JP2016088000A - Laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film suitable for suppressing creak generated from an article and providing matte appearance by coating a resin layer consisting of a rubber reinforced aromatic vinyl resin composition having crystallinity on a surface of the article, especially a surface of an article consisting of a resin molded article by a molding method such as thermal molding, insert molding and in-mold molding.SOLUTION: There is provided a laminate film having an epidermal layer (I) on at least a single face of a substrate layer (II), where the epidermal layer (I) consists of a thermoplastic resin composition containing a rubber reinforced aromatic vinyl resin (A) and a delustering material (Y), the melting point of the epidermal layer (I) measured according to JIS K 7121-1987 in a range of 0 to 120°C and dimensional change rate of the laminate film in the range of ±1% or less when standing at 120°C for 30 minutes.SELECTED DRAWING: None

Description

  The present invention is a laminated film having a skin layer (I) that has a matte appearance and reduces the occurrence of squeaking noise on at least one surface of the base material layer (II), and the surface of the article, in particular, When it is laminated on the surface of an article made of a resin molded article by thermoforming, insert molding, in-mold molding, etc., and the article is in dynamic contact with another article via the skin layer (I) of the laminated film The present invention relates to a laminated film suitable for suppressing the generation of stagnation noise.

  Today, resin molded products are widely used as parts of various products such as vehicles, electrical / electronic devices, OA (office automation) devices, home appliances, building materials, and sanitary products. These products are usually composed of an assembly of a plurality of parts, and these parts are arranged adjacent to or in contact with each other by being fitted, abutted, overlaid, or fastened with screws or the like. Often. Such an assembly is known to generate a squeaking sound (friction sound) when vibration, rotation, twisting, sliding, impact, etc. are applied, and adjacent parts dynamically contact and rub against each other. It has been. For example, a squeaking noise may be generated when an air outlet of an air conditioner or an audio housing part arranged in an automobile and a fitting part arranged in the periphery or inside of the parts rub against each other due to vibration or the like. The above-mentioned squeaking noise is known as an abnormal noise caused by a stick-slip phenomenon that occurs when two objects rub against each other, and is caused by a property different from mere sliding of resin.

  As shown in FIG. 8, the stick-slip phenomenon is understood as a phenomenon in which the frictional force largely fluctuates periodically, and more specifically, occurs as shown in FIG. That is, as shown in the model of FIG. 9A, when an object M connected by a spring is placed on a driving table that moves at a driving speed V, the object M first moves at the driving speed V by the action of a static frictional force. It moves to the right as shown in FIG. When the force to be restored by the spring becomes equal to the static friction force, the object M starts to slide in the direction opposite to the driving speed V. At this time, the object M receives a dynamic frictional force, so that the sliding stops at the time of FIG. 9C when the dynamic force of the spring becomes equal to the dynamic frictional force, that is, 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. As shown in FIG. 8, it is said that if the difference Δμ between the static friction coefficient μs and the friction coefficient μl at the lower end of the sawtooth waveform is large, itching is likely to occur. 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, a squeaking noise is likely to occur. These squeaking noises are a major cause of impairing the comfort and quietness in automobiles, offices, and residential rooms, and there is a strong demand for reducing squeaking noises.

  Conventionally, by using a rubber-reinforced aromatic vinyl resin reinforced with a crystalline rubber such as ethylene / α-olefin rubber having a melting point as a molding material, it is possible to suppress the occurrence of squeaking noise in the molded product. Known (see Patent Document 1 and Patent Document 2). However, attention has not yet been paid to using this molding material by laminating it 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 protective resin sheet comprising a transparent protective layer, a pattern layer formed with a pattern showing letters, numbers, pictures, etc., and a support layer in sequence, insert molding, in-mold on the surface of the resin molded product A technique for stacking and decorating by molding or the like is already known. Specifically, after the decorative resin sheet is placed in the cavity of the injection mold, the thermoplastic resin such as acrylic resin, polycarbonate resin, and ABS resin is melted toward the surface of the support layer. By injection-filling an object into a cavity, a resin molded product having the same shape as the cavity is formed, and at the same time, a decorative resin sheet is bonded and integrated on the surface (see FIG. 1).

  As the decorative resin sheet, there is conventionally known a picture insert film in which a pattern is provided on a transparent acrylic film and an ABS resin film is laminated on the pattern as a base film (see Patent Document 3). ). Also, on the back side of the front sheet made of transparent acrylic resin, the binder resin is a pattern ink layer made of a mixture of acrylic resin and vinyl chloride / vinyl acetate copolymer, and a mixture of acrylic resin and vinyl chloride / vinyl acetate copolymer. An injection-molding simultaneous decorating sheet is known in which an adhesive layer made of and a base sheet made of an ABS resin with a butadiene component ratio 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 the resin molded product, not for the purpose of preventing the squeaking noise. The decorative resin sheet cannot prevent stagnation.

  In addition, as a laminate including a layer made of a rubber-reinforced aromatic vinyl resin, a sheet in which a skin layer made of polycarbonate is formed on at least one side of a base material layer made of a thermoplastic resin composition containing an ABS resin (Patent Document) 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 material 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 a rubber-reinforced styrene resin having crystallinity is used as a skin layer.

  In addition, when parts made of thermoplastic resin are used for automobile interiors, the driver may be obscured by sunlight reflected on the surface of the parts, or the instrument may be difficult to visually recognize. From the viewpoint of ensuring, the parts must have a matte appearance. In addition, in recent years, matte appearances are often required from the viewpoint of design properties in cases such as home appliances, OA equipment, chassis, and the like. In addition, when used for the above-mentioned automobile interior, similarly, a matte appearance is often required from the viewpoint of design.

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

JP 2011-137066 A JP 2013-111281 A Japanese Patent Laid-Open No. 11-091041 JP 2003-170546 A JP-A-2005-007684 JP 2009-051207 A Japanese Patent Laid-Open No. 2007-062194

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

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

Thus, according to one aspect of the present invention, a laminated film comprising a skin layer (I) on at least one surface of a base material layer (II) made of a thermoplastic resin, the skin layer (I) being And a thermoplastic resin composition containing a rubber-reinforced aromatic vinyl resin (A) and a matting material (Y), and the melting point of the skin layer (I) measured in accordance with JIS K 7121-1987 is 0. There is provided a laminated film in a range of ˜120 ° C. and having a dimensional change rate of ± 1% or less when the laminated film is left at 120 ° C. for 30 minutes.
Since the laminated film of the present invention is excellent in heat resistance as apparent from the dimensional change rate, it is excellent in molding processability in thermoforming, insert molding, in-mold molding and the like. Therefore, an article having a matte appearance and suppressing generation of squeaking noise by laminating the surface of each article such that the skin layer (I) of the laminated film is the outermost layer by these molding methods. Can be provided.

According to another aspect of the present invention, a step of disposing the laminated film of the present invention in a cavity of an injection mold, and a molded product of the laminated film in the cavity of the injection mold There is provided a method for producing an insert-molded product comprising a step of injecting a resin composition from the side opposite to the outermost skin layer (I).
According to another aspect of the present invention, an insert molding film comprising the laminated film of the present invention is provided.

According to the other aspect of this invention, the laminated body by which the laminated | multilayer film of this invention was laminated | stacked on the resin molded product on the surface on the opposite side to the skin layer (I) is provided. This laminate is useful as a part of an article having at least two parts in contact with each other.
Furthermore, according to another aspect of the present invention, there is provided an article having at least two parts that are in contact with each other, wherein at least one of the parts comprises the laminate of the present invention. An article in which the skin layer (I) is in contact with other parts is provided.

  When a resin film made of rubber-reinforced aromatic vinyl resin is subjected to high temperatures during thermoforming, insert molding, in-mold molding, etc., it may expand or contract, tear on the film surface, and cause wrinkles, cracks, etc. Thus, 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 made of a thermoplastic resin composition containing a matting material (Y) and having crystallinity is laminated on a base material layer to form a laminated film satisfying a predetermined dimensional change rate. Therefore, it has excellent heat resistance, in particular, dimensional stability during heating in thermoforming, insert molding, in-mold molding, and the like. Further, since the laminated film of the present invention can be laminated on the surface of various articles, particularly the surface of a resin molded product so that the skin layer (I) is the outermost layer, adjacent articles are in dynamic contact with each other. It is possible to suppress the generation of squeaking noise when rubbing against each other, and at the same time, it is possible to give a matte appearance. Further, as described above, the laminated film of the present invention is excellent in dimensional stability during heating, so it has excellent vacuum formability, and is a resin formed by a molding method such as thermoforming, insert molding, in-mold molding, etc. in which the laminated film becomes high temperature. Even when laminated on a molded product, the occurrence of defects such as tears, wrinkles, and cracks is suppressed, and not only the generation of squeaking noise is suppressed, but also the outermost layer with a good matte appearance is imparted to the resin molded product. can do.

It is a schematic sectional drawing explaining an example of the method of manufacturing the laminated body provided with the skin layer (I) of the laminated | multilayer film of this invention as an 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 product of this invention. It is a schematic sectional drawing which shows an example of the articles | goods which consist of several components made from 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 from 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 from 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 from 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 from 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 from the laminated body of this invention. It is a schematic perspective view which shows the type | mold used for the 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 squeaking sound evaluation in an Example and a comparative example. It is a schematic perspective view which shows the method of the squeaking sound evaluation in an Example and a comparative example. It is explanatory drawing of a stick-slip phenomenon. (A), (b), (c), (d) is a model figure of a stick-slip phenomenon.

The present invention will be described in detail below.
In the present invention, “(co) polymerization” means homopolymerization and / or copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Acrylate and / or methacrylate.
Further, the melting point measured in accordance with JIS K 7121-1987 (in this specification, sometimes referred to as “Tm”) is a constant temperature increase of 20 ° C. per minute using DSC (differential scanning calorimeter). This is a value obtained by measuring the endothermic change at a speed and reading 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 composed of a thermoplastic resin composition containing a rubber-reinforced aromatic vinyl resin (A) and a matte material (Y). The melting point (Tm) of the skin layer (I) and the thermoplastic resin composition forming the skin layer (I) is the effect of reducing the squeaking noise when laminated on the surface of another article to prevent the squeaking noise, and the machine From the viewpoint of mechanical strength, it needs 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. However, the number of endothermic patterns in the range of 0 to 120 ° C. is not limited to one, and two or more. But you can. The Tm (melting point) found in the range of 0 to 120 ° C. may be derived from the rubber-reinforced aromatic vinyl resin (A), particularly the rubber part (a1), or the rubber-reinforced aromatic vinyl. It 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) is composed of a rubber part (a1) derived from a rubbery polymer and a (co) polymer part (a2) having a structural unit derived from a vinyl monomer, The rubber part (a1) preferably forms a graft copolymer obtained by graft polymerization of the (co) polymer part (a2). Therefore, the rubber-reinforced aromatic vinyl resin (A) is preferably composed of at least the graft copolymer and the (co) polymer part (a2) not graft-polymerized to the rubber part (a1). In addition, the (co) polymer part (a2) may contain other components such as an ungrafted rubber part (a1) or additives.

  The rubber part (a1) may be a homopolymer or a copolymer as long as it is rubbery (having rubber elasticity) at 25 ° C. The rubber part (a1) may be composed of either a diene polymer (hereinafter referred to as “diene rubber”) or a non-diene polymer (hereinafter referred to as “non-diene rubber”). Further, these polymers may be cross-linked polymers or non-cross-linked polymers. Among these, in the present invention, from the viewpoint of the effect of preventing the squeaking sound of the skin layer (I), it is preferable that at least a part of the rubber part (a1) is composed of a non-diene rubber, and the rubber part ( It is particularly preferred that all of a1) is 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. Examples thereof include a hydrogenated polymer obtained by hydrogenation (however, the hydrogenation rate is 50% or more). This 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 preventing the squeaking noise of the skin layer (I). The ethylene / α-olefin rubber is a copolymer rubber including a structural unit derived from ethylene and a structural unit derived from an α-olefin. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-hexadecene, Eikosen etc. are mentioned. These α-olefins can be used alone or in combination of two or more. The number of carbon atoms 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 to 5, preferably 50 to 95:50 to 5, more preferably 60 to 95:40 to 5. When the mass ratio of ethylene: α-olefin is within the above range, the resulting molded article is more excellent in impact resistance, which is preferable. The ethylene / α-olefin rubber may contain a structural unit derived from a non-conjugated diene, if necessary. Non-conjugated dienes include alkenyl norbornenes, cyclic dienes and aliphatic dienes, with 5-ethylidene-2-norbornene and dicyclopentadiene being preferred. These non-conjugated dienes can be used alone or in admixture of two or more. The ratio of the non-conjugated diene to the total amount of the rubbery polymer is usually 0 to 10% by mass, preferably 0 to 5% by mass, 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., and 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 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 expressed, and the effect of preventing itching can be expressed in the epidermis layer (I). When the rubber-reinforced aromatic vinyl resin (A) has such crystallinity, the occurrence of the stick-slip phenomenon is suppressed, so that the skin layer (I) containing this and other parts are in dynamic contact with each other It is considered that the generation of itching sound is suppressed.

  The Mooney viscosity (ML1 + 4, 100 ° C .; conforming to JIS K 6300) of the ethylene / α-olefin rubber is usually 5 to 80, preferably 10 to 65, 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 obtained laminate are further excellent, which is preferable.

    The ethylene / α-olefin rubber is preferably an ethylene / α-olefin copolymer containing no non-conjugated diene component from the viewpoint of reducing squeaking noise. Among these, an ethylene / propylene copolymer, ethylene / 1-butene are preferable. A copolymer and an ethylene / 1-octene copolymer are more preferable, and an ethylene / propylene copolymer is particularly preferable.

  The rubber part of the component (A) is preferably composed entirely of non-diene rubber, particularly ethylene / α-olefin rubber, from the viewpoint of stagnation noise reduction effect, but does not impair the stagnation noise reduction effect. In addition to the non-diene rubber, the diene rubber may be used. When the rubber part 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 laminated film, and the appearance of the obtained laminate are further increased. It will be enough.

    Diene rubbers include homopolymers such as polybutadiene and polyisoprene; butadienes such as styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / styrene / butadiene copolymers, and acrylonitrile / butadiene copolymers. Examples thereof include styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, and isoprene 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 mass based on 100 mass% of the entire rubber-reinforced aromatic vinyl resin (A). %, More preferably 3 to 65% by mass, further preferably 4 to 55% by mass, further preferably 5 to 50% by mass, and particularly preferably 7 to 45% by mass. When the content of the rubber part (a1) is within the above range, the squeaking noise reduction effect, dimensional stability, vacuum formability, and the like of the laminated film of the present invention are excellent.

  The (co) polymer part (a2) of the rubber-reinforced aromatic vinyl resin (A) comprises a structural unit derived from a vinyl monomer, and the vinyl monomer contains an aromatic vinyl compound as an essential component. If desired, a compound copolymerizable with the aromatic vinyl compound may be contained. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinyl. And naphthalene. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.

  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 if necessary, a copolymer with these compounds can be used. Other polymerizable vinyl monomers can also be used. Such other vinyl monomers include 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, and the like. These may be used alone or in combination of two or more.

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

  Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid 2 -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-phenylmaleimide and N-cyclohexylmaleimide. 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 hydroxyl group-containing unsaturated compound 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 of the content of the structural unit derived from the aromatic vinyl compound in the rubber-reinforced aromatic vinyl resin (A) is copolymerizable with the structural unit derived from the aromatic vinyl compound and the aromatic vinyl compound. When the total of structural units derived from the 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 part (a2) of the rubber-reinforced aromatic vinyl resin (A) contains a structural unit derived from an aromatic vinyl compound and a vinyl cyanide compound as a structural unit, it is derived from the aromatic vinyl compound. The content of the structural unit is usually 40 to 90% by mass, preferably 55 to 85% by mass when the total of both is 100% by mass, and the content of the structural unit derived from the vinyl cyanide compound Is 10 to 60% by mass, preferably 15 to 45% by mass, when the total of both is 100% by mass.

  For example, the rubber-reinforced aromatic vinyl resin (A) is prepared 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) composed 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 graft copolymer is obtained, and a known method can be applied. As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used. In these polymerization methods, known polymerization initiators, chain transfer agents (molecular weight regulators), emulsifiers and the like can be appropriately used.

  In the above production method, usually, a (co) polymer of vinyl monomers is graft-polymerized to a rubbery polymer, and a vinyl monomer that is not graft-polymerized to the rubbery polymer. A mixed product of the (co) polymer is obtained. In some cases, the mixed product may contain a rubbery polymer in which the (co) polymer is not graft-polymerized. The rubber-reinforced aromatic vinyl resin (A) of the present invention comprises a rubber part (a1) derived from a rubbery polymer and a (co) polymer part (a2) having a structural unit derived from an aromatic vinyl monomer. The rubber part (a1) preferably forms a graft copolymer in which the (co) polymer part (a2) is graft-polymerized, so that the graft copolymer produced as described above is used. And a (co) polymer mixed product can be used as the rubber-reinforced aromatic vinyl resin (A) as it is.

  A rubber-reinforced aromatic vinyl resin (A) is a vinyl comprising an aromatic vinyl compound and optionally another vinyl compound copolymerizable with the aromatic vinyl compound in the absence of the rubbery polymer (a). What added the (co) polymer (A ') manufactured by superposing | polymerizing a system monomer may be used. When this (co) polymer (A ′) is added to the rubber-reinforced aromatic vinyl resin (A), it forms a (co) polymer portion (a2) that is not graft-polymerized to the rubber portion (a1). Will do.

  As described above, the rubber-reinforced aromatic vinyl resin (A) of the present invention may include a diene rubber in addition to the non-diene rubber. As a method for producing such a rubber-reinforced aromatic vinyl resin (A) containing a plurality of 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 a non-diene rubbery polymer, the vinyl monomer (b) is graft polymerized 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 Can do.

  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 vacuum moldability of the laminated film of the present invention are further improved.

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

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

  Intrinsic viscosity (30 ° C. in methyl ethyl ketone) of an 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: 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 moldability of the resin composition become better.

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

  The intrinsic viscosity [η] is, for example, the type and amount of a chain transfer agent used when graft-polymerizing the 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 suitably the addition method and addition time of a component, polymerization temperature, polymerization time, etc. Further, the rubber-reinforced aromatic vinyl resin (A) is mixed with a (co) polymer (A ′) having an intrinsic viscosity [η] different from the intrinsic viscosity [η] of the acetone-soluble component. Can do.

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 product having a matte surface (matte appearance). In the present invention, an inorganic material (metal or inorganic compound) (hereinafter referred to as “inorganic matte material”) and an organic material (polymer) (hereinafter referred to as “organic matte material”). Any of these may be used, or a combination of these may be used.
The shape of the matting material (Y) is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a linear shape, a plate shape, a polyhedron, and an indefinite shape, and may include a hollow portion. Further, the size of the matting material (Y) is not particularly limited.
Examples of inorganic matting materials include powdered and granular materials such as calcium carbonate, magnesium carbonate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, calcium oxide, silicon oxide, magnesium hydroxide, magnesium sulfate. , Barium sulfate, silicate, talc, mica, kaolin, glass flakes, etc., as microballoons, glass balloons, phenolic resin balloons, etc., as fibers, glass fibers, carbon fibers, metal fibers, Examples of whisker-like carbon fibers include ceramic whiskers and titanium whiskers.
Examples of organic matting materials include crosslinked resins (such as crosslinked acrylic resins) polymerized using an unsaturated carboxylic acid alkyl ester monomer and a crosslinking agent, unsaturated nitrile monomers, and aromatic vinyl monomers. Examples thereof include a crosslinked resin (crosslinked acrylonitrile, styrene resin, etc.) polymerized using a monomer and a crosslinking agent.
As the matting material (Y), an inorganic matting material is preferable. When an inorganic matte material is used as the matte material (Y), the matte appearance of the resulting laminate and the contact with other parts are maintained while maintaining the flexibility and vacuum formability of the laminated film. The effect of suppressing the occurrence of stagnation noise at the time is further excellent and preferable.
The ratio of the matte material (Y) contained in the thermoplastic resin composition is preferably 1 to 20 parts by mass, more preferably 100 parts by mass when the rubber-reinforced aromatic vinyl resin (A) is 100 parts by mass. Is 2 to 15 parts by mass, more preferably 3 to 12 parts by mass. If the matte material (Y) contained in the laminated film of the present invention is in the above range, the matte appearance of the resulting laminate and other parts while maintaining the flexibility and vacuum formability of the film The effect of suppressing the generation of stagnation noise upon contact is further excellent and preferable.

  The thermoplastic resin composition may further contain additives other than the matting material (Y) as appropriate. Examples of such additives include low molecular weight oxidized polyethylene (c1), ultrahigh molecular weight polyethylene (c2), polytetrafluoroethylene (c3), and low molecular weight (for example, several) as described in JP2011-137066A. And an average molecular weight of 10,000 or less) polyolefin wax.

  Examples of such a polyolefin wax include polyethylene wax having a melting point of 0 to 120 ° C. In addition, when a polyolefin wax having such a melting point and other additives having a melting point of 0 to 120 ° C. are 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 part of) does not have a melting point (Tm). These additives can be used alone or in combination of two or more.

Other additives include antioxidants, UV absorbers, weathering agents, anti-aging agents, fillers, antistatic agents, flame retardants, antifogging agents, lubricants, antibacterial agents, fungicides, and tackifiers. , Plasticizers, colorants, graphite, carbo black, carbon nanotubes, pigments (for example, including pigments having infrared absorption and reflection ability and functionality). 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 material layer (II)
The base material layer (II) is made of a thermoplastic resin and is laminated on the skin layer (I) to give heat resistance to the entire laminated film, and the dimensional change when left at 120 ° C. for 30 minutes. There is no particular limitation as long as the rate is within a range of ± 1%. Therefore, the thermoplastic resin constituting the base layer (II) is 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 depends on the material of the other party's goods.

  As the thermoplastic resin constituting the base material layer (II), a thermoplastic resin having high heat resistance is preferable, and usually the one having a dimensional change rate within a range of ± 1% when left at 120 ° C. for 30 minutes. For example, the same dimensional change rate can be given to the whole laminated film. Therefore, the dimensional change rate when the thermoplastic resin constituting the base material layer (II) is left at 120 ° C. for 30 minutes is preferably ± 1% or less, more preferably ± 0.8% or less, and ± 0.5%. The following is more preferable, and ± 0.4% or less is particularly preferable.

  Specific examples of the thermoplastic resin constituting the base layer (II) include aromatic vinyl resins (for example, styrene resins, rubber-reinforced styrene resins, acrylonitrile / styrene resins, and other aromatic vinyl compounds ( Co) polymers), polyolefin resins (eg, polyethylene resins, polypropylene resins, ethylene-α-olefin resins, etc.), polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, saturated Polyester resins, polycarbonate resins, acrylic resins (for example, (co) polymers containing structural units derived from (meth) acrylate compounds), fluorine resins, ethylene / vinyl acetate resins, polyamide resins Etc. These can be used individually by 1 type or in combination of 2 or more types. Among these, rubber-reinforced styrene resin, α-methylstyrene, N-phenyl, which has improved heat resistance by including structural units derived from maleimide compounds such as α-methylstyrene, N-phenylmaleimide, N-cyclohexylmaleimide, etc. Heat resistance is improved by alloying with rubber-reinforced styrene resin and polycarbonate resin containing (co) polymer, which has improved heat resistance by including structural units derived from maleimide compounds such as maleimide and N-cyclohexylmaleimide. The rubber-reinforced styrene resin obtained is preferably used.

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

  The thermoplastic resin constituting the base layer (II) includes antioxidants, ultraviolet absorbers, weathering agents, anti-aging agents, fillers, antistatic agents, flame retardants, antifogging agents, lubricants, antibacterial agents, Fungi, tackifiers, plasticizers, colorants, graphite, carbo black, carbon nanotubes, pigments (for example, pigments having infrared absorption and reflection ability and functionality) are included in the object of the present invention. It can also be added as long as it is not impaired. These can be used individually by 1 type or in combination of 2 or more types.

Laminated film The laminated film of the present invention can be produced, for example, by methods that can be used for producing thermoplastic films and sheets, such as solution casting, melt extrusion, melt pressing, and coextrusion. The melt extrusion method and coextrusion method are excellent for large-scale production, but the solution cast method and the melt press method are also useful for the purpose of small scale, special purpose use, and quality evaluation. In the melt extrusion method, a T-die method or an inflation method is used. In the melt press method, a calendar method is used.

  In the T-die method, there is an advantage that it can be produced at a high speed. In that case, the resin temperature at the time of molding is not lower than the melting temperature and lower than the decomposition temperature of the resin, and is generally a temperature of 150 to 250 ° C. Is appropriate.

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

  Furthermore, the laminated film of the present invention may be produced by, for example, producing a single-layer film by T-die molding or inflation molding and then heat lamination (thermal welding) or extrusion lamination. Moreover, you may manufacture a laminated | multilayer film at once, without manufacturing a single layer film by multilayer extrusion molding using a T-die multilayer extrusion molding machine etc.

The thickness of the skin layer (I) of the laminated film thus obtained is usually 25 to 600 μm, preferably 50 to 500 μm, more preferably 75 to 400 μm. If the thickness is within this range, not only the generation of squeaking noise is suppressed, but also the film formability when producing a single layer film by T-die molding or inflation molding, laminated film by lamination or multilayer extrusion molding, etc. It is preferable because it is possible to obtain a laminate having excellent adhesion between the base material layer and the skin layer when producing the product, and excellent appearance.
The thickness of the base material layer (II) of the laminated film of the present invention thus obtained is usually 25 to 1200 μm, preferably 50 to 1000 μm, more preferably 75 to 800 μm. If the thickness is within this range, not only the generation of squeaking noise is suppressed, but also the film formability when producing a single layer film by T-die molding or inflation molding, laminated film by lamination or multilayer extrusion molding, etc. It is preferable because it is possible to obtain a laminate having excellent adhesion between the base material layer and the skin layer when producing the product, and excellent appearance. The total thickness of the laminated film of the present invention thus obtained 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, winding property, etc.) is good, the generation of squeaking noise can be further reduced sufficiently, and the surface of the resulting laminate is torn, It is preferable because the appearance becomes more satisfactory without appearance defects such as wrinkles and cracks.

  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, the design, and the like, as long as the effects of the present invention are not lost. Other layers such as a layer and a layer made of a recycled resin produced during production may be interposed between the skin layer (I) and the base material layer (II).

Laminated body in which laminated film is laminated The laminated film of the present invention can be laminated on the surface of the article with the base 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 other articles are in dynamic contact with the skin layer (I). It is possible to suppress the generation of itching sound. Thus, by laminating the laminated film of the present invention on the surface of an article, it is possible to produce a laminate having a surface with a matte appearance and suppressed generation of squeaking noise.

  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 mold. It is suitable for laminating on the surface of the article by the method (film insert molding method). Schematically, the step of disposing the laminated film of the present invention in the cavity of the injection mold, and the skin layer (I that is the outermost layer of the obtained laminate in the cavity of the injection mold) ), An insert molded product, that is, a laminate can be produced by injecting the resin composition from the opposite side. More specifically, when the laminated film of the present invention has the skin layer (I) only on one side of the base layer (II), the resin composition is injected to the base layer (II) side, When the laminated film of the present invention has the skin layer (I) on both sides of the base material layer (II), the resin composition is an insert-molded product, that is, the skin layer (I) that forms the outermost layer of the laminate. Is injected on the opposite side. The laminated film of the present invention may have another layer on the side on which the 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 be interposed.

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

  Next, the male mold 11 and the female mold 12 are clamped, and the thermoplastic resin composition that is in a heat-melted state from the introduction port 14 formed in the male mold 11 into the cavity formed by both molds, or room temperature curing. The molding material 2 which consists of a thermosetting or thermosetting resin composition is supplied (refer FIG.1 (C)). When the molding material 2 is made 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 appropriately trimmed. Through the above steps, a laminated body 5 is obtained in which the laminated film 1 is bonded as the laminated portion 4 to the surface of the resin molded portion 3 made of the thermoplastic resin composition or the cured resin composition (see FIG. 1D). . Since this laminated body 5 is provided with the skin layer (I) of the laminated film 1 as an outermost layer, the generation of squeaking noise when other articles dynamically contact the outermost layer is suppressed.

  In the manufacturing method using FIG. 1, trimming of unnecessary portions of the laminated film has been described, but the present invention is not limited to this. For example, when manufacturing the laminated body 5 as shown in FIG. 2, the laminated film of the present invention is cut into a predetermined size and placed at a predetermined position inside the injection mold. The molding material can be introduced at. FIG. 2 shows a laminated body 5 in which two laminated parts 4 are formed on the surface of the resin molded part 3. As a method for producing such a laminated body 5, the molding material injection step shown in FIG. Can be performed only once to form a plurality of laminated portions 4 or a method of forming the laminated portions 4 by performing the molding material injection step a plurality of times.

  Examples of the thermoplastic resin composition that can be used as the molding material 2 include a polystyrene resin, a styrene / acrylonitrile copolymer, a styrene / acrylonitrile / methyl methacrylate copolymer, a styrene / acrylonitrile / N-phenylmaleimide copolymer, Aromatic vinyl resins such as rubber reinforced styrene resins (ABS resin, AES resin, ASA resin, MBS resin, etc.), acrylic resins (polymethyl methacrylate, etc.), polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, Polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polycarbonate resin, polyarylate resin, polyacetal resin, polyamide resin, fluororesin, polyphenylene ether, polyphenylene 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.

  Examples of the curable resin composition that can be used as the molding material 2 include curable resins (prepolymers) made of acrylic resin, phenol resin, furan resin, acrylic silicon resin, urethane resin, melamine resin, epoxy resin, and the like. Examples thereof include an uncured curable composition containing a curing agent (such as a polymerization initiator).

  In the laminate 5 obtained by the present invention, since the laminate portion 4 includes the skin layer (I) of the laminate film of the present invention as the outermost layer, plastic, crosslinked rubber (including vulcanized rubber), fiber assembly When it comes into contact dynamically with other articles made of metal (including alloys), glass, ceramics, etc., it has the performance of suppressing the generation of squeaking noise. Therefore, in an article having at least two parts that are in contact with each other, one part is composed of the laminated body 5 and is brought into contact with another part at the place of the laminated part 4, so that the squeaky sound caused by vibration, twist, impact, etc. The effect of suppressing the generation can be obtained. Even if the above two parts are always in contact by adhesion, contact, etc., they are arranged with a predetermined gap, and one or both of them are moved or deformed by vibration, torsion, impact, etc. and dynamically contacted. Even in the case of (for example, surface contact, line contact, point contact), the effect of suppressing the generation of stagnation noise is exhibited. Specifically, as shown in FIG. 3A, an article that is in contact with each of the two parts 50 being in contact with each other, as shown in FIGS. 3B to 3F, a part of the part 60 is a part. The article | item etc. which are contacting in the state fitted to the recessed part formed in 50 are mentioned.

  As a specific example of an article that is in contact with each other in a state in which the parts are fitted, as shown in FIG. 3B, contact is made in a state where one end of the part 60 is closely fitted in a complementary recess formed in the part 50. An article in contact with each of the two complementary recesses formed in the corners of the part 50 with each end of the part 60 fitted tightly, as shown in FIG. 3C, As shown in FIG. 3D, an article in which each end of the part 60 is in close contact with a complementary recess formed in each of the two parts 50 arranged substantially in parallel, FIG. 3E As shown in FIG. 3, a part 60 having an outer surface dimension that is the same as the inner surface dimension of the part 50 is inserted into the part 50 in a nested manner, and the inner surface and the outer surface of both the parts 50 are closely fitted. For example, an article in contact. In addition, the two parts 50 and 60 in the article of the present invention do not need to be closely fitted to each other, and are fitted to each other with a certain amount of gap or play as shown in FIG. The article may repeat contact and non-contact with each other when an external force such as an impact is applied to the article.

  3A to 3F, the component 50 has a configuration in which the laminated film 1 of the present invention is laminated as a laminated portion 4 on at least a surface in contact with the component 60, and the component 60 is a skin layer (I ), It is possible to obtain an effect of suppressing generation of squeaking noise caused by vibration, twisting, impact, or the like.

  The laminates 5 and 50 obtained by the present invention are composed of at least two parts that come into contact with each other, such as a vehicle, an electric / electronic device, an OA (office automation) device, a home appliance, a building material, and a sanitary product. It is suitable as a component constituting an article, and is suitable as a component of an article composed of components that fit together in a recess or a hole, such as an automobile interior material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited only to a following example. In the examples, parts and% are based on mass unless otherwise specified.

Production Examples of Molding Resins 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 a Henschel mixer at the blending ratio shown in Table 1. Then, using a twin screw extruder (model name “TEX44, Nippon Steel Works”), it was melt-kneaded at a barrel temperature of 270 ° C. to be pelletized.
1. Raw material [P]
As a thermoplastic resin including a portion derived from a rubbery polymer, the ethylene / α-olefin rubber-reinforced aromatic vinyl resin (raw materials P1 to P4) obtained in Synthesis Examples 1 to 4 below 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))
A stainless steel autoclave equipped with a ribbon stirrer blade, a continuous additive addition device, a thermometer, etc., is subjected to ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C., glass transition temperature: −50 ° C., Mooney viscosity (ML1 + 4, 100 ° C.): 20) 25 parts, 11 parts of styrene, 4 parts of acrylonitrile, 0.5 part of tert-dodecyl mercaptan and 110 parts of toluene were heated and heated. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.09 part of tert-butyl peroxyisopropyl monocarbonate was added, and the temperature was further increased. While maintaining the internal temperature at 100 ° C., the polymerization was started at a stirring rotation speed of 100 rpm. After polymerization for 60 minutes, 44 parts of styrene, 16 parts of acrylonitrile and 0.86 part of tert-butylperoxyisopropyl monocarbonate were added continuously over 3 hours. After 4 hours from the start of polymerization, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion rate was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Subsequently, the reaction liquid was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Thereafter, the volatile matter was substantially degassed using an extruder with a 40 mmφ vent (cylinder temperature 220 ° C., degree of vacuum 760 mmHg), pelletized, a portion made of ethylene / propylene copolymer rubber, a vinyl cyanide compound ( An ethylene / α-olefin rubber graft copolymer (graft resin) comprising a structural unit derived from acrylonitrile) and a vinyl copolymer copolymer containing 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 obtained from the polymerization recipe and the polymerization conversion rate. 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%. The intrinsic viscosity [η] of the solute (in methyl ethyl ketone, 30 ° C.) was 0.42 dl / g. Then, when Tm of raw material P1 was measured using this pellet, it was 40 degreeC.

1-2. Synthesis Example 2 (Synthesis of raw material P2 (AES resin))
A stainless steel autoclave equipped with a ribbon stirrer blade, a continuous additive addition device, a thermometer, etc., is subjected to ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C., glass transition temperature: −50 ° C., Mooney viscosity (ML1 + 4, 100 ° C.): 20), 7.3 parts of styrene, 2.7 parts of acrylonitrile, 0.3 part of tert-dodecyl mercaptan and 220 parts of toluene were charged and heated. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.07 part of tert-butyl peroxyisopropyl monocarbonate was added, and the temperature was further increased. While maintaining the internal temperature at 100 ° C., the polymerization was started at a stirring rotation 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 from the start of polymerization, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion rate was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Subsequently, the reaction liquid was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Thereafter, the volatile matter was substantially degassed using an extruder with a 40 mmφ vent (cylinder temperature 220 ° C., degree of vacuum 760 mmHg), pelletized, a portion made of ethylene / propylene copolymer rubber, a vinyl cyanide compound ( An ethylene / α-olefin rubber graft copolymer (graft resin) comprising a structural unit derived from acrylonitrile) and a vinyl copolymer copolymer containing 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 obtained from the polymerization recipe and the polymerization conversion rate. 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] (30 ° C. in methyl ethyl ketone) of this acetone-soluble matter is It was 0.35 dl / g. Then, when Tm of raw material P2 was measured using this pellet, it was 40 degreeC.

1-3. Synthesis Example 3 (Synthesis of raw material P3 (AES resin))
To a stainless steel autoclave equipped with a ribbon-type stirrer blade, an auxiliary agent continuous addition device, a thermometer, etc., an ethylene / propylene copolymer rubber (ethylene / propylene = 74/26 (%), Tm: 29 ° C., glass transition temperature: −50 ° C., Mooney viscosity (ML1 + 4, 100 ° C.): 20) 25 parts, 11 parts of styrene, 4 parts of acrylonitrile, 0.5 part of tert-dodecyl mercaptan and 110 parts of toluene were heated and heated. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.09 part of tert-butyl peroxyisopropyl monocarbonate was added, and the temperature was further increased. While maintaining the internal temperature at 100 ° C., the polymerization was started at a stirring rotation speed of 100 rpm. After polymerization for 60 minutes, 44 parts of styrene, 16 parts of acrylonitrile and 0.86 part of tert-butylperoxyisopropyl monocarbonate were added continuously over 3 hours. After 4 hours from the start of polymerization, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion rate was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Subsequently, the reaction liquid was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Thereafter, the volatile matter was substantially degassed using an extruder with a 40 mmφ vent (cylinder temperature 220 ° C., degree of vacuum 760 mmHg), pelletized, a portion made of ethylene / propylene copolymer rubber, a vinyl cyanide compound ( An ethylene / α-olefin rubber graft copolymer (graft resin) containing a structural unit derived from acrylonitrile) and a vinyl copolymer 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 made 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 the calculation of the graft ratio was determined from the polymerization recipe and the polymerization conversion rate. The content of the ungrafted vinyl copolymer (hereinafter also referred to as “acetone soluble content”) contained in the raw material P3 is 61% when the entire raw material P3 is 100%. The intrinsic viscosity [η] of the solute (in methyl ethyl ketone, 30 ° C.) was 0.45 dl / g. Then, when Tm of raw material P3 was measured using this pellet, it was 29 degreeC.

1-4. Synthesis Example 4 (Synthesis of raw material P4 (AES resin))
Into a 20 liter stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary agent addition device, thermometer, etc., ethylene / propylene / dicyclopentadiene copolymer (ethylene / propylene / dicyclopentadiene = 63/32/5) (%), Mooney viscosity (ML1 + 4, 100 ° C.) 33, no melting point (Tm), glass transition temperature (Tg) of −52 ° C.) 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 part of tert-butylperoxyisopropyl monocarbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. went. From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature to complete the polymerization reaction. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Subsequently, the reaction liquid was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Thereafter, using a 40 mmφ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), the volatile matter was substantially degassed, pelletized, and a portion made of ethylene / propylene / dicyclopentadiene copolymer rubber; And α-olefin rubber graft copolymer (graft) comprising a structural unit derived from a vinyl fluoride compound (acrylonitrile) and a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene) Resin) and a rubber-reinforced aromatic vinyl resin (raw material P4) which is a resin mixture composed of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer). 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 obtained from the polymerization recipe and the polymerization conversion rate. The content of the acetone-soluble component contained in the raw material P4 is 52% when the entire raw material P4 is 100%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component 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 part of potassium rosinate, 0.2 part of tert-dodecyl mercaptan, polybutadiene rubber having an average particle diameter of 300 nm (gel content: 80% ) 80 parts of latex containing 32 parts, 19 parts of latex containing 8 parts of styrene / butadiene copolymer rubber (styrene unit amount 30%) having an average particle size of 600 nm, 14 parts of styrene and 6 parts of acrylonitrile are accommodated and stirred. The temperature rose. When the internal temperature reached 40 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.3 parts of glucose were dissolved in 8 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerizing for 30 minutes, 45 parts of ion-exchanged water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.13 part of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide were added for 3 hours. Over time. Thereafter, the polymerization was further continued for 1 hour, and 0.2 part 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 wash it with water. Then, using a potassium hydroxide aqueous solution, washed and neutralized, further washed with water, dried, a portion made of styrene-butadiene copolymer rubber, a structural unit derived from a vinyl cyanide compound (acrylonitrile), and A diene rubber graft copolymer (graft resin) containing a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene), and an ungrafted vinyl copolymer (acrylonitrile A rubber-reinforced aromatic vinyl resin (raw material P5), which is a resin mixture made of a styrene copolymer), was obtained. The graft ratio of the diene rubbery 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 recipe and the polymerization conversion rate. 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 [η ] (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 that do not contain a portion derived from a rubbery polymer.

2-1. Raw material Q1 (AS resin)
An acrylonitrile / styrene copolymer having a ratio of acrylonitrile units and styrene units of 27% and 73%, respectively, and an intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.30 dl / g. The glass transition temperature (Tg) was 103 ° C.

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

2-3. Raw material Q3 (PMI resin)
N-phenylmaleimide / acrylonitrile / styrene copolymer “Polyimilex PAS1460 (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)
A 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 matte material)
As an inorganic matting material, a granular glass flake “Micro Glass Freca REFG-101” (trade name) manufactured by Nippon Sheet Glass Co., Ltd. was 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)
As the organic matting material, a partially cross-linked acrylic additive “methabrene F-410” (trade name, cross-linked methyl methacrylate-alkyl acrylate-styrene copolymer) manufactured by Mitsubishi Rayon Co., Ltd. was used.

Reference example (production and evaluation of a single layer film)
1. Preparation of Single Layer Film Using each thermoplastic resin pellet shown in Table 1, a single layer film test piece was prepared by extrusion film formation with a T-die. For the production of the single layer film, a film forming machine provided with a T die having a die width of 1,600 mm and a lip interval of 0.25 mm and an extruder having a screw diameter of 115 mm was used. Each molding resin pellet shown in Table 1 was supplied to an extruder and melted at a temperature of 270 ° C., and the molten resin was continuously discharged from a T die to obtain a single layer film. Then, this single layer film was cooled and solidified while being in surface contact with a cast roll whose surface temperature was controlled at 70 ° C. with an air knife, and a single layer film having a thickness (100 μm) described in Table 1 was obtained. It was.

2. Dimensional stability of single layer film The dimensions of the resin extrusion direction (MD) from the T die of the single layer film obtained in 1 above and the direction (TD) perpendicular to MD were measured before and after heat treatment.
A square of 100 mm (MD) × 100 mm (TD) was drawn at the center of the surface of a test piece of 120 mm (MD) × 120 mm (TD) cut out from the center in the TD direction of the single-layer film obtained in 1 above. This test piece was left still in a thermostat and heat-treated at 120 ° C. for 30 minutes in an air atmosphere. Thereafter, the test piece was taken out, the length of each side in the square MD and TD directions was measured at 25 ° C., and the shrinkage was calculated according to the following formula.
Shrinkage rate (%) = {(length after heating) − (length before heating)} / (length before heating) × 100
From the shrinkage rate obtained from the above formula, the heat resistance was evaluated according to the following criteria, and the results are shown in Table 1. In addition, the following shrinkage rate becomes a negative value when the test piece contracts after heating, and becomes a positive value when the test piece expands after heating.
A: Shrinkage rate (s) was −0.5% ≦ s ≦ 0% or 0% ≦ s ≦ 0.5%.
○: Shrinkage rate (s) was −1.0% ≦ s <−0.5% or 0.5% <s ≦ 1.0%.
X: Shrinkage rate (s) was −2.0% ≦ s <−1.0% or 1.0 <s ≦ 2.0%.
Xx: Shrinkage 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 “DSC2910” (model name) manufactured by TA Instruments in accordance with JIS K7121-1987. The measurement was performed by observing the endothermic change at a constant temperature increase 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 using a thickness gauge “ID-C1112C” (model name) manufactured by Mitutoyo Corporation. , And measured from the center toward both ends at intervals of 10 mm to obtain an average value. Measurement point values in the range of 20 mm from the edge of the film were excluded from the above average calculation.

Examples 1-15 and Comparative Examples 1-6 (Production and Evaluation of Laminated Film)
1. Production of laminated film A film forming machine equipped with a T-die having a die width of 1.600 mm and a lip interval of 0.25 mm and an extruder having a screw diameter of 115 mm was used. Each molding resin pellet shown in Table 2 was supplied to an extruder and melted at a temperature of 270 ° C., and the molten resin was continuously discharged from a T-die to obtain a single layer film. Then, the surface layer (I) and the base material layer (II) having the thicknesses described in Table 2 while the surface of the single-layer film is closely adhered to a cast roll whose surface temperature is controlled to 70 ° C. by an air knife. A single-layer film constituting each of the above was obtained. Then, an adhesive layer forming material (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, on the surface of the adhesive layer side of the skin layer film with an adhesive layer, the single layer film constituting the base material layer (II) is brought into contact with the surface, and this is thermally welded by a rotary heat press machine. The laminated film shown in Table 2 was obtained.

2. Dimensional stability of laminated film The dimensions of the laminated film obtained in 1 above in the direction of extrusion (MD) of the resin from the T-die and the direction perpendicular to MD (TD) were measured before and after the heat treatment.
A square of 100 mm (MD) × 100 mm (TD) was drawn at the center of the surface of a test piece of 120 mm (MD) × 120 mm (TD) cut out from the center in the TD direction of the laminated film obtained in 1 above. This test piece was left still in a thermostat and heat-treated at 120 ° C. for 30 minutes in an air atmosphere. Thereafter, the test piece was taken out, the length of each side in the square MD and TD directions was measured at 25 ° C., and the shrinkage was calculated according to the following formula.
Shrinkage rate (%) = {(length after heating) − (length before heating)} / (length before heating) × 100
From the shrinkage rate obtained from the above formula, the heat resistance was evaluated according to the following criteria, and the results are shown in Table 2. In addition, the following shrinkage rate becomes a negative value when the test piece contracts after heating, and becomes a positive value when the test piece expands after heating.
A: Shrinkage rate (s) was −0.5% ≦ s ≦ 0% or 0% ≦ s ≦ 0.5%.
○: Shrinkage rate (s) was −1.0% ≦ s <−0.5% or 0.5% <s ≦ 1.0%.
X: Shrinkage rate (s) was −2.0% ≦ s <−1.0% or 1.0 <s ≦ 2.0%.
Xx: Shrinkage rate (s) was s <-2.0% or 2.0% <s.

3. Vacuum Formability of Laminated Film From the center in the TD direction of the laminated film obtained in 1 above, a laminated film having a size of 300 mm (MD) × 210 mm (TD) is cut out, and the molded product shown in FIG. It was produced using a small vacuum forming machine “300X” manufactured by Seiko Sangyo Co., Ltd. equipped with a vacuum forming die 8 shown in FIG. The vacuum forming die 8 shown in FIG. 4 has a height of 45 mm, a bottom surface size of 150 mm × 150 mm, a top surface size of 140 m × 140 mm, and a center of the top surface of 100 mm × 100 mm. A recess having a size of 20 mm in depth is formed and has fine through holes throughout.
The laminated film of the above size was fixed upward from the upper surface of the vacuum forming die 8 with an interval of 40 mm (FIG. 5I). Then, the laminated film was heated from the peripheral side using a heater (not shown) heated to 450 ° C. in advance. Next, the vacuum forming die 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 die 8, the laminated film was brought into close contact with the inner surface of the recess of the vacuum forming die 8, and vacuum forming was carried out (FIG. 5 (III)). Next, the vacuum forming die 8 was removed to obtain a molded product shown in FIG. 5 (IV). The followability of the laminated film to the recesses of the vacuum forming die 8 was visually observed, evaluated according to the following criteria, and the results are shown in Table 2.
◯: The followability to the concave portion of the vacuum forming die 8 was good, and no wrinkles were observed on the film surface of the molded product shown in FIG.
(Triangle | delta): Although the followable | trackability to the recessed part of the type | mold 8 for vacuum forming was favorable, wrinkles were observed on the film surface of the molded article shown in FIG.5 (IV).
X: The followability to the recessed part of the vacuum forming die 8 was poor, and wrinkles were observed on the film surface of the molded product shown in FIG.

4). Stick-slip test of laminated film (abnormal noise risk index)
The stick-slip test is performed by using a stick slip tester “SSP-02” (model name) manufactured by ZIEGLER, a test piece 18 and an ABS / PC alloy “EXCELLOY CK20” (manufactured by Technopolymer). Was set as shown in FIG. 7, and the two were rubbed together three times to measure the abnormal noise risk index. The results are shown in Table 2. The measurement conditions are temperature: 23 ° C., humidity: 50% RH, load: 40 N, speed: 10 mm / second, and amplitude: 20 mm. The smaller the abnormal noise risk index, the lower the risk of itching.
In addition, the test body 18 cuts out the laminated | multilayer film 4 in the magnitude | size of 50 mm (MD) x 25 mm (TD) from the center of the TD direction of the laminated | multilayer 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” (manufactured by Techno Polymer Co., Ltd.) melted at 240 ° C. is injected onto the surface of the base film layer (II) side of the laminated film 4 to form a resin. A part 16 (50 mm × 25 mm × 4 mm) was formed (see FIG. 6).

5. Flexibility of laminated film After cutting out a laminated film having a size of 100 mm (MD) × 100 mm (TD) from the center in the TD direction of the laminated film obtained in 1 above and bending it along the axis of symmetry in the MD direction And bent along the axis of symmetry in the TD direction. Next, the film in the folded state as described above was reciprocated twice on each crease at a speed of 5 mm / second using a manual crimping roll (2,000 g) according to JIS Z0237, and then the crease was spread. It returned to the original state, the crease | fold was observed visually, and the following reference | standard determined. Those in which the folds are not broken are excellent in flexibility.
○: The crease was not cracked, and the crease did not break even when folded and expanded again.
(Triangle | delta): Although the crease | fold is not cracked, when it was folded again and spread, the crease | fold was cracked.
X: The crease was broken.

6). Matting property A test specimen 18 produced by the method described in the above item 4 (stick-slip test) was placed in a dark room so that the resin film 4 faced upward. Thereafter, a fluorescent lamp “FLR40SW / M / 36” (trade name) manufactured by Mitsubishi Electric Lighting Co., Ltd., which is disposed on the ceiling of the dark room, which is directly above the test body 18 and has a distance of 2 m from the resin film 4, is emitted. The matte property of the resin film 4 was visually observed by five panelists and evaluated according to the following criteria. The results are shown in Table 2.
○: All five panelists judged that there was no reflection or reflection of a fluorescent lamp on the film surface, and a good matte appearance was obtained.
Δ: 1-4 persons out of 5 panelists judged that there was a reflection or reflection of a fluorescent lamp on the film surface, and a good matte appearance was not obtained.
X: All five panelists judged that there was reflection or reflection of a fluorescent lamp on the film surface, and a good matte appearance was not obtained.

Table 2 shows the following.
Examples 1 to 15 using the laminated film of the present invention showed good results in any of dimensional stability, vacuum formability, flexibility, stick-slip test, and matteness. On the other hand, Comparative Examples 1, 5 and 6 which do not have a skin layer (I) made of a rubber-reinforced aromatic vinyl resin having a melting point of 0 to 120 ° C. are flexible and vacuum molded as a result of the stick-slip test. Inferior in nature and mattness. Comparative Example 2 having a skin layer (I) made of a rubber-reinforced aromatic vinyl resin having no melting point was inferior in the result of the stick-slip test. Comparison in which a layer made of a thermoplastic resin having a dimensional stability of ± 1% or less is a skin layer (I), and a layer made of a rubber-reinforced aromatic vinyl resin having a melting point of 0 to 120 ° C. is a base material layer (II) In Example 3, the results of the stick-slip test and the matte property were inferior. Comparative Example 4 in which the skin layer (I) does not contain a matting material was inferior in matting properties.

  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 product by thermoforming, insert molding, in-mold molding, etc. A surface layer having a matte appearance can be imparted while suppressing the squeaking noise that is generated, and the obtained molded product can be suitably used as a component of an article composed of two or more components that are in contact with each other.

Claims (10)

A laminated film comprising a skin layer (I) on at least one surface of a base material layer (II) made of a thermoplastic resin,
The skin layer (I) is composed of a thermoplastic resin composition containing a rubber-reinforced aromatic vinyl resin (A) and a matting material (Y),
The melting point of the skin 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 rate of ± 1% or less when the laminated film is left at 120 ° C. for 30 minutes. The laminated film according to claim 1, wherein the rubber portion of the rubber-reinforced aromatic vinyl resin (A) is an ethylene / α-olefin rubber. The laminated film according to claim 2, wherein the ethylene / α-olefin rubber has a melting point (measured according to JIS K 7121-1987) in the range of 0 to 120 ° C. The laminated film according to any one of claims 1 to 3, wherein the matting material (Y) is an inorganic matting material. A step of disposing the laminated film according to any one of claims 1 to 4 in a cavity of an injection mold, and an outermost part of the laminated film in the cavity of the injection mold. A process for injecting a resin composition from the side opposite to the outer skin layer (I). The film for insert molding which consists of a laminated | multilayer film of any one of Claims 1-4. The laminated body by which the laminated film of any one of Claims 1-4 was laminated | stacked on the resin molded product on the surface on the opposite side to the skin layer (I) of the said laminated film. The laminate according to claim 7, wherein the skin layer (I) of the laminate film is present as an outermost layer. The laminate according to claim 8, wherein the skin layer (I) of the laminate film is in contact with another member. An article having at least two parts in contact with each other, wherein at least one of the parts comprises the laminate according to any one of claims 7 to 9, and the skin layer of the laminated film of the laminate Articles where (I) contacts other parts.

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