JP6506948B2 - Laminated film - Google Patents

Description

  The present invention is a laminated film provided on at least one surface of a substrate layer (II) with a skin layer (I) which has a matte appearance and reduces the generation of a squeaking noise, and in particular, a surface of an article, When laminated by thermoforming, insert molding, in-mold molding or the like on the surface of an article made of a resin molded article, the article is in dynamic contact with another article via the surface layer (I) of the laminated film. The present invention relates to a laminated film suitable for suppressing the generation of stagnant noise.

  Resin molded articles are widely used today as parts of various products such as vehicles, electric and electronic devices, OA (office automation) devices, home appliances, building materials, and sanitary products. These products usually consist of an assembly of multiple parts, which are placed adjacent to or in contact with each other by being fitted, abutted, superposed, screwed etc. Often. It is known that such an assembly generates a squeaking noise (scrubbing noise) when adjacent parts are in dynamic contact with each other and rub against each other due to vibration, rotation, twist, sliding, impact or the like. It is done. For example, a stagnant noise may be generated when the air outlet of an air conditioner or the housing of an audio device disposed in a car and a fitting component disposed in the periphery or inside thereof rub against each other due to vibration or the like. The above-mentioned stagnant sound is known as abnormal noise caused by the stick-slip phenomenon which occurs when two objects rub against each other, and is caused by properties different from mere resin sliding.

  The stick-slip phenomenon is understood as a phenomenon in which the frictional force fluctuates periodically and largely as shown in FIG. 8, and more specifically, occurs as shown in FIG. That is, as shown by the model in FIG. 9A, when a spring-connected object M is placed on a driving base moving at a driving speed V, the object M first moves at a driving speed V by the action of static friction. It moves rightward as shown in FIG. Then, when the force to be returned by the spring becomes equal to this static friction force, the object M slides in the direction opposite to the driving speed V. At this time, the object M is subjected to a dynamic friction force, so the slip stops at the point of FIG. 9 (c) when the force of the spring and this dynamic friction force become equal, that is, the object M adheres to the drive base. It moves in the same direction as the driving speed V (FIG. 9 (d)). This is called a stick-slip phenomenon, and as shown in FIG. 8, when the difference Δμ between the static friction coefficient μs and the friction coefficient μl at the lower end of the sawtooth waveform is large, it is said that a stagnant noise is easily generated. The dynamic friction coefficient is an intermediate value between μs and μl. Therefore, even if the absolute value of the static friction coefficient is small, if Δμ is large, it is likely that a stagnant noise will occur. These noises are a major cause of impairing the comfort and quietness of a car room, an office, and a housing room, and there is a strong demand for reduction of the noise.

  In the prior art, it is possible to suppress the generation of stagnant noise of a molded article by using a rubber-reinforced aromatic vinyl resin reinforced with a rubber having crystallinity such as ethylene / α-olefin rubber having a melting point as a molding material It is known (refer patent document 1 and patent document 2). However, it has not yet been noted that the molding material is laminated on the surface of a member, in particular, the surface of a member made of a resin molded product by thermoforming, insert molding, in-mold molding or the like.

  On the other hand, a decorative resin sheet provided with a transparent protective layer, a pattern layer on which a pattern showing letters, numbers, patterns, etc. is formed, and a support layer sequentially is insert-molded on the surface of a resin molded article, in-mold Techniques for laminating and decorating by molding or the like are already known. Specifically, after disposing the above-mentioned decorated resin sheet in the cavity of the injection molding die, melting of thermoplastic resin such as acrylic resin, polycarbonate resin, ABS resin, etc. toward the surface on the above-mentioned supporting layer side By injection-filling the product into the cavity, it is possible to form a resin molded product having the same shape as the cavity and at the same time adhere a decorative resin sheet to the surface thereof for integration (see FIG. 1).

  Conventionally, as the above-mentioned decoration resin sheet, a picture is provided on a transparent acrylic film, and a pictured insert film in which an ABS resin film is laminated as a base film on the picture is known (see Patent Document 3) ). In addition, on the back of the surface sheet made of transparent acrylic resin, a pattern ink layer whose binder resin is a mixture of acrylic resin and vinyl chloride / vinyl acetate copolymer, a mixture of acrylic resin and vinyl chloride / vinyl acetate copolymer A sheet for injection molding simultaneous decoration is known, in which an adhesive layer consisting of the above and a base sheet consisting of an ABS resin having a proportion of butadiene component of less than 20% by mass are laminated in this order (see Patent Document 4). However, these resin sheets are only for the purpose of decorating the surface of a resin molded product, and are not for the purpose of preventing stagnant noise, and in fact, the above-mentioned addition of which the surface is made of transparent acrylic resin The decorative resin sheet can not prevent stagnation noise.

  In addition, a sheet having a skin layer made of polycarbonate formed on at least one side of a base material layer made of a thermoplastic resin composition containing an ABS resin as a laminate having a layer made of a rubber reinforced aromatic vinyl resin 5) A layer made of a rubber reinforced aromatic vinyl resin having a glass transition temperature lower than that of the thermoplastic resin is laminated on one side or both sides of a base layer made of a thermoplastic resin having a glass transition temperature of 120 ° C. or higher A laminated body (Patent Document 6) is known. However, there is no disclosure of a configuration in which the rubber-reinforced styrenic resin having crystallinity is used as the skin layer.

  In addition, when parts made of thermoplastic resin are used for car interiors, for example, the driver may be dazzled by sunlight reflected on the parts surface, or the meter may not be easily visible. From the viewpoint of securing, the parts are required to have a matte appearance. In addition, in recent years, in the case of home appliances, cases such as office automation equipment, chassis, etc., a matt appearance is often required from the viewpoint of design. In addition, also when using for above-mentioned motor vehicle interiors, it is increasing from the viewpoint of the designability that the matte appearance is calculated | required similarly.

  Patent Document 7 discloses a matte acrylic resin film having a matte layer containing a matte material and a binder resin on an acrylic resin film substrate as a film having a matte appearance used for insert molding or in-mold molding. The difference between the degree of yellowness of the matte acrylic resin film after heating the surface temperature of the matte layer side to 200 ° C. and the degree of yellowness of the matte acrylic resin film before heating is 1.3 or less. A film is disclosed. However, such films can not prevent the generation of stagnant noise.

JP, 2011-137066, A JP, 2013-112812, A JP-A-11-091041 JP 2003-170546 A JP, 2005-007684, A JP, 2009-051207, A Unexamined-Japanese-Patent No. 2007-062194

  An object of the present invention is to provide a rubber-reinforced aromatic vinyl resin composition having crystallinity by a molding method such as thermoforming, insert molding, in-mold molding, etc. on the surface of an article, in particular, the surface of an article comprising a resin molded article. It is an object of the present invention to provide a laminated film suitable for suppressing the stagnant noise generated from the article and giving a matte appearance by coating the resin layer comprising the above.

  As a result of intensive studies to solve the above problems, the present inventors have found that a skin layer having a melting point in the range of 0 to 120 ° C. measured according to JIS K 7121 to 1987 is a rubber-reinforced aromatic vinyl resin (A And a matting material (Y), and the skin layer is laminated on a base material layer, and the dimensional change is ± 1% or less when left at 120 ° C. for 30 minutes. It has been found that the resin film having a matte appearance on the surface of the article and capable of suppressing the stagnation noise can be easily formed by a known method by using the laminated film in the range of 1. Thus, the present invention has been completed.

Thus, according to one aspect of the present invention, it is a laminated film comprising a skin layer (I) on at least one surface of a substrate layer (II) made of a thermoplastic resin, wherein the skin layer (I) is A thermoplastic resin composition containing a rubber-reinforced aromatic vinyl resin (A) and a matting material (Y), and the melting point of the surface layer (I) measured according to JIS K 7121-1987 is 0 A laminated film is provided, which has a range of -120 ° C, and a dimensional change of the laminated film when left to stand at 120 ° C for 30 minutes is ± 1% or less.
The laminated film of the present invention is excellent in heat resistance as apparent from the above-mentioned dimensional change rate, and therefore excellent in molding processability in thermoforming, insert molding, in-mold molding and the like. Therefore, by laminating the skin layer (I) of the laminate film of the present invention as the outermost layer on the surface of various articles by these molding methods, an article having a matte appearance and suppressing generation of stagnant noise Can be provided.

According to another aspect of the present invention, there is provided a process of disposing the laminated film of the present invention in a cavity of an injection mold, and a molded article of the laminated film in the cavity of the injection mold. And E. injecting the resin composition from the side opposite to the outermost surface layer (I).
According to another aspect of the present invention, there is provided an insert-molding film comprising the laminated film of the present invention.

According to another aspect of the present invention, there is provided a laminate in which the laminated film of the present invention is laminated on a resin molded product on the side opposite to the skin layer (I). The laminate is useful as a part of an article having at least two parts in contact with one another.
Furthermore, according to another aspect of the present invention, there is provided an article having at least two mutually contacting parts, wherein at least one of the parts comprises the laminate of the present invention, wherein the laminated film of the laminate An article is provided in which the skin layer (I) is in contact with other parts.

  Resin films made of rubber-reinforced aromatic vinyl resins may undergo expansion and contraction, tears on the film surface, wrinkles, cracks, etc. when placed under high temperature by thermoforming, insert molding, in-mold molding, etc. As a result, the appearance of the resulting laminate may be significantly impaired and the yield may be significantly reduced.

  According to the present invention, a resin layer comprising a thermoplastic resin composition containing a matting material (Y) and having crystallinity is laminated on a substrate layer to form a laminated film satisfying a predetermined dimensional change rate. Therefore, it is excellent in heat resistance, in particular, dimensional stability at the time of heating in thermoforming, insert molding, in-mold molding and the like. Moreover, since the laminated film of the present invention can be laminated on the surface of various articles, particularly the surface of a resin molded article, so that the skin layer (I) is the outermost layer, adjacent articles are in dynamic contact with each other. As a result, it is possible to suppress the generation of a stagnant sound when rubbing against each other, and at the same time, it is possible to give a matte appearance. Further, as described above, since the laminated film of the present invention is excellent in dimensional stability at the time of heating, it is excellent in vacuum formability, and is a resin by a forming method such as thermoforming, insert forming, in-mold forming Even when laminated to a molded article, the occurrence of defects such as tears, wrinkles and cracks is suppressed, and generation of stagnant noise is suppressed, and the outermost layer having a good matte appearance is imparted to a resin molded article can do.

It is a schematic sectional drawing explaining an example of the method of manufacturing the laminated body provided with surface layer (I) of laminated film of this invention as outermost layer by insert molding. It is a schematic sectional drawing which shows an example of the laminated body obtained by the manufacturing method of the insert molded article of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made by the laminated body of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made by the laminated body of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made by the laminated body of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made by the laminated body of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made by the laminated body of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made by the laminated body of this invention. It is a schematic perspective view which shows the type | mold used for evaluation of the vacuum formability in an Example and a comparative example. It is a schematic sectional drawing explaining the evaluation method of the vacuum formability in an Example and a comparative example. It is a schematic sectional drawing which shows the test body used by the stagnation sound evaluation in an Example and a comparative example. It is a schematic perspective view which shows the method of squeaky-sound evaluation in an Example and a comparative example. It is explanatory drawing of the stick-slip phenomenon. (A), (b), (c) and (d) are model diagrams of the stick-slip phenomenon.

Hereinafter, the present invention will be described in detail.
In the present invention, "(co) polymerization" means homopolymerization and / or copolymerization, "(meth) acrylic" means acrylic and / or methacrylic, and "(meth) acrylate" means , Acrylate and / or methacrylate.
Moreover, melting | fusing point (It may describe as "Tm" in this specification) measured according to JIS K 7121-1987 uses DSC (differential scanning calorimeter), constant temperature rising of 20 degreeC in 1 minute. It is the value which measured the endothermic change by speed and read the peak temperature of the obtained endothermic pattern.

  The laminated film of the present invention comprises a substrate layer (II) and a skin layer (I) laminated on at least one side of the substrate layer (II).

Skin layer (I)
The skin layer (I) is made of a thermoplastic resin composition containing a rubber-reinforced aromatic vinyl resin (A) and a matting material (Y). The melting point (Tm) of the surface layer (I) and the thermoplastic resin composition forming the same is the effect of reducing stagnation sound when laminated on the surface of other articles to prevent the occurrence of stagnation sound and the machine From the viewpoint of the target strength, it is necessary to be in the range of 0 to 120 ° C., preferably in the range of 10 to 90 ° C., and more preferably in the range of 20 to 80 ° C. As described above, the melting point (Tm) is obtained according to JIS K 7121-1987, but the number of endothermic pattern peaks in the range of 0 to 120 ° C is not limited to one, and two or more May be. Further, the Tm (melting point) observed in the range of 0 to 120 ° C. may be derived from the rubber-reinforced aromatic vinyl resin (A), particularly from the rubber portion (a1), or, the rubber-reinforced aromatic vinyl The additive may be derived from an additive contained in the resin (A), for example, a low molecular weight polyolefin wax having a number average molecular weight of 10,000 or less.

  The rubber-reinforced aromatic vinyl resin (A) comprises a rubber portion (a1) derived from a rubbery polymer and a (co) polymer portion (a2) having a structural unit derived from a vinyl monomer. The rubber portion (a1) preferably forms a graft copolymer in which the (co) polymer portion (a2) is graft polymerized. Therefore, the rubber-reinforced aromatic vinyl resin (A) is preferably at least composed of the graft copolymer and a (co) polymer portion (a2) which is not graft polymerized on the rubber portion (a1). Furthermore, the (co) polymer portion (a2) may contain a non-grafted rubber portion (a1) or other components such as additives.

  The rubber portion (a1) may be a homopolymer or a copolymer as long as it is rubbery (having rubber elasticity) at 25 ° C. The rubber portion (a1) may be composed of any of a diene polymer (hereinafter referred to as "diene rubber") and a non-diene polymer (hereinafter referred to as "non diene rubber"). Moreover, these polymers may be crosslinked polymers or non-crosslinked polymers. Among them, in the present invention, it is preferable that at least a part of the rubber portion (a1) is made of non-diene rubber, in view of the effect of preventing the stagnant sound of the skin layer (I). It is particularly preferred that all of a1) be composed of non-diene rubber.

  Non-diene rubbers include ethylene / α-olefin rubbers; urethane rubbers; acrylic rubbers; silicone rubbers; silicone / acrylic IPN rubbers; (co) polymers containing structural units derived from conjugated diene compounds The hydrogenated polymer (however, a hydrogenation rate is 50% or more) etc. which are formed by hydrogenation etc. are mentioned. The hydrogenated polymer may be a block copolymer or a random copolymer.

  In the present invention, it is preferable to use an ethylene / α-olefin rubber as the non-diene rubber from the viewpoint of the effect of preventing the stagnation noise of the skin layer (I). The ethylene / α-olefin rubber is a copolymer rubber containing a structural unit derived from ethylene and a structural unit derived from an α-olefin. As an α-olefin, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-hexene Eikosen etc. are mentioned. These α-olefins can be used alone or in combination of two or more. The carbon atom number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8 from the viewpoint of impact resistance. The mass ratio of ethylene: α-olefin in the ethylene / α-olefin rubber is usually 5 to 95:95, preferably 50 to 95:50 to 5, more preferably 60 to 95:40 to 5. When the mass ratio of ethylene: α-olefin is in the above range, the impact resistance of the resulting molded article is further excellent and preferable. The ethylene / α-olefin rubber may optionally contain a structural unit derived from a non-conjugated diene. Nonconjugated dienes include alkenyl norbornenes, cyclic dienes and aliphatic dienes, preferably 5-ethylidene-2-norbornene and dicyclopentadiene. These nonconjugated dienes can be used alone or in combination of two or more. The proportion of the nonconjugated diene to the total amount of the rubbery polymer is usually 0 to 10% by mass, preferably 0 to 5% by mass, and more preferably 0 to 3% by mass.

  In the present invention, it is preferable to use an ethylene / α-olefin rubber having a melting point (Tm) of 0 to 120 ° C. The Tm (melting point) of the ethylene / α-olefin rubber is more preferably 10 to 90 ° C., still more preferably 20 to 80 ° C. The fact that the ethylene / α-olefin rubber has a melting point (Tm) means that the rubber has crystallinity. Therefore, by using the ethylene / α-olefin rubber having such a melting point (Tm), the rubber-reinforced aromatic vinyl resin (A) constituting the skin layer (I) has a melting point in the range of 0 to 120 ° C. It can be made to express and it can make the epidermal layer (I) express the prevention effect of itching sound. When the rubber-reinforced aromatic vinyl-based resin (A) has such crystallinity, the occurrence of the stick-slip phenomenon is suppressed, and thus the skin layer (I) containing it dynamically contacts other parts. It is considered that the generation of a stagnant sound is suppressed.

  The Mooney viscosity (ML1 + 4, 100 ° C .; in accordance with JIS K 6300) of the ethylene / α-olefin rubber is generally 5 to 80, preferably 10 to 65, and more preferably 10 to 45. When the Mooney viscosity is in the above range, the moldability, the impact strength of the laminated film, and the appearance of the resulting laminate are further excellent and preferable.

    The ethylene / α-olefin rubber is preferably an ethylene / α-olefin copolymer which does not contain a non-conjugated diene component from the viewpoint of reducing the squeaking noise, and among these, ethylene / propylene copolymer, ethylene / 1-butene Copolymers and ethylene / 1-octene copolymers are more preferred, with ethylene / propylene copolymers being particularly preferred.

  The rubber portion of the component (A) is preferably composed entirely of non-diene rubber, in particular ethylene / α-olefin rubber, from the viewpoint of the squeak noise reduction effect, but the squeak noise reduction effect is not impaired Within the range, in addition to the non-diene rubber, it may be composed of the diene rubber. When the rubber portion of the component (A) is composed of the diene rubber in addition to the non-diene rubber, the vacuum formability and impact resistance of the laminate film and the appearance of the obtained laminate are further increased. It will be enough.

    Examples of diene rubbers include homopolymers such as polybutadiene and polyisoprene; butadienes such as styrene butadiene copolymer, styrene butadiene styrene copolymer, acrylonitrile styrene butadiene copolymer, acrylonitrile butadiene copolymer and the like Examples of such copolymers include styrene-isoprene copolymers, styrene-isoprene-styrene copolymers, and isoprene-based copolymers such as acrylonitrile-styrene-isoprene copolymers. These may be random copolymers or block copolymers. These can be used alone or in combination of two or more. The diene rubbery polymer may be a crosslinked polymer or an uncrosslinked polymer.

  In the present invention, the content of the rubber portion (a1) in the rubber-reinforced aromatic vinyl resin (A) is preferably 3 to 80% with respect to 100% by mass of the entire rubber-reinforced aromatic vinyl resin (A). %, More preferably 3 to 65% by mass, still more preferably 4 to 55% by mass, still more preferably 5 to 50% by mass, and particularly preferably 7 to 45% by mass. When the content of the rubber portion (a1) is in the above range, the laminated film of the present invention is excellent in the effect of reducing the stagnant sound, the dimensional stability, the vacuum formability, and the like.

  The (co) polymer portion (a2) of the rubber-reinforced aromatic vinyl resin (A) is composed of a structural unit derived from a vinyl monomer, and the vinyl monomer contains an aromatic vinyl compound as an essential component. You may contain and the compound which can be copolymerized with this aromatic vinyl compound optionally. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinyl Naphthalene etc. are mentioned. These compounds can be used alone or in combination of two or more. Among these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  As the compound copolymerizable with the aromatic vinyl compound, preferably, at least one selected from a vinyl cyanide compound and a (meth) acrylic acid ester compound can be used, and further, if necessary, these compounds may be used together with these compounds. Other polymerizable vinyl monomers can also be used. As such other vinyl monomers, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, etc. These may be used alone or in combination of two or more.

  Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethyl acrylonitrile, α-isopropyl acrylonitrile and the like. These compounds can be used alone or in combination of two or more. Among these, acrylonitrile is preferred.

  Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2 (meth) acrylate -Ethylhexyl, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. These compounds can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

  Specific examples of the maleimide compound include N-phenyl maleimide, N-cyclohexyl maleimide and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Specific examples of the above-mentioned hydroxyl group-containing unsaturated compounds include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3 -Hydroxy-2-methyl-1-propene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and the like. These compounds can be used alone or in combination of two or more.

  The lower limit value of the content of the structural unit derived from the above aromatic vinyl compound in the rubber-reinforced aromatic vinyl resin (A) can be copolymerized with the structural unit derived from the aromatic vinyl compound and the aromatic vinyl compound When the sum total of structural units derived from a compound is 100% by mass, it is preferably 40% by mass, more preferably 50% by mass, and still more preferably 60% by mass. The upper limit is usually 100% by mass.

  When the (co) polymer portion (a2) of the rubber-reinforced aromatic vinyl resin (A) contains structural units derived from an aromatic vinyl compound and a vinyl cyanide compound as structural units, it is derived from an aromatic vinyl compound The content of the structural unit is usually 40 to 90% by mass, preferably 55 to 85% by mass, based on 100% by mass of the total of the two, and the content of the structural unit derived from the vinyl cyanide compound When the total of both is 100 mass%, it is 10-60 mass%, Preferably it is 15-45 mass%.

  The rubber-reinforced aromatic vinyl resin (A) is, for example, an aromatic vinyl compound and optionally, in the presence of a rubbery polymer (a) containing a crystalline rubber component having a melting point (Tm) of 0 to 120 ° C. It can be produced by graft polymerization of a vinyl monomer (b) consisting of another vinyl compound copolymerizable with the aromatic vinyl compound. The polymerization method in this production method is not particularly limited as long as the above graft copolymer can be obtained, and known methods can be applied. The polymerization method may be emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these. In these polymerization methods, known polymerization initiators, chain transfer agents (molecular weight modifiers), emulsifiers and the like can be appropriately used.

  In the above production method, a graft copolymer obtained by graft polymerizing a (co) polymer of vinyl monomers with a rubbery polymer, and a vinyl copolymer which is not graft polymerized with a rubbery polymer are generally used. A mixture product with the (co) polymer of In some cases, the mixed product may include a rubbery polymer to which the (co) polymer is not graft polymerized. The rubber-reinforced aromatic vinyl resin (A) of the present invention has a rubber portion (a1) derived from a rubbery polymer and a (co) polymer portion (a2) having a structural unit derived from an aromatic vinyl monomer And the rubber portion (a1) preferably forms a graft copolymer in which the (co) polymer portion (a2) is graft-polymerized, and thus the graft copolymer produced as described above The mixed product of the (co) polymer and the (co) polymer can be used as it is as a rubber-reinforced aromatic vinyl resin (A).

  The rubber-reinforced aromatic vinyl resin (A) is a vinyl comprising an aromatic vinyl compound and, if desired, another vinyl compound copolymerizable with the aromatic vinyl compound, in the absence of the rubbery polymer (a) The (co) polymer (A ') produced by polymerizing a system monomer may be added. When this (co) polymer (A ') is added to the rubber-reinforced aromatic vinyl resin (A), it constitutes a (co) polymer portion (a2) which is not graft polymerized on the rubber portion (a1). It will be done.

  As described above, in the rubber-reinforced aromatic vinyl resin (A) of the present invention, the rubber portion may contain a diene rubber in addition to the non-diene rubber. As a method for producing a rubber-reinforced aromatic vinyl resin (A) containing a plurality of such rubbers, for example, a rubbery polymer containing a non-diene rubber polymer and a diene rubber polymer (a In addition to the method of graft polymerization of the vinyl monomer (b) in the presence of) and graft polymerization of the vinyl monomer (b) in the presence of a non-diene rubber polymer Obtained by mixing rubber reinforced aromatic vinyl resin and rubber reinforced aromatic vinyl resin produced by graft polymerization of vinyl monomer (b) in the presence of diene rubber polymer, etc. Can.

  The graft ratio of the rubber-reinforced aromatic vinyl resin (A) is usually 10 to 150%, preferably 15 to 120%, more preferably 20 to 100%, and particularly preferably 20 to 80%. When the graft ratio of the rubber-reinforced aromatic vinyl resin (A) is in the above range, the impact resistance and the vacuum formability of the laminated film of the present invention are further improved.

The grafting rate can be determined by the following formula (1).
Graft ratio (mass%) = ((S−T) / T) × 100 (1)
In the above formula, 1 gram of a rubber-reinforced aromatic vinyl resin (A) is charged into 20 ml of acetone, and shaken at 25 ° C. for 2 hours with a shaker, then at 5 ° C. Mass (g) of the insolubles obtained by centrifuging for 60 minutes in a centrifuge (rotational speed: 23,000 rpm) and separating the insolubles from the solubles, T is a rubber-reinforced aromatic vinyl It is mass (g) of the rubber part (a1) contained in 1 gram of system resin (A). The mass of the rubber portion (a1) can be determined by the method of calculating from the polymerization formulation and the polymerization conversion rate.

  The grafting ratio is, for example, the kind and amount of chain transfer agent used in graft polymerization when producing a rubber-reinforced aromatic vinyl resin (A), the kind and amount of polymerization initiator, monomer components at the time of polymerization The addition method, the addition time, the polymerization temperature and the like can be appropriately selected.

  The limiting viscosity (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component (hereinafter, also referred to as “acetone-soluble component”) of the rubber-reinforced aromatic vinyl resin (A) in the thermoplastic resin composition of the present invention is It is usually 0.05 to 0.9 dl / g, preferably 0.07 to 0.8 dl / g, more preferably 0.1 to 0.7 dl / g. When the intrinsic viscosity is in the above range, the impact resistance and the moldability of the resin composition become better.

  The measurement of the intrinsic viscosity [η] can be performed by the following method. First, the acetone-soluble component of the rubber-reinforced aromatic vinyl resin (A) was dissolved in methyl ethyl ketone to make five different concentrations. The limiting viscosity [η] was determined from the result of measuring the reduced viscosity at each concentration at 30 ° C. using a Ubbelohde viscosity tube. The unit is dl / g.

  The intrinsic viscosity [粘度] is, for example, the type and amount of a chain transfer agent used when graft polymerizing a rubber-reinforced aromatic vinyl resin (A), the type and amount of a polymerization initiator, and the monomer at the time of polymerization It can adjust by selecting the addition method and addition time of a component, superposition | polymerization temperature, superposition | polymerization time etc. suitably. In addition, a rubber-reinforced aromatic vinyl resin (A) is mixed with a (co) polymer (A ′) having an intrinsic viscosity []] different from the intrinsic viscosity [η] of the acetone-soluble component. Can.

Next, the matte material (Y) will be described.
The matting material (Y) according to the present invention is not particularly limited as long as it gives a molded article having a matte tone (matt appearance) on the surface. In the present invention, those comprising an inorganic material (metal or inorganic compound) (hereinafter referred to as “inorganic matting material”) and those comprising an organic material (polymer) (hereinafter “organic matting” Or any combination of these.
The shape of the matting material (Y) is not particularly limited, and examples thereof include a spherical shape, an oval spherical shape, a linear shape, a plate shape, a polyhedron, an irregular shape and the like, and a hollow portion may be provided. In addition, the size of the matte material (Y) is also not particularly limited.
Examples of inorganic matting materials include, as powdery and granular materials, calcium carbonate, magnesium carbonate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, calcium oxide, silicon oxide, silicon oxide, magnesium hydroxide, magnesium sulfate , Barium sulfate, silicates, talc, mica, kaolin, glass flakes, etc. in the form of microballoons, glass balloons, phenolic resin balloons etc., in the form of fibers, glass fibers, carbon fibers, metal fibers, Examples of the whisker-like carbon fibers include ceramic whiskers and titanium whiskers.
Examples of organic matting agents include crosslinked resins (crosslinked acrylic resins, etc.) polymerized using unsaturated carboxylic acid alkyl ester monomers and a crosslinking agent, unsaturated nitrile monomers and aromatic vinyl monomers. A crosslinked resin (crosslinked acrylonitrile styrene resin, etc.) polymerized using a monomer and a crosslinking agent can be mentioned.
As the above-mentioned matting material (Y), an inorganic type matting material is preferable. When an inorganic matting material is used as the matting material (Y), the matted appearance of the obtained laminate and the other parts are contacted while maintaining the flexibility and vacuum formability of the laminated film. The suppression effect of the generation of stagnant noise at the time of is further excellent and preferable.
The proportion of the matting material (Y) contained in the thermoplastic resin composition is preferably 1 to 20 parts by mass, more preferably 100 parts by mass of the rubber-reinforced aromatic vinyl resin (A). Is 2 to 15 parts by mass, more preferably 3 to 12 parts by mass. If the matting material (Y) contained in the laminate film of the present invention is in the above range, the matte appearance of the obtained laminate and the other parts, while maintaining the flexibility and vacuum formability of the film The effect of suppressing the generation of a stagnant sound upon contact is further excellent and preferred.

  The thermoplastic resin composition may further optionally contain an additive other than the matting material (Y). As such additives, low molecular weight oxidized polyethylene (c1), ultra high molecular weight polyethylene (c2), polytetrafluoroethylene (c3) as described in JP-A-2011-137066, low molecular weight (e.g. Average molecular weight 10,000 or less) polyolefin wax etc. are mentioned.

  As such a polyolefin wax, the polyethylene wax etc. which exist in 0-120 degreeC of melting | fusing point are mentioned. When a polyolefin wax having such a melting point or other additives having a melting point of 0 to 120 ° C. is added to the rubber-reinforced aromatic vinyl resin (A), the rubber-reinforced aromatic vinyl resin (A) The effect of the present invention can be obtained even if the rubber portion of (1) does not have a melting point (Tm). These additives can be used singly or in combination of two or more.

Moreover, as other additives, antioxidants, ultraviolet light absorbers, weathering agents, anti-aging agents, fillers, antistatic agents, flame retardants, anti-fog agents, lubricants, antibacterial agents, anti-mold agents, tackifiers And plasticizers, colorants, graphite, carbon black, carbon nanotubes, pigments (for example, having infrared absorbing and reflecting ability, including functional pigments). These may be used alone or in combination of two or more. These additives can be blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the rubber-reinforced aromatic vinyl resin (A).
The rubber-reinforced aromatic vinyl resin (A) may contain other resins as long as the object of the present invention is not impaired.

Base layer (II)
The base material layer (II) is made of a thermoplastic resin and is laminated on the skin layer (I) to impart heat resistance to the entire laminated film, and dimensional change when left at 120 ° C. for 30 minutes There is no particular limitation as long as the rate is in the range of ± 1%. Therefore, the thermoplastic resin constituting the substrate layer (II) is formed by laminating the kind of the thermoplastic resin composition constituting the skin layer (I), the thickness of the skin layer (I), and the laminated film of the present invention It differs according to the material etc. of the goods of the other party.

  As the thermoplastic resin constituting the substrate layer (II), a thermoplastic resin having high heat resistance is preferable, and in general, the dimensional change rate when left at 120 ° C. for 30 minutes is in the range of ± 1%. For example, the same dimensional change rate can be given to the entire laminated film. Accordingly, the dimensional change of the thermoplastic resin constituting the substrate layer (II) when it is left at 120 ° C. for 30 minutes is preferably ± 1% or less, more preferably ± 0.8% or less, ± 0.5% The following are more preferable, and ± 0.4% or less is particularly preferable.

  Specific examples of the thermoplastic resin constituting the substrate layer (II) include aromatic vinyl resins (for example, styrene resins, rubber-reinforced styrene resins, acrylonitrile / styrene resins, and other aromatic vinyl compounds Co) polymers etc., polyolefin resin (eg polyethylene resin, polypropylene resin, ethylene-α-olefin resin etc), polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, saturated Polyester resin, polycarbonate resin, acrylic resin (for example, (co) polymer containing a structural unit derived from (meth) acrylic acid ester compound, fluorine resin, ethylene / vinyl acetate resin, polyamide resin Etc. These can be used singly or in combination of two or more. Among these, rubber-reinforced styrene resins having enhanced heat resistance by containing structural units derived from maleimide compounds such as α-methylstyrene, N-phenyl maleimide, N-cyclohexyl maleimide, α-methyl styrene, N-phenyl Heat resistance is enhanced by alloying with a rubber-reinforced styrenic resin containing a (co) polymer, whose heat resistance is enhanced by containing a structural unit derived from a maleimide compound such as maleimide or N-cyclohexyl maleimide, or polycarbonate resin. Preferably, the rubber-reinforced styrenic resin is used.

  When the thermoplastic resin constitutes the substrate layer (II), it preferably has a glass transition temperature higher than that of the skin layer (I), and has a glass transition temperature higher than that of the skin layer (I) by 10 ° C. or more. It is more preferable that the glass transition temperature is 20 ° C. or more higher than the skin layer (I). The glass transition temperature of the substrate layer (II) is 120 ° C. or higher, preferably 120 to 220 ° C., more preferably 130 to 190 ° C., still more preferably 140 to 170 ° C., particularly preferably 145 to 160 ° C. When the glass transition temperature is 120 ° C. or more, the heat resistance of the obtained laminated film is further sufficient, which is preferable.

  The thermoplastic resin constituting the substrate layer (II) includes an antioxidant, an ultraviolet absorber, a weathering agent, an antiaging agent, a filler, an antistatic agent, a flame retardant, an antifogging agent, a lubricant, an antibacterial agent, Fungus agent, tackifier, plasticizer, colorant, graphite, carbon black, carbon nanotube, pigment (for example, having infrared absorbing and reflecting ability, including a functional pigment added), etc. It can also be added in the range which does not impair. These can be used singly or in combination of two or more.

Laminated Film The laminated film of the present invention can be produced, for example, by a method which can be used for producing thermoplastic films and sheets, for example, solution casting, melt extrusion, melt pressing, coextrusion and the like. Although melt extrusion and coextrusion are excellent for large-scale production, solution casting and melt pressing are also useful for small scale, special purpose, and quality evaluation purposes. In the melt extrusion method, a T-die method or an inflation method is used. In the melt pressing method, the calendar method is used.

  The T-die method has the advantage of being able to produce at high speed, in which case the resin temperature during molding should be a temperature above the melting temperature and below the decomposition temperature of the resin, generally a temperature of 150-250 ° C. Is appropriate.

  The specification and molding conditions of the molding machine of the inflation method are not particularly limited, and conventionally known methods and conditions can be used. For example, the bore diameter of the extruder is 10 to 600 mm, and the bore diameter D and the ratio L / D of the length L from the bottom of the hopper to the tip of the cylinder are 8 to 45. The die has a shape generally used for inflation molding, and has, for example, a channel shape such as a spider type, a spiral type, or a stacking type, and the diameter is 1 to 5000 mm. As a molding machine of the calendar method, any of serial type, L type, inverted L type, Z type, etc. can be used, for example.

  Furthermore, the laminated film of the present invention may be produced, for example, by producing a single-layer film by T-die molding, inflation molding or the like, and then performing heat lamination (heat welding) or extrusion lamination. In addition, multilayer films may be produced at one time without producing a single layer film by multilayer extrusion using a T-die multilayer extruder or the like.

The thickness of the skin layer (I) of the laminated film of the present invention thus obtained is usually 25 to 600 μm, preferably 50 to 500 μm, more preferably 75 to 400 μm. When the thickness is in this range, not only the generation of stagnant noise is suppressed but also the film formability at the time of producing a single layer film by T-die molding, inflation molding, etc., laminated film by lamination, multilayer extrusion molding etc. Is preferable because it is possible to obtain a laminate excellent in the adhesion between the base material layer and the skin layer in the production of the above and in the appearance.
The thickness of the substrate layer (II) of the laminated film of the present invention thus obtained is usually 25 to 1200 μm, preferably 50 to 1000 μm, and more preferably 75 to 800 μm. When the thickness is in this range, not only the generation of stagnant noise is suppressed but also the film formability at the time of producing a single layer film by T-die molding, inflation molding, etc., laminated film by lamination, multilayer extrusion molding etc. Is preferable because it is possible to obtain a laminate excellent in the adhesion between the base material layer and the skin layer in the production of the above and in the appearance. The total thickness of the laminated film of the present invention obtained in this manner is usually 50 to 1800 μm, preferably 100 to 1500 μm, more preferably 150 to 1200 μm. When the thickness is in this range, the productivity of the laminated film (curling does not occur, the winding property, etc.) is good, and the generation of stagnant noise can be sufficiently reduced, and the surface of the obtained laminate is broken. The appearance is further sufficient without causing appearance defects such as wrinkles and cracks, which is preferable.

  In the laminated film of the present invention, the skin layer (I) may be directly laminated on the surface of the base material layer (II), but if necessary, the adhesive layer and the pattern may be used as long as the effects of the present invention are not lost. Another layer such as a layer or a layer made of recycled resin produced at the time of production can also be interposed between the skin layer (I) and the substrate layer (II).

A laminate obtained by laminating a laminate film The laminate film of the present invention can be laminated on the surface of an article with the substrate layer (II) side facing the article. In this case, since the outermost layer on the surface side of the obtained laminate is the skin layer (I) of the laminated film of the present invention, when another article is in dynamic contact with the skin layer (I) It is possible to suppress the generation of stagnation noise. Thus, by laminating the laminated film of the present invention on the surface of an article, it is possible to create a laminate having a matte appearance and a surface in which the generation of stagnant noise is suppressed.

  The laminated film of the present invention may be adhered to the surface of the article using an adhesive, but is excellent in heat resistance, flexibility and vacuum moldability, so insert molding using an injection molding die It is suitable for laminating on the surface of the above-mentioned article by a method (film insert molding method). Schematically, the process of disposing the laminated film of the present invention in the cavity of an injection mold, and the outer layer (I) which is the outermost layer of the resulting laminate in the cavity of the injection mold An insert-molded article or laminate can be produced by the step of injecting the resin composition from the opposite side of More specifically, when the laminate film of the present invention is provided with the skin layer (I) only on one side of the substrate layer (II), the above resin composition is injected to the side of the substrate layer (II), When the laminate film of the present invention is provided with the skin layer (I) on both sides of the substrate layer (II), the above-mentioned resin composition comprises the insert molded article, ie, the skin layer (I) forming the outermost layer of the laminate. Is injected on the other side. The laminated film of the present invention may have another layer on the side from which the above resin composition is injected, that is, another layer between the laminated film of the present invention and an article on which the film is laminated. May intervene.

  More specifically, the laminated film of the present invention can be used for insert molding in the process illustrated in FIG. First, as shown in FIG. 1A, the laminated film 1 of the present invention is disposed between a male mold 11 and a female mold 12 of an injection mold. At that time, the skin layer (I) of the laminated film 1 of the present invention is oriented to the female die 12 and the base layer (II) is oriented to the male die 11. Thereafter, the laminated film 1 is brought into close contact with the inner surface of the female mold 12 by using suction means such as the suction holes 13 arranged in the female mold 12. Since the laminated film 1 has flexibility, it can be easily adhered along the inner surface of the female die 12 to form a film structure 1a having a predetermined shape (see FIG. 1 (B)). Although not shown in FIG. 1A, the laminated film 1 may be fixed by, for example, a frame-like sheet clamp.

  Next, the male mold 11 and the female mold 12 are clamped, and a thermoplastic resin composition in a heated and molten state or a room temperature curing is obtained from the inlet 14 formed in the male mold 11 in the cavity formed by both molds. The molding material 2 which consists of a heat-resistant or thermosetting resin composition is supplied (refer FIG.1 (C)). When the molding material 2 consists of a thermoplastic resin composition or a thermosetting resin composition, the laminated film 1 (film structure 1a) may be preheated. Then, after the molding material 2 is solidified by cooling or the like, the mold is opened and the integrated laminate 5 is taken out. At this time, if there is an unnecessary portion of the laminated film, it is trimmed appropriately. Through the above steps, a laminate 5 is obtained in which the laminate film 1 is joined as the laminate 4 on the surface of the resin molded part 3 made of the thermoplastic resin composition or the cured resin composition (see FIG. 1 (D)). . The laminate 5 is provided with the skin layer (I) of the laminated film 1 as the outermost layer, so that generation of stagnant noise when another article dynamically contacts the outermost layer is suppressed.

  Although the manufacturing method using FIG. 1 demonstrated trimming an unnecessary part of laminated | multilayer film, this invention is not limited to this. For example, in the case of producing a laminate 5 as shown in FIG. 2, the laminated film of the present invention is cut to a predetermined size and placed at a predetermined position inside an injection molding die. Molding materials can be introduced. FIG. 2 shows the laminate 5 in which the two laminated parts 4 are formed on the surface of the resin molded part 3. As a method of manufacturing such a laminated body 5, the molding material injection step of FIG. A method of forming a plurality of laminated portions 4 by performing only once, or a method of forming the laminated portions 4 by performing a molding material injection step a plurality of times can be adopted.

  The thermoplastic resin composition that can be used as the molding material 2 includes, for example, polystyrene resin, styrene / acrylonitrile copolymer, styrene / acrylonitrile / methyl methacrylate copolymer, styrene / acrylonitrile / N-phenylmaleimide copolymer, Aromatic vinyl resins such as rubber reinforced styrene resin (ABS resin, AES resin, ASA resin, MBS resin etc.), acrylic resin (polymethyl methacrylate etc.), polyolefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, Polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate etc.), polycarbonate resin, polyarylate resin, polyacetal resin, polyamide resin, fluorocarbon resin, polyphenylene ether, polyphen Sulfide, imide resins, polyether ketone, ketone resins such as polyether ether ketone, polysulfone, sulfonated resins polyether sulfone, biodegradable plastic, plant-derived resin such as polylactic acid and the like.

  As a curable resin composition which can be used as the molding material 2, for example, a curable resin (prepolymer etc.) comprising acrylic resin, phenol resin, furan resin, acrylic silicone resin, urethane resin, melamine resin, epoxy resin etc., Examples thereof include uncured curable compositions containing a curing agent (polymerization initiator and the like) and the like.

  The laminate 5 obtained by the present invention is provided with the skin layer (I) of the laminate film of the present invention as the laminate part 4 as the outermost layer, so that plastic, crosslinked rubber (including vulcanized rubber), fiber assembly When it comes into dynamic contact with other articles made of metals (including alloys), glass, ceramics, etc., the generation of stagnant noise is suppressed. Therefore, in an article having at least two mutually contacting parts, when one part is formed of the laminate 5 and is brought into contact with another part at the location of the laminated portion 4, a stagnant noise due to vibration, twist, impact or the like The effect of suppressing the occurrence can be obtained. Even when the two parts are always in contact by adhesion, contact or the like, they are arranged with a predetermined gap, and one or both are moved or deformed by vibration, twist, impact or the like to be in dynamic contact Even in the case of (for example, surface contact, line contact, point contact), the effect of suppressing the generation of the above-mentioned stagnant noise is exhibited. Specifically, as shown in FIG. 3A, an article in contact with each other with one side of each of two parts 50 in a state in which the parts are in contact with each other, and as shown in FIGS. The article etc. which are contacting in the state where it fitted in the crevice formed in 50, etc. are mentioned.

  A specific example of an article in which parts are in contact with each other is, as shown in FIG. 3B, a contact in which one end of the part 60 is fitted in a complementary recess formed in the part 50. An article being in contact with each of the two complementary recesses formed in the corners of the part 50, as shown in FIG. 3C, with each end of the part 60 in a snug fit, An article in which each end of the part 60 is in close-fitting contact with complementary recesses formed in each of two substantially parallel arranged parts 50, as shown in FIG. 3E. As shown in FIG. 5, a component 60 having an outer surface dimension equal to the inner surface dimension of the component 50 is inserted into the component 50 in a nested manner, with the inner and outer surfaces of the two closely fitted. The article etc. which are contacting are mentioned. Also, the two parts 50 and 60 in the article of the present invention do not have to be a close fit with each other, but with one another with a certain amount of clearance or play, as shown in FIG. The article may be such that when an external force such as an impact is applied to the article, the contact and non-contact repeat each other.

  3A to 3F, the component 50 has a structure in which the laminated film 1 of the present invention is laminated as the laminated portion 4 on at least the surface contacting the component 60, and the component 60 is the outermost layer of the component 50 (I Since it is in contact with the above, it is possible to obtain the effect of suppressing the generation of stagnant noise due to vibration, twisting, impact or the like.

  The laminates 5, 50 obtained according to the present invention consist of at least two mutually contacting parts such as vehicles, electric and electronic devices, OA (office automation) equipment, home appliances, building materials, sanitary products etc. It is suitable as a component that constitutes an article, and is suitable, for example, as a component of an article composed of components that fit together in a recess or a hole, such as automobile interior materials.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples. In the examples, parts and percentages are by mass unless otherwise specified.

Preparation Examples of Molding Resin Molding resins S1 to S13 and B1 to B3 were prepared as follows. The following raw materials [P], [Q], [R] and [T] were mixed by the Henschel mixer at the mixing ratio shown in Table 1. Thereafter, using a twin-screw extruder (type name "TEX 44, Japan Steel Works"), the mixture was melt-kneaded at a barrel temperature of 270 ° C and pelletized.
1. Raw material [P]
As a thermoplastic resin containing a portion derived from a rubbery polymer, ethylene / α-olefin rubber reinforced aromatic vinyl resin (raw materials P1 to P4) obtained in the following synthesis examples 1 to 4 and the following synthesis The diene rubber reinforced aromatic vinyl resin (raw material P5) obtained in Example 5 was used.

1-1. Synthesis Example 1 (Synthesis of Raw Material P1 (AES Resin))
Ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C, glass transition temperature: in a stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc. 25 parts of Mooney viscosity (ML1 + 4, 100 degrees C): 20, 11 parts of styrene, 4 parts of acrylonitrile, 0.5 parts of tert-dodecyl mercaptan and 110 parts of toluene were charged, and the temperature was raised. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.09 parts of tert-butylperoxyisopropyl monocarbonate was added, and the temperature was further raised. While maintaining the internal temperature at 100 ° C., polymerization was started at a stirring rotational speed of 100 rpm. After polymerization for 60 minutes, 44 parts of styrene, 16 parts of acrylonitrile and 0.86 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours. After 4 hours of initiation of polymerization, the internal temperature was raised to 120 ° C., and reaction was carried out for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, and a portion made of ethylene-propylene copolymer rubber, and a vinyl cyanide compound ( An ethylene / α-olefin rubber graft copolymer (graft resin) comprising a structural unit derived from acrylonitrile) and a portion comprising a vinyl copolymer including a structural unit derived from an aromatic vinyl compound (styrene), and A rubber-reinforced aromatic vinyl resin (raw material P1), which is a resin mixture composed of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer), was obtained. The graft ratio of the graft resin (acetone insoluble matter) contained in the raw material P1 was 48%. The rubber content contained in the raw material P1 used for the calculation of the graft ratio was determined from the polymerization formulation and the polymerization conversion ratio. The content of the ungrafted vinyl copolymer (hereinafter, also referred to as "acetone-soluble component") contained in the raw material P1 is 63% when the entire raw material P1 is 100%, and this acetone The limiting viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the solution was 0.42 dl / g. Then, when Tm of the raw material P1 was measured using this pellet, it was 40 degreeC.

1-2. Synthesis example 2 (synthesis of raw material P2 (AES resin))
Ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C, glass transition temperature: in a stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc. 50 parts of Mooney viscosity (ML1 + 4, 100 degreeC): 20 50 parts, 7.3 parts of styrene, 2.7 parts of acrylonitrile, 0.3 parts of tert-dodecyl mercaptan and 220 parts of toluene were charged, and the temperature was raised. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.07 part of tert-butylperoxyisopropyl monocarbonate was added, and the temperature was further raised. While maintaining the internal temperature at 100 ° C., polymerization was started at a stirring rotational speed of 100 rpm. After polymerization for 60 minutes, 29.3 parts of styrene, 10.7 parts of acrylonitrile and 0.25 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 2 hours and 30 minutes. After 3 hours and 30 minutes of initiation of the polymerization, the internal temperature was raised to 120 ° C., and the reaction was further carried out for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, and a portion made of ethylene-propylene copolymer rubber, and a vinyl cyanide compound ( An ethylene / α-olefin rubber graft copolymer (graft resin) comprising a structural unit derived from acrylonitrile) and a portion comprising a vinyl copolymer including a structural unit derived from an aromatic vinyl compound (styrene), and A rubber-reinforced aromatic vinyl resin (raw material P2), which is a resin mixture composed of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer), was obtained. The graft ratio of the graft resin (acetone insoluble matter) contained in the raw material P2 was 25%. The rubber content contained in the raw material P2 used for the calculation of the graft ratio was determined from the polymerization formulation and the polymerization conversion ratio. The content of acetone soluble matter contained in the raw material P2 is 38% when the whole raw material P2 is 100%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone soluble matter is It was 0.35 dl / g. Then, when Tm of the raw material P2 was measured using this pellet, it was 40 degreeC.

1-3. Synthesis example 3 (synthesis of raw material P3 (AES resin))
Ethylene / propylene copolymer rubber (ethylene / propylene = 74/26 (%), Tm: 29 ° C, glass transition temperature: in a stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc. 25 parts of Mooney viscosity (ML1 + 4, 100 degrees C): 20, 11 parts of styrene, 4 parts of acrylonitrile, 0.5 parts of tert-dodecyl mercaptan and 110 parts of toluene were charged, and the temperature was raised. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.09 parts of tert-butylperoxyisopropyl monocarbonate was added, and the temperature was further raised. While maintaining the internal temperature at 100 ° C., polymerization was started at a stirring rotational speed of 100 rpm. After polymerization for 60 minutes, 44 parts of styrene, 16 parts of acrylonitrile and 0.86 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours. After 4 hours of initiation of polymerization, the internal temperature was raised to 120 ° C., and reaction was carried out for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, and a portion made of ethylene-propylene copolymer rubber, and a vinyl cyanide compound ( Ethylene / α-olefin rubber graft copolymer (graft resin) comprising a structural unit derived from acrylonitrile) and a portion comprising a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene), and A rubber-reinforced aromatic vinyl resin (raw material P3), which is a resin mixture composed of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer), was obtained. The graft ratio of the graft resin (acetone insoluble matter) contained in this raw material P3 was 53%. The rubber content contained in the raw material P3 used for calculation of the graft ratio was determined from the polymerization formulation and the polymerization conversion ratio. The content of the ungrafted vinyl copolymer (hereinafter also referred to as "acetone-soluble component") contained in the raw material P3 is 61%, based on 100% of the entire raw material P3. The limiting viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the solution was 0.45 dl / g. Then, when Tm of the raw material P3 was measured using this pellet, it was 29 ° C.

1-4. Synthesis example 4 (synthesis of raw material P4 (AES resin))
A 20-liter stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc., ethylene / propylene / dicyclopentadiene copolymer (ethylene / propylene / dicyclopentadiene = 63/32/5 (%), Mooney viscosity (ML 1 + 4, 100 ° C) 33, no melting point (Tm), glass transition temperature (Tg) 30 parts, styrene 45 parts, acrylonitrile 25 parts, tert-dodecyl mercaptan 0.5 parts Then, 140 parts of toluene was charged, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.45 parts of tert-butylperoxyisopropyl monocarbonate is added, the internal temperature is further raised, and after reaching 100 ° C., while maintaining this temperature, the polymerization reaction is carried out at a stirring rotational speed of 100 rpm. went. Four hours after initiation of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was carried out for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg) and pelletized, and a portion comprising ethylene-propylene-dicyclopentadiene copolymer rubber, and cyanide・ Α-olefin rubber graft copolymer (graft comprising ethylene-α-olefin rubber graft copolymer (a graft comprising a structural unit derived from a fluorinated vinyl compound (acrylonitrile) and a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene)) A rubber-reinforced aromatic vinyl resin (raw material P4), which is a resin mixture comprising a resin) and an ungrafted vinyl copolymer (acrylonitrile-styrene copolymer), was obtained. The graft ratio of the graft resin (acetone insoluble matter) contained in this raw material P4 was 60%. The rubber content contained in the raw material P4 used for the calculation of the graft ratio was determined from the polymerization formulation and the polymerization conversion ratio. The content of acetone soluble matter contained in the raw material P4 is 52% when the whole raw material P4 is 100%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone soluble matter is It was 0.45 dl / g. Then, when Tm of raw material P4 was measured using this pellet, melting | fusing point did not exist in the range of 0-120 degreeC.

1-5. Synthesis example 5 (synthesis of raw material P5 (ABS resin))
In a glass flask equipped with a stirrer, in a nitrogen stream, 42 parts of ion exchanged water, 0.35 parts of potassium rosinate, 0.2 parts of tert-dodecyl mercaptan, polybutadiene rubber with an average particle size of 300 nm (gel content 80% Containing 80 parts of a latex containing 32 parts, 19 parts of a latex containing 8 parts of a styrene-butadiene copolymer rubber (30% styrene unit weight) having an average particle diameter of 600 nm, 14 parts of styrene and 6 parts of acrylonitrile while stirring The temperature rose. When the internal temperature reached 40 ° C, a solution of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.3 parts of glucose in 8 parts of ion-exchanged water was added . Thereafter, 0.07 parts of cumene hydroperoxide was added to initiate polymerization. After polymerization for 30 minutes, 45 parts of ion exchanged water, 0.7 parts of potassium rosin acid, 30 parts of styrene, 10 parts of acrylonitrile, 0.13 parts of tert-dodecyl mercaptan and 0.1 parts of cumene hydroperoxide for 3 hours Was added continuously. Thereafter, the polymerization was continued for an additional hour, and 0.2 parts of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) was added to the reaction system to complete the polymerization. Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and washed with water. Thereafter, the resultant is washed, neutralized, washed with water, and dried using a potassium hydroxide aqueous solution, and a portion made of a styrene-butadiene copolymer rubber, a structural unit derived from a vinyl cyanide compound (acrylonitrile), A diene rubber graft copolymer (graft resin) containing a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene) (graft resin), and an ungrafted vinyl copolymer (acrylonitrile. A rubber-reinforced aromatic vinyl resin (raw material P5), which is a resin mixture comprising a styrene copolymer, was obtained. The graft ratio of the diene rubber polymer reinforced aromatic vinyl resin (graft resin, acetone insoluble matter) contained in this raw material P5 was 55%. The rubber content contained in the raw material P5 used for the calculation of the graft ratio was determined from the polymerization formulation and the polymerization conversion ratio. The content of the ungrafted (co) polymer (acetone-soluble component) contained in the raw material P5 is 38% when the entire raw material P5 is 100%, and the intrinsic viscosity of this acetone-soluble portion [[ (In methyl ethyl ketone, 30 ° C.) was 0.45 dl / g. In addition, Tm of this raw material P5 was not observed.

2. Raw material [Q]
The following raw materials Q1 to Q4 were used as thermoplastic resins not containing a portion derived from a rubbery polymer.

2-1. Raw material Q1 (AS resin)
The acrylonitrile styrene copolymer whose ratio of an acrylonitrile unit and a styrene unit is 27% and 73%, respectively, and whose intrinsic viscosity [eta] (in methyl ethyl ketone, 30 degreeC) is 0.30 dl / g. The glass transition temperature (Tg) was 103.degree.

2-2. Raw material Q2 (AMS resin)
Acrylonitrile having a ratio of an acrylonitrile unit, a styrene unit and an α-methylstyrene unit of 70%, 5% and 25%, respectively, and an intrinsic viscosity [30] (in methyl ethyl ketone, 30 ° C.) of 0.40 dl / g Styrene / α-methylstyrene copolymer. The glass transition temperature (Tg) was 140.degree.

2-3. Raw material Q3 (PMI resin)
N-phenylmaleimide-acrylonitrile-styrene copolymer "Polyimirex PAS 1460 (trade name)" manufactured by Nippon Shokubai Co., Ltd. was used. The content of N-maleimide units was 40%. The glass transition temperature (Tg) was 167 ° C.

2-4. Raw material Q4 (PC resin)
A polycarbonate resin "TAFLON A2200 (trade name)" manufactured by Idemitsu Kosan Co., Ltd. was used. The viscosity average molecular weight (Mv) was 22,000, and the glass transition temperature (Tg) was 153 ° C.

3. Raw material [R]
3-1. Raw material R1 (polyolefin wax)
Polyethylene wax "Sun wax 171-P (trade name)" manufactured by Sanyo Chemical Industries, Ltd. was used. The number average molecular weight (Mn) was 1500, and the melting point measured using DSC was 101 ° C.
4. Raw material [T]
4-1. Raw material T1 (inorganic matting material)
As an inorganic type matting material, granular glass flakes made by Nippon Sheet Glass Co., Ltd. "Micrograss Freca REFG-101" (trade name) were used. The glass flakes are scaly, the average thickness of the base glass is 5 μm, and the average particle size of the base glass is 600 μm.
4-2. Raw material T1 (organic matting material)
A partially crosslinked acrylic additive "Metabrene F-410" (trade name, crosslinked methyl methacrylate-alkyl acrylate-styrene copolymer) manufactured by Mitsubishi Rayon Co., Ltd. was used as the organic matting agent.

Reference example (preparation and evaluation of single layer film)
1. Production of Single-Layer Film Using pellets of each thermoplastic resin shown in Table 1, a test piece of the single-layer film was produced by extrusion film formation with a T-die. A film forming machine equipped with a T-die having a die width of 1,600 mm and a lip spacing of 0.25 mm and an extruder having a screw diameter of 115 mm was used for producing a single-layer film. Pellets of each molding resin shown in Table 1 were supplied to an extruder and melted at a temperature of 270 ° C., and the melted resin was continuously discharged from a T-die to obtain a single layer film. Thereafter, the single layer film is solidified by cooling while being in surface contact with a cast roll whose surface temperature is controlled to 70 ° C. by an air knife, and a single layer film having a thickness (100 μm) described in Table 1 is obtained. The

2. Dimensional Stability of Monolayer Film The dimensions of the extrusion direction (MD) of the resin from the T-die of the monolayer film obtained in 1 above and the direction (TD) orthogonal to MD were measured before and after heat treatment.
A 100 mm (MD) × 100 mm (TD) square was drawn at the center of the surface of a 120 mm (MD) × 120 mm (TD) test piece cut out from the center of the single layer film obtained in 1 above in the TD direction. The test piece was allowed to stand in a constant temperature bath and heat treated at 120 ° C. for 30 minutes in the air atmosphere. Thereafter, the test piece was taken out, the length of each side in the MD and TD directions of the above square was measured at 25 ° C., and the contraction rate was calculated by the following equation.
Shrinkage rate (%) = {(length after heating) − (length before heating)} / (length before heating) × 100
The heat resistance was evaluated according to the following criteria from the shrinkage factor determined from the above equation, and the results are shown in Table 1. In addition, the following contraction ratio becomes a negative value when a test piece shrink | contracts after heating, and becomes a positive value when a test piece expand | swells after heating.
◎: The contraction rate (s) was −0.5% ≦ s ≦ 0% or 0% ≦ s ≦ 0.5%.
○: The contraction rate (s) was −1.0% ≦ s <−0.5% or 0.5% <s ≦ 1.0%.
X: The contraction rate (s) was −2.0% ≦ s <−1.0% or 1.0 <s ≦ 2.0%.
××: The contraction rate (s) was s <−2.0% or 2.0% <s.

3. Measurement of Melting Point (Tm) The melting point (Tm) was measured using a differential scanning calorimeter “DSC 2910” (type name) manufactured by TA Instruments in accordance with JIS K 7121-1987. The measurement was performed by observing the endothermic change at a constant temperature rising rate of 20 ° C. per minute, and reading the melting point from the peak temperature of the obtained endothermic pattern.

4. Thickness of single-layer film The thickness of various films was measured by using Michitoyo's thickness gauge “ID-C1112C” (type name), and after 1 hour from the start of film production, cut off the film, and centered in the film width direction (TD) And it measured at intervals of 10 mm toward both ends from the center, and made it the average value. The values of measuring points in the range of 20 mm from the end of the film were excluded from the calculation of the above average value.

Examples 1 to 4 and Comparative Examples 1 to 6 (Production and Evaluation of Laminated Film)
1. Preparation of Laminated Film A film forming machine equipped with a T-die having a die width of 1.600 mm and a lip spacing of 0.25 mm and an extruder having a screw diameter of 115 mm was used. Pellets of each molding resin shown in Table 2 were supplied to an extruder and melted at a temperature of 270 ° C., and the melted resin was continuously discharged from a T-die to obtain a single layer film. Thereafter, a surface layer (I) and a substrate layer (II) having thicknesses described in Table 2 while bringing this single layer film into surface contact with a cast roll whose surface temperature is controlled to 70 ° C. by an air knife. The single layer film which comprises each of was obtained. Then, a material for forming an adhesive layer (adhesive composition) was applied to one surface of the single layer film constituting the skin layer (I) by a gravure roll coating method to obtain a skin layer film with an adhesive layer.
Next, a single layer film constituting the substrate layer (II) is brought into contact with the surface on the adhesive layer side in the adhesive layer-carrying skin layer film, and this is heat-welded by a rotary heat press. The laminated film shown in Table 2 was obtained.

2. Dimensional Stability of Laminated Film The dimensions of the extrusion direction (MD) of the resin from the T-die of the laminated film obtained in the above 1 and the direction (TD) orthogonal to the MD were measured before and after heat treatment.
A square of 100 mm (MD) x 100 mm (TD) was drawn at the center of the surface of a 120 mm (MD) x 120 mm (TD) test piece cut out from the center of the laminated film obtained in 1 above in the TD direction. The test piece was allowed to stand in a constant temperature bath and heat treated at 120 ° C. for 30 minutes in the air atmosphere. Thereafter, the test piece was taken out, the length of each side in the MD and TD directions of the above square was measured at 25 ° C., and the contraction rate was calculated by the following equation.
Shrinkage rate (%) = {(length after heating) − (length before heating)} / (length before heating) × 100
The heat resistance was evaluated according to the following criteria from the shrinkage factor determined from the above equation, and the results are shown in Table 2. In addition, the following contraction ratio becomes a negative value when a test piece shrink | contracts after heating, and becomes a positive value when a test piece expand | swells after heating.
◎: The contraction rate (s) was −0.5% ≦ s ≦ 0% or 0% ≦ s ≦ 0.5%.
○: The contraction rate (s) was −1.0% ≦ s <−0.5% or 0.5% <s ≦ 1.0%.
X: The contraction rate (s) was −2.0% ≦ s <−1.0% or 1.0 <s ≦ 2.0%.
××: The contraction rate (s) was s <−2.0% or 2.0% <s.

3. Vacuum Formability of Laminated Film A laminated film having a size of 300 mm (MD) × 210 mm (TD) is cut out from the center of the laminated film obtained in 1 above in the TD direction, and a molded product shown in FIG. A compact vacuum forming machine "300X" manufactured by SEIKO INDUSTRIES CO., LTD. Equipped with a vacuum forming mold 8 shown in FIG. 4 was used. The vacuum forming mold 8 shown in FIG. 4 has a height of 45 mm, a bottom size of 150 mm × 150 mm, an upper surface size of 140 m × 140 mm, and a central area of 100 mm × 100 mm on the upper surface. A recess of 20 mm in depth is formed and has fine through holes throughout.
A laminated film of the above-described size was fixed at an interval of 40 mm above the upper surface of the vacuum forming mold 8 (FIG. 5 (I)). Then, the laminated film was heated from the peripheral side using the heater (not shown) beforehand heated at 450 degreeC. Next, the vacuum forming mold 8 was moved upward to bring the upper surface into contact with the laminated film (FIG. 5 (II)). Thereafter, the pressure was reduced from the bottom side of the vacuum forming mold 8, the laminated film was brought into close contact with the inner surface of the recess of the vacuum forming mold 8, and vacuum forming was performed (FIG. 5 (III)). Next, the vacuum forming mold 8 was released to obtain a molded article shown in FIG. 5 (IV). The followability of the laminated film to the concave portion of the vacuum forming mold 8 was visually observed, evaluated based on the following criteria, and the results are shown in Table 2.
Good: The ability to follow the recesses of the vacuum forming mold 8 was good, and no wrinkles were observed on the film surface of the molded product shown in FIG. 5 (IV).
B: The ability to follow the recesses of the vacuum forming mold 8 was good, but wrinkles were observed on the film surface of the molded article shown in FIG. 5 (IV).
X: The ability to follow the recess of the vacuum forming mold 8 was poor, and wrinkles were observed on the film surface of the molded article shown in FIG. 5 (IV).

4. Stick-slip test of laminated film (noise noise risk index)
In the stick-slip test, a test strip 18 made of Zigler (ZIEGLER) stick-slip tester “SSP-02” (type name), a test body 18 and an ABS / PC alloy “EXCELOY CK 20” (manufactured by Techno Polymer Co., Ltd.) Were set as shown in FIG. 7 and both were rubbed three times to measure the allophone risk index, and the results are shown in Table 2. The measurement conditions are temperature: 23 ° C., humidity: 50% RH, load: 40 N, speed: 10 mm / sec, amplitude: 20 mm. The smaller the allophone risk index, the lower the risk of itching.
In addition, the test body 18 cuts out the laminated film 4 in the magnitude | size of 50 mm (MD) x 25 mm (TD) from the center of TD direction of the laminated film obtained by said 1, and fixes in the metal mold | die of an injection molding machine Then, the mold is closed, and a heat-resistant ABS resin “TECHNO MUH E1500” (made by Techno Polymer Co., Ltd.) melted at 240 ° C. is injected into the surface of the base layer (II) side of the laminated film 4 and resin molded The part 16 (50 mm × 25 mm × 4 mm) was molded and produced (see FIG. 6).

5. Flexibility of Laminated Film From the center of the laminated film obtained in 1 above in the TD direction, a laminated film with a size of 100 mm (MD) × 100 mm (TD) is cut out and bent along the symmetry axis in the MD direction , Bent along the symmetry axis in the TD direction. Next, the film in this folded state is reciprocated twice on each crease at a speed of 5 mm / sec using a manual pressure bonding roll (2,000 g) according to JIS Z0237, and then the crease is expanded. It returned to the original state, the crease was observed visually, and it judged by the following standard. The one in which the crease is not broken is excellent in flexibility.
:: The fold was not broken, and the fold was not broken even if it was folded and spread again.
:: The crease was not broken, but the crease was broken when it was folded and spread again.
X: The crease was broken.

6. Matting property The test body 18 produced by the method described in the item 4 (stick-slip test) was placed in a dark room so that the resin film 4 faced upward. After that, the fluorescent lamp “FLR40SW / M / 36” (trade name) manufactured by Mitsubishi Electric Lighting Co., Ltd., which is disposed on the ceiling of a dark room, which is directly above the test body 18 and at a distance of 2 m to the resin film 4 The five layers of panelists visually observed the matting property of the resin film 4 and evaluated it based on the following criteria. The results are shown in Table 2.
:: All five panelists judged that the film surface had no reflection or reflection of fluorescent light, and a good matte appearance was obtained.
Fair: 1 to 4 of 5 panelists judged that the film surface had reflections or reflections of fluorescent light, and that a good matte appearance was not obtained.
X: All five panelists judged that the film surface had reflection and reflection of fluorescent light, and did not have a good matte appearance.

The following can be seen from Table 2.
Example 1-1 4 using a laminated film of the present invention, dimensional stability, vacuum formability, flexibility, stick-slip test, also showed good results in any of the matte properties. On the other hand, Comparative Examples 1, 5 and 6 which do not have the skin layer (I) made of a rubber-reinforced aromatic vinyl resin having a melting point of 0 to 120 ° C. are flexible and vacuum formed as a result of the stick-slip test. Sex and mattness were inferior. The comparative example 2 provided with the skin layer (I) which consists of rubber | gum reinforcement | strengthening aromatic vinyl-type resin which does not have melting | fusing point has the result of the stick-slip test inferior. Comparison in which the layer consisting of a thermoplastic resin having a dimensional stability of ± 1% or less is a skin layer (I), and the layer consisting of a rubber-reinforced aromatic vinyl resin having a melting point at 0 to 120 ° C is a substrate layer (II) Example 3 was inferior in stick-slip test and matting results. Comparative Example 4 in which the surface layer (I) did not contain a matting material was inferior in matting property.

  The laminated film of the present invention is laminated on the surface of an article, in particular, the surface of an article made of a resin molded article by thermoforming, insert molding, in-mold molding, etc., when other articles are in dynamic contact. A surface layer having a matte appearance can be applied while suppressing the generation of stagnant noise, and the obtained molded product can be suitably used as a component of an article composed of two or more components in contact with each other.

Claims (8)

A laminated film comprising a skin layer (I) on at least one surface of a substrate layer (II) made of a thermoplastic resin,
The surface layer (I) comprises a thermoplastic resin composition comprising a rubber-reinforced aromatic vinyl resin (A) and an additive ,
The thermoplastic resin composition contains, as the additive, 1 to 20 parts by mass of a matting material (Y) with respect to 100 parts by mass of the rubber-reinforced aromatic vinyl resin (A),
Does the thermoplastic resin composition contain an ethylene / α-olefin rubber having a melting point of 0 to 120 ° C. measured according to JIS K 7121-1987 as the rubber portion of the rubber-reinforced aromatic vinyl resin (A)? Or a polyolefin wax having a melting point of 0 to 120 ° C. as another additive,
The melting point of the surface layer (I) measured according to JIS K 7121-1987 is in the range of 0 to 120 ° C.
A laminated film having a dimensional change of ± 1% or less when left to stand at 120 ° C. for 30 minutes. The laminated film according to claim 1 , wherein the matte material (Y) is an inorganic matte material. A step of disposing the laminated film according to claim 1 or 2 in a cavity of an injection molding die, and a surface layer which is the outermost layer of a molded article of the laminated film in the cavity of the injection molding die. Injecting the resin composition from the side opposite to (I), a method for producing an insert-molded article. A film for insert molding comprising the laminated film according to claim 1 or 2 . The laminated film according to claim 1 or 2, in the surface opposite to the skin layer (I) of the laminated film, the laminated body which is laminated on the resin molded article. The laminate according to claim 5 , wherein the skin layer (I) of the laminated film is present as the outermost layer. The laminate according to claim 6 , wherein the skin layer (I) of the laminated film is in contact with another member. An article comprising at least two mutually contacting parts, wherein at least one of the parts consists of a laminate according to any one of claims 5 to 7 , and the skin layer of the laminated film of the laminate Articles in which (I) contacts other parts.

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