. Moldability (1) Mold moldability After printing on the polyester film laminate, contact heating with a hot plate heated to 100-140 ° C for 4 seconds, then mold temperature 30-70 ° C, pressure holding time 5 seconds And press-molded. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold is a cup shape, the opening has a diameter of 50 mm, the bottom has a diameter of 40 mm, a depth of 30 mm, and all corners are curved with a diameter of 0.5 mm. .

The moldability and finish of the five molded products molded under optimal conditions were evaluated and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (a) The molded product is not torn,
(B) the corner radius of curvature is 1 mm or less, and the printing deviation is 0.1 mm or less,
(C) Further, there is no appearance defect corresponding to ×: (d) The molded product is not torn,
(E) Corner radius of curvature is over 1 mm and 1.5 mm or less, or printing deviation is 0.1
greater than 0.2 mm and less than 0.2 mm,
(F) Furthermore, there is no appearance defect corresponding to x, and there is no problem in practical use. X: The molded product is broken or even if it is not broken, it falls under any of the following items (g) to (j) (G) A corner with a radius of curvature exceeding 1.5 mm (h) A large wrinkle and a poor appearance (i) A whitened film with reduced transparency (j) A printing deviation of 0.2 mm More than

(2) Vacuum moldability After 5 mm square printing is performed on the polyester film laminate, the film is heated with an infrared heater heated to 500 ° C. for 10 to 15 seconds, and then vacuum molded at a mold temperature of 30 to 100 ° C. Went. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 40 mm, the depth was 50 mm, and all corners were curved with a diameter of 0.5 mm. .

Five molded products that were vacuum-molded under the optimum conditions were evaluated for moldability and finish, and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (a) The molded product is not torn,
(B) the corner radius of curvature is 1 mm or less, and the printing deviation is 0.1 mm or less,
(C) Further, there is no appearance defect corresponding to ×: (d) The molded product is not torn,
(E) The radius of curvature of the corner exceeds 1 mm and is 1.5 mm or less, or printing misalignment
More than 0.1mm and 0.2mm or less,
(F) Furthermore, there is no appearance defect corresponding to x, and there is no problem in practical use. X: The molded product is broken or even if it is not broken, it falls under any of the following items (g) to (j) (G) A corner with a radius of curvature exceeding 1.5 mm (h) A large wrinkle and a poor appearance (i) A whitened film with reduced transparency (j) A printing deviation of 0.2 mm More than

Example 1
Polyethylene terephthalate (inherent viscosity 0.65 dl / g) pellets containing 0.04% by mass of amorphous silica having an average particle size (SEM method) of 1.5 μm are sufficiently dried in vacuum, and then heated at 280 ° C. for extrusion. It was supplied to a machine, extruded from a T-shaped base into a sheet shape, wound around a mirror casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method, and cooled and solidified. The unstretched film was stretched 3.0 times in the longitudinal direction while passing through a heating roll group at 105 ° C. to obtain a uniaxially oriented film. Both surfaces of this film were subjected to corona discharge treatment, and the following coating solutions were applied to both treated surfaces so that the thickness after drying was 0.15 μm. The coated uniaxially stretched film is guided to the preheating zone while being gripped with a clip, dried at 110 ° C., continuously stretched 3.2 times in the width direction in the heating zone of 125 ° C., and further at 235 ° C. A polyester film having a thickness of 100 μm was obtained by performing 6% relaxation in the direction and heat treatment for 6 seconds.

[Coating solution]
5 parts by mass of a methylolated melamine resin in a solid content ratio was mixed with 100 parts by mass of an ammonium salt type aqueous dispersion of a polyester resin having the following composition in terms of solid content to obtain a coating solution.
(Acid component)
Terephthalic acid / isophthalic acid / trimellitic acid / sebacic acid = 28/9/10/3 (mol%)
(Glycol component)
Ethylene glycol / neopentyl glycol / 1,4-butanediol = 15/18/17 (mol%)

[Formation of decorative layer]
A decorative layer forming ink obtained by mixing a binder resin (30 parts by mass), a dye (12 parts by mass) and a solvent (100 parts by mass) having the following composition on one side of the polyester film obtained by the above method. Was screen printed using a silk screen printer and dried at 100 ° C. for 60 minutes to obtain a decorated polyester film. The printed surface of the decorated polyester film was corona treated. Further, a coating solution containing 100: 3 (parts by mass) of the solid content ratio of Byron 30SS and Coronate HX on the corona-treated surface was applied to a thickness of 1 μm after drying using a coater. did. Next, a crosslinked polymer layer was provided by crosslinking at 160 ° C. Further, aging treatment was performed at 40 ° C. for 3 days.

(Decoration layer forming ink)
(A) Binder resin Polycarbonate resin (specific viscosity; 0.612, Tg; 192 ° C.):
The polycarbonate resin includes 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as “biscresol fluorene”) and 2,2-bis (4-hydroxyphenyl) propane (hereinafter “bisphenol”). A dihydric phenol (abbreviated as A ″) {biscresolfluorene: bisphenol A = 30: 70 (molar ratio)}, phosgene, and p-tert-butylphenol as a terminal terminator, Obtained.
(B) Dye Anthraquinone red dye (Arimoto Chemical Industry, Plas Red 8370)
(C) Solvent cyclohexanone / dioxolane = 50/50 (parts by mass)

[Thermoplastic resin laminate for decorative molding]
EPDM (manufactured by Nippon Synthetic Rubber, EP21; ethylene content: 34% by mass) as rubber, and zinc salt of 2-mercaptobenzimidazole (Ouchi Shinsei Chemical Co., Ltd., NOCRACK MBZ) as aging inhibitor A As the inhibitor B, 4,4- (α, α-dimethylbenzyl) diphenylamine (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., NOCRACK CD) was used, respectively, and kneaded by a conventional method at the following blending ratio.

(Composition composition)
(A) EPDM: 100.0 parts by mass (b) Polyethylene glycol (molecular weight 4000): 2.5 parts by mass (c) Stearic acid: 0.5 parts by mass (d) Anti-aging agent A: 1.5 parts by mass e) Anti-aging agent B: 0.7 parts by mass (f) Phenol formaldehyde resin: 2.0 parts by mass (g) MAF carbon: 30.0 parts by mass (h) FT carbon: 40.0 parts by mass (i) Polybutene : 15.0 parts by mass (j) N, N'-m phenylenedimaleimide: 1.5 parts by mass (k) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane: 5.0 Parts by mass

  The kneaded rubber was formed into a sheet having a thickness of 3 mm. This unvulcanized rubber sheet is cut into 1 cm square pieces, and these pieces are weighed so that the ratio to toluene is 30% by mass and put into a stirrer with a vacuum deaerator together with toluene. Under stirring for 15 hours, the strip was dissolved in toluene. Next, pentaerythritol tetraacrylate was added to the solution so as to be 8 parts by mass with respect to 100 parts by mass of the EPDM rubber, and after stirring uniformly, the vacuum deaerator was driven and under vacuum (gauge pressure: 750 mmHg) ) For 20 minutes and defoamed.

Next, the EPDM rubber solution obtained by the above dissolution and defoaming was supplied to a roll coater, and applied to the polyester film so that the thickness after drying was 0.15 mm. Then, it introduce | transduced into oven and dried at 80 degreeC. On the surface of the EPDM rubber, a mat processed film (Opylan X-60YMT4 manufactured by Mitsui Petrochemical Co., Ltd.) having a thickness of 0.035 mm made of a copolymer of poly-4-methylpentene-1 is applied to the EPDM rubber surface. The layers were stacked so as to face each other, and were continuously stacked while being pressed with a pressure roll of 5 kgf / cm. Furthermore, the obtained laminate was further continuously introduced into an electron beam irradiation apparatus, and pre-crosslinking was performed by irradiating an electron beam with an energy of 200 KV and 3 Mrad from the polyester film side. Subsequently, the cover sheet was peeled off to obtain a composite composed of an EPDM rubber layer and a polyester film. Then, this composite was further introduced into an electron beam irradiation apparatus, post-crosslinking was performed from the EPDM rubber layer side by electron beam irradiation of 200 KV and 30 Mrad, and a polyester film laminate was obtained and wound into a roll.
Table 1 shows the properties of the obtained decorative molding thermoplastic resin laminate.

  The decorative molding thermoplastic resin laminate obtained in this example had high delamination strength and good durability of the adhesion. Moreover, it is excellent in mold moldability and is suitable as a member of a molded body.

Example 2
In Example 1, a polyester film was obtained in the same manner as in Example 1 except that the application of the coating solution was stopped when the polyester film was produced.
Using the obtained polyester film, a thermoplastic resin laminate for decoration molding was obtained in the same manner as in Example 1. The results are shown in Table 1.

Example 3
In Example 1, a polyester film was obtained in the same manner as in Example 1 except that the blending of the methylolated melamine resin, which was a crosslinking agent for the coating solution used in the production of the polyester film, was stopped.
Using the obtained polyester film, a thermoplastic resin laminate for decoration molding was obtained in the same manner as in Example 1. The results are shown in Table 1.

Example 4
In Example 1, a polyester film was obtained in the same manner as in Example 1 except that the coating amount of the coating solution was changed to 30 μm as the thickness after drying at the time of production of the polyester film.
A polyester film laminate was obtained in the same manner as in Example 1 using the obtained polyester film. The results are shown in Table 1.

Example 5
Copolymer polyester chip having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 40 mol% of ethylene glycol units and 60 mol% of neopentyl glycol units as diol components. (A), 0.04% by mass of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method) of 1.5 μm, and a benzotriazole-based ultraviolet absorber (N) (Ciba -Chips (B) made of polyethylene terephthalate containing 0.67% by mass of Tinuvin 326) manufactured by Specialty Chemicals Co., Ltd. were dried. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 25:75. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.

  The obtained unstretched sheet was stretched 3.3 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the coating solution used in Example 1 was applied to both sides of the uniaxially stretched film. The coated uniaxially stretched film is guided to a preheating zone while being gripped with a clip, dried at 110 ° C., guided to a tenter, preheated to 120 ° C. for 10 seconds, and the first half of transverse stretching is 110 ° C. and the latter half is 100 ° C. The film was stretched 3.9 times. Furthermore, the first heat treatment (TS1) was 210 ° C. and the second heat treatment (TS2) was heat-set at 225 ° C. while performing a 7% relaxation treatment in the transverse direction, and a biaxially stretched polyester having a thickness of 100 μm. A film was obtained.

  In the heat setting zone, an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and the limit position where the shielding plate in each section does not contact the film Expanded and installed. Also in the cooling section after heating, section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C., and the clip temperature at the tenter outlet is set to 40. Measures were taken to prevent clip fusion to below ℃.

A thermoplastic resin laminate for decorative molding was obtained in the same manner as in Example 1 using the obtained polyester film. The results are shown in Table 1.
The obtained thermoplastic resin laminate for decorative molding had better moldability, higher vacuum quality, and higher quality than the polyester film laminate obtained in Example 1. .

Example 6
In Example 1, a polyester film was obtained in the same manner as in Example 1 except that the application of the coating solution was stopped when the polyester film was produced. Corona treatment was applied to both sides of the obtained polyester film, and furthermore, a coating solution was blended so that the solid content ratio of Byron 30SS and Coronate HX was 100: 3 (parts by mass) on both sides of the corona treatment. The film was dried so as to have a thickness of 1 μm after drying to provide a crosslinked polymer layer. Using the obtained polyester film, a thermoplastic resin laminate for decoration molding was obtained in the same manner as in Example 1. The results are shown in Table 1.
The obtained polyester film laminate had the same properties as the decorative molding thermoplastic resin laminate obtained in Example 1 and was of high quality.

Example 7
In Example 1, a polyester film was obtained in the same manner as in Example 1 except that an acrylonitrile butadiene rubber (NBR) composition was used as the rubber composition. Using the polyester film obtained in this example, a thermoplastic resin laminate for decorative molding was obtained in the same manner as in Example 1. The results are shown in Table 2.
The obtained decorative molding thermoplastic resin laminate had the same characteristics as the decorative molding thermoplastic resin laminate obtained in Example 1 and was of high quality.

Example 8
In Example 4, a polyester film was obtained in the same manner as in Example 4 except that the application of the coating solution was stopped when the polyester film was produced.
A thermoplastic resin laminate for decorative molding was obtained by the same method as in Example 4 using the obtained polyester film. The results are shown in Table 2.

Example 9
In Example 2, a decorative thermoplastic resin laminate was obtained in the same manner as in Example 2 except that an acrylonitrile butadiene rubber (NBR) composition was used as the rubber composition. The results are shown in Table 2.
The obtained decorative molding thermoplastic resin laminate had the same properties as the decorative molding thermoplastic resin laminate obtained in Example 2 and was of high quality.

Example 10
In Example 2, a thermoplastic resin laminate for decorative molding was obtained in the same manner as in Example 2 except that a chloroprene rubber (CR) composition was used as the rubber composition. The results are shown in Table 2.
The obtained decorative molding thermoplastic resin laminate had the same properties as the decorative molding thermoplastic resin laminate obtained in Example 2 and was of high quality.

Example 11
A glass fiber reinforced polypropylene resin sheet (thickness 3.7 mm) obtained by melt-impregnating a continuous glass fiber mat (a swirl roving mat subjected to needle punching) with a polypropylene resin as a core layer made of a fiber reinforced thermoplastic resin sheet. The fiber content was 40% by weight. The thermoplastic resin laminate for decorative molding obtained in Examples 1 to 5 was laminated on both sides of the core layer so that the decorative surface side of the thermoplastic resin laminate for decorative molding was the core layer side. Next, this is inserted into a curved mold, heated and pressed at a temperature of 200 ° C. and a pressure of 10 kg / cm ² by hot pressing to thermally seal the core layer and the surface layer, and then cooled to form a plastic molding with a curved structure A body (hereinafter abbreviated as a molded body) was obtained.
Since the surface of the obtained molded body had a highly smooth surface so that a map was projected, the appearance of printing was extremely excellent. Further, the dimensional accuracy of the molded body was good, and there was no distortion of the shape.

Comparative Example 1
In Example 11, a plastic molded body was obtained in the same manner as in Example 1 without laminating the thermoplastic resin laminate for decorative molding.
The obtained molded product had surface irregularities such as glass fiber embossing and the surface condition was not good. Therefore, although the same printing as the case where it was performed on the thermoplastic resin laminate for decorative molding used in Example 1 on the surface of the molded body, the appearance was not good.

Comparative Example 2
In Example 11, instead of the decorative molding thermoplastic resin laminate, an EPDM rubber sheet having a thickness of 250 μm was laminated, and a molding was obtained in the same manner as in Example 11.
Although the surface state of the obtained molded body was better than that of the molded body obtained in Comparative Example 1, the molded body obtained in Example 11 had surface irregularities such as partially raised glass fibers. The surface condition was not good compared. Moreover, in this comparative example, since the EPDM rubber sheet was thin and not integrated with the polyester film, it was difficult to handle and the operability during the production of the molded body was poor.

Comparative Example 3
In Example 11, instead of the thermoplastic resin laminate for decorative molding, a molded body was obtained in the same manner as in Example 11 using only a polyester film provided with a decorative layer in which the lamination of the rubber layer was stopped. .
Although the surface state of the obtained molded body was good, the dimensional accuracy and shape distortion of the molded body were inferior to those of the molded body obtained in Example 11.

Example 12
A carbon fiber woven fabric 4ply cut so that each side is a square with a side of 300 mm parallel to either warp or weft was laminated in a mold, and a peel ply and a resin distribution medium were laminated thereon. Next, bagging was performed using a nylon film, and the pressure was reduced to (atmospheric pressure−0.1) MPa using a vacuum pump. Next, the mold is kept at 90 ° C., 100 parts by mass of bisphenol A type epoxy resin (Japan Epoxy Resin, Epicoat 828), 3 masses of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Curazole 2E4MZ) A liquid epoxy resin composition RTM resin composition was blended.

The injection was terminated 5 minutes after the RTM resin composition flowed into the mold. Next, demolding was started 40 minutes after the RTM resin composition flowed into the mold, and a core layer made of a fiber-reinforced plastic member was obtained. An uncrosslinked acrylonitrile butadiene rubber (NBR) composition containing a peroxide having a thickness of 10 μm is laminated on both sides of the obtained core layer on the rubber surface of the polyester film laminate obtained in Examples 1 to 5. The laminated polyester film was laminated so that the rubber surface side was the core layer side. Furthermore, this was inserted into a curved mold and molded and cured by hot pressing at a temperature of 170 ° C. and a pressure of 10 kg / cm ² for 2 hours. Next, it was cooled to obtain a plastic molded body having a curved surface structure (hereinafter abbreviated as a molded body).

  The surface of the obtained molded body had a highly smooth surface so that a map was projected. Therefore, the appearance of printing was extremely excellent. Further, the dimensional accuracy of the molded body was good, and there was no distortion of the shape.

Comparative Example 4
In Example 12, a plastic molded body was obtained in the same manner as in Example 12 without laminating the thermoplastic resin laminate for decorative molding.
The obtained molded product had surface irregularities such as carbon fiber embossing and the surface condition was not good. Accordingly, although the same printing as that applied to the decorative molding thermoplastic resin laminate used in Example 1 was performed on the surface of the molded body, the appearance was not good.

Comparative Example 5
In Example 12, instead of the decorative molding thermoplastic resin laminate, an EPDM rubber sheet having a thickness of 250 μm was laminated, and a molding was obtained in the same manner as in Example 12.
Although the surface state of the obtained molded body was better than that of the molded body obtained in Comparative Example 4, the molded body obtained in Example 12 had surface irregularities such as partially raised carbon fibers. Compared with, surface condition was not good. Further, as in Comparative Example 2, since the EPDM rubber sheet was thin and not integrated with the polyester film, it was difficult to handle and the operability during the production of the molded body was poor.

Comparative Example 6
In Example 12, instead of the thermoplastic resin laminate for decorative molding, a molded body was obtained in the same manner as in Example 12 using only a polyester film provided with a decorative layer in which the lamination of the rubber layer was stopped. .
Although the surface state of the obtained molded body was good, the dimensional accuracy and shape distortion of the molded body were inferior to those of the molded body obtained in Example 12.

Example 13
In Example 12, the thermoplastic resin laminate for decorative molding obtained in Examples 7 to 11 was used, and the lamination of the uncrosslinked NBR composition carried out in the method of Example 12 was stopped. In the same manner as in No. 12, a molded body was obtained.
The obtained molded body had a surface state equivalent to those obtained in Example 12 and was of high quality.

Example 14
In Example 6, instead of the polyester film, using a thermoplastic resin laminate obtained by using a polycarbonate sheet having a thickness of 300 μm and an A-PET sheet having a thickness of 500 μm, a molded body was obtained in the same manner as in Example 12. Obtained.
The obtained molded body had a surface state equivalent to those obtained in Example 12 and was of high quality.

Example 15
In Example 1, a molded body was obtained in the same manner as in Example 1 except that the decoration of the thermoplastic resin laminate for decorative molding was changed from printing to aluminum metal deposition.
The obtained molded article had a metallic luster excellent in image clarity and was of high quality as a decorative glitter molded article.

  The plastic molded body of the present invention is formed by laminating a thermoplastic resin laminate comprising at least a thermoplastic resin layer / decorative layer / rubber layer on the surface of the plastic molded body so that the thermoplastic resin layer side is a surface layer. The surface smoothness of the thermoplastic resin layer and the print-through effect of the rubber layer have the advantage that extremely high surface smoothness can be obtained.

  In addition, since the strain that occurs during molding of the molded body can be reduced by utilizing the elasticity of rubber, for example, the surface state of the molded body can be improved as described above, and the distortion that occurs during molding can be reduced. Furthermore, the external force applied to the molded body in the use of the molded body can be relaxed by the elasticity of the rubber. For example, the durability of the plastic molded body can be improved. Can be granted.

  In addition, the thermoplastic resin laminate is provided with a decorative layer and has excellent surface characteristics as described above, and thus has an advantage that a molded body having high gloss and high decorativeness and design can be obtained.

  Further, as described above, the plastic molded body of the present invention is incorporated into the plastic molded body as a laminated body in which the thermoplastic resin layer is integrated as described above. Compared to the method of incorporating the molded article, there are advantages of improving workability when producing a molded body and reducing the occurrence frequency of defective products. Therefore, it is important to contribute to the industry.

Claims (9)

  A plastic molded body comprising a thermoplastic resin layer, a decorative layer, a rubber layer, and a resin molded body layer laminated in this order.   The plastic molding according to claim 1, wherein the decorative layer is at least a printed layer and / or a metal thin film layer.   The plastic molded body according to claim 1 or 2, wherein the resin molded body layer is a fiber-reinforced plastic layer.   The plastic molded body according to any one of claims 1 to 3, wherein the thermoplastic resin layer comprises an unstretched film or a sheet.   The plastic molded body according to any one of claims 1 to 3, wherein the thermoplastic resin layer is a biaxially stretched polyester film having a plane orientation degree of 0.005 to 0.15.   The plastic molded body according to any one of claims 1 to 5, wherein a polymer film layer made of at least one selected from polyester, polyurethane and acrylic polymer is disposed between the rubber layer and the decorative layer.   The plastic molded body according to claim 6, wherein a polymer film is disposed on a surface side of the thermoplastic resin layer in contact with the decorative layer.   The molded product according to any one of claims 1 to 7, wherein the plastic molded product is a sheet.   The plastic molding according to claim 8, wherein the plastic molding has a curved portion.