JP2016014125A - Film for insert molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for insert molding suitable for forming a resin film part which prevents generation of rubbing and squeaking noises when dynamically in contact with other parts on the surface of a base part composed of a resin composition and has good matte appearance, and a method for producing a composite comprising the base part and the resin film part.SOLUTION: There is provided a film for insert molding which comprises a thermoplastic resin containing a moiety (a-1) derived from a rubbery polymer such as an ethylene-α-olefin based rubber and a matting material and is composed of a thermoplastic resin composition having a melting point (according to JIS K 7121-1987) of 0 to 120°C. The thermoplastic resin preferably comprises a rubber-reinforced vinyl-based resin containing a moiety (a1) derived from a rubbery polymer and a moiety (a2) derived from a vinyl-based polymer containing a structural unit derived from a vinyl-based monomer.

Description

  The present invention can suppress the generation of rubbing noise (hereinafter referred to as “stagnation sound”) on the surface of the base portion made of a resin composition when it dynamically contacts other parts, and provides a good matte appearance. The present invention relates to a film for insert molding suitable for producing a laminate having a resin film part (hereinafter also referred to as “insert molded product” or “compression reducing composite”).

  Conventionally, a film made of a thermoplastic resin composition is placed inside an injection mold, the resin composition is injected into the cavity of the injection mold, and the base made of the film and the resin composition is joined. Insert molding methods for producing composites are known. Conventionally, for example, this method uses a film (decorative film consisting of a single layer or multiple layers) on which images such as letters, numbers, patterns, designs, pictures, photographs, etc. are formed. Widely applied as a manufacturing method (for example, Patent Documents 1 to 3).

  By the way, a thermoplastic resin composition or a cured resin composition is used as a raw material for parts having performance according to the purpose in every scene today. However, in recent years, thermoplastic resin parts (referred to as “parts made of thermoplastic resin composition Z”) used in the fields of vehicles, OA (office automation) equipment, household electrical appliances, electrical / electronic equipment, building materials, etc. Used in combination with other parts such as thermoplastic resin parts made of the same or different materials as the thermoplastic resin composition Z, cured resin parts, or inorganic material parts made of metal or inorganic compounds Is being increased. For example, a part made of thermoplastic resin and another part are placed in contact with each other, or these parts are placed at a predetermined interval. In such an embodiment, the parts made of thermoplastic resin are placed between each other. Are adjacent (simply touching each other, or both are in contact with each other, or both are arranged at a predetermined interval), vibration, rotation, twisting, It is known that one or both of them are moved or deformed by sliding, impact, etc., and dynamically contacted to generate a squeaking sound (rubbing sound). For example, an air conditioner or audio casing component arranged in an automobile and a fitting component arranged on the periphery or inside of the casing generate frictional noises (smearing sounds). is there. This squeaking sound is said to be a sound caused by a stick-slip phenomenon that occurs when two objects rub against each other. The stick-slip phenomenon is said to be a phenomenon different from the sliding phenomenon between objects as conventionally known.

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 is first driven by the action of a static friction force. And 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 again in the same direction as the driving speed V (FIG. 9D). 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. Itching is a major cause of impairing comfort and quietness in automobiles, offices, and residential rooms, and there is a strong demand for suppression and reduction of itching.

  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.

  As a film having a matte appearance used for insert molding or in-mold molding, a matte acrylic resin film having a matte layer containing a matting material and a binder resin on an acrylic resin fat film substrate, on the matte layer side A matte acrylic resin film is disclosed in which the difference between the yellowness of the matte acrylic resin film after heating to a surface temperature of 200 ° C. and the yellowness of the matte acrylic resin film before heating is 1.3 or less. (Patent Document 4).

JP 2002-338797 A JP 2005-349839 A JP2013-001855A Japanese Patent Laid-Open No. 2007-062194

However, even if a composite is manufactured using the films as described in Patent Documents 1 to 4 above, it is possible to suppress the generation of rubbing noise when dynamically contacting other parts, and a good matte appearance. It was not possible to obtain a laminate provided with a resin film portion that gave the.
The present invention is excellent in flexibility and vacuum moldability, suppresses the generation of squeaking noise when dynamically contacting other parts on the surface of the base made of a resin composition, and has a good matte appearance. An object of the present invention is to provide a film for insert molding suitable for forming a resin film part, and a method for producing a laminate (a squeaking noise reducing composite, an insert molded article) including these base part and resin film part. .

The present invention is as follows.
1. Thermoplastic resin containing a thermoplastic resin containing a part (a1) derived from a rubbery polymer and a matting material (Y) and having a melting point in the range of 0 to 120 ° C. according to JIS K 7121-1987 A film for insert molding comprising the composition.
2. 2. The film for insert molding as described in 1 above, wherein the rubbery polymer is ethylene / α-olefin rubber.
3. 3. The insert molding film according to 2 above, wherein the ethylene / α-olefin rubber is a copolymer having a melting point in the range of 0 to 120 ° C. according to JIS K 7121-1987.
4). The film for insert molding according to any one of 1 to 3 above, wherein the thermoplastic resin is a rubber-reinforced vinyl resin including the part (a1) and a part (a2) derived from a vinyl resin.
5. The film for insert molding according to any one of 1 to 5 above, wherein the matting material (Y) is an inorganic matting material.
6). The film for insert molding according to any one of 1 to 5 above, wherein the thickness is 50 to 300 µm.
7). The step of disposing the insert molding film according to any one of 1 to 6 above in an injection mold, and the step of injecting a resin composition into a cavity of the injection mold. A method for producing an insert-molded product, comprising:

In this specification, “(meth) acryl” refers to acryl and methacryl, “(meth) acrylate” refers to acrylate and methacrylate, “(meth) acryloyl group” refers to acryloyl group or methacryloyl group, “Polymer” means homopolymers and copolymers.
The melting point (hereinafter referred to as “Tm”) according to JIS K 7121-1987 was obtained by measuring endothermic changes at a constant temperature increase rate of 20 ° C. per minute using DSC (differential scanning calorimeter). It is a value obtained by reading the peak temperature of the obtained endothermic pattern.

  Since the film for insert molding of the present invention is formed of a specific thermoplastic resin composition, it is excellent in flexibility and vacuum moldability, and is formed by an insert molding method (film insert molding method) using an injection mold. Suppresses the occurrence of squeaking noise when dynamically contacting other parts on the surface of the base made of the same or different thermoplastic resin composition or thermosetting resin composition as this composition, and good It is suitable for the formation of a resin film part having a smooth matte appearance, that is, for the production of a laminate (a squeaking noise reducing composite, an insert molded product) including these base part and resin film part. The resin film part of the obtained laminate is adjacent to another part made of the same or other material as the thermoplastic resin composition constituting the insert molding film (simply touching or partly adhering part) Or both of them are in contact with each other, or both are arranged at a predetermined interval), or one or both of them are moved or moved by vibration, rotation, twisting, sliding, impact, etc. Even when deformed and dynamically contacted (surface contact, line contact, or point contact), the generated squeaking noise is reduced or the generation of squeaking noise is suppressed. In addition, the obtained laminate (smear noise-reducing composite, insert-molded product) includes a member used for fitting and inserting another part having a hole or a recess into the hole or the recess, and the hole. In addition, since any squeaking noise is suppressed in any of the members having recesses, it can be suitably used for applications that are used in contact with other parts such as automobile interior parts.

It is a schematic sectional drawing explaining an example of the method of manufacturing a laminated body (smack noise reduction composite, insert molding goods) using the film for insert molding of this invention. It is a schematic sectional drawing which shows an example of the laminated body (smack noise reduction composite, insert molding product) obtained by the method of this invention. It is a schematic sectional drawing which shows an example of the composite formed using the laminated body (smack noise reduction composite, insert molded article) obtained by the method of this invention, and another component. It is a schematic perspective view which shows the type | mold used for the evaluation of the vacuum formability in [Example]. It is a schematic sectional drawing explaining the evaluation method of the vacuum formability in [Example]. It is a schematic sectional drawing which shows the test body used by the stagnation sound evaluation in [Example]. It is a schematic perspective view which shows the method of the squeaking sound evaluation in [Example]. It is explanatory drawing of a stick-slip phenomenon. (A), (b), (c), (d) is a model diagram of stick-slip.

The film for insert molding of the present invention comprises a thermoplastic resin (hereinafter referred to as “thermoplastic resin (X1)”) containing a portion (a1) derived from a rubber polymer (hereinafter also referred to as “rubber polymer portion (a1)”). ))) And a matte material (Y) and a thermoplastic resin composition having a Tm (melting point) in the range of 0 to 120 ° C., and has a matte matte appearance , Has flexibility. The film for insert molding of the present invention is a thermoplastic resin composition, a cured resin composition, a rubber (processed), or a laminate obtained by the insert molding method that is the same as or different from the thermoplastic resin composition constituting the insert molding film. (Including vulcanized rubber), fiber aggregates, metals (including alloys), glass, ceramics, etc., even if it is in dynamic contact, it has the performance that generation of squeaking noise is reduced or suppressed. Therefore, the insert molding film 1 and the injection molds 11 and 12 of the present invention are used for the insert molding method according to (A), (B), (C) and (D) in FIG. As a result, the resin film part 4 (hereinafter, simply referred to as “resin film part”) having an effect of reducing the generation of squeaking noise when dynamically contacting other parts is joined to the surface of the resin molded part 3. Thus, a laminate (smudge noise reducing composite) 5 can be suitably manufactured. Furthermore, this laminate (smudge noise reducing composite) 5 is obtained by converting the insert molding film 1 of the present invention into a film structure 1a that has been previously adjusted to a predetermined shape by another process. It can also be manufactured by using the insert molding method according to (B), (C) and (D) in FIG.
As a result of subjecting the film for insert molding of the present invention to insert molding, the thickness of the resin film part in the obtained laminate may be thinner than the thickness of the film for insert molding used. The laminate is efficiently manufactured without being damaged.

  The Tm (melting point) of the thermoplastic resin composition is in the range of 0 to 120 ° C., preferably 10 from the viewpoint of the effect of reducing the occurrence of squeaking noise in the resin film portion formed by the insert molding method and the mechanical strength. It is -90 degreeC, More preferably, it exists in the range of 20-80 degreeC. As described above, Tm (melting point) is obtained according to JIS K 7121-1987, but 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. Moreover, Tm (melting point) seen in the range of 0 to 120 ° C. may be derived from the thermoplastic resin (X), other thermoplastic resins blended as necessary, and weight average molecular weight. May be derived from a low molecular weight polyolefin wax such as 10,000 or less.

The thermoplastic resin (X) is a thermoplastic resin containing a rubbery polymer part (a1) derived from a rubbery polymer, and the rubbery polymer part (a1) constituting the thermoplastic resin (X) is , May be only one kind, or may be two or more kinds.
The rubbery polymer may be a homopolymer or a copolymer as long as it is rubbery (having rubber elasticity) at 25 ° C. The rubbery polymer may be 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.

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubbers such as styrene / isoprene copolymers, styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymer rubbers such as acrylonitrile / styrene / isoprene copolymers, etc. . These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%).

  Examples of the non-diene rubber include ethylene / α-olefin copolymer rubber (hereinafter referred to as “ethylene / α-olefin rubber”); urethane rubber; acrylic rubber; silicone rubber; Examples include IPN rubbers; hydrogenated polymers obtained by hydrogenating (co) polymers containing structural units derived from conjugated diene compounds. This hydrogenated polymer may be a block copolymer or a random copolymer. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more).

  In the present invention, the rubbery polymer preferably includes an ethylene / α-olefin rubber which is a non-diene rubber.

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.
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 content ratio of the structural unit derived from ethylene and the structural unit derived from α-olefin constituting the ethylene / α-olefin rubber is the effect of reducing the occurrence of squeaking noise in the resin film portion formed by the insert molding method and From the viewpoint of impact resistance, when the total of both is 100% by mass, preferably 5 to 95% by mass and 95 to 5% by mass, more preferably 50 to 95% by mass and 50 to 5% by mass, and still more preferably. Are 60-95 mass% and 40-5 mass%.

  In the present invention, a preferable ethylene / α-olefin rubber is an ethylene / α-olefin copolymer having a Tm (melting point) in the range of 0 to 120 ° C. As long as it is derived from other monomers. It may have a structural unit. Examples of the other monomer include non-conjugated diene compounds such as alkenyl norbornenes, cyclic dienes, and aliphatic dienes. These non-conjugated diene compounds can be used alone or in combination of two or more. The upper limit of the content ratio of the structural unit derived from the non-conjugated diene compound is preferably 10% by mass, more preferably 5% when the total amount of the structural units constituting the ethylene / α-olefin rubber is 100% by mass. % By mass, more preferably 3% by mass.

  The Tm (melting point) of the ethylene / α-olefin rubber is preferably 10 to 90 ° C., more preferably from the viewpoint of the effect of reducing squeaking noise in the resin film portion formed by the insert molding method and impact resistance. 20 to 80 ° C. The Tm (melting point) of the ethylene / α-olefin-based rubber being in the range of 0 to 120 ° C. means that the rubber has crystallinity. If the ethylene / α-olefin rubber has a crystalline part, the occurrence of stick-slip phenomenon is suppressed, so even if the resin film part containing it and other parts are in dynamic contact, itching sound It is thought that the occurrence of is reduced or suppressed.

  The ethylene / α-olefin rubber is composed of a structural unit derived from ethylene and a structural unit derived from α-olefin, from the viewpoint of the effect of reducing the generation of stagnation noise in the resin film portion formed by the insert molding method. It is preferably an ethylene / α-olefin copolymer, more preferably an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-octene copolymer, and an ethylene / propylene copolymer. Particularly preferred is a coalescence.

  When the rubbery polymer part (a1) is derived from ethylene / α-olefin rubber, from the viewpoint of the effect of reducing the occurrence of squeaking noise in the resin film part formed by the insert molding method and the impact resistance, The content of the rubber polymer part (a1) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, when the thermoplastic resin (X) is 100% by mass.

  In the present invention, the rubbery polymer part (a1) can be derived from ethylene / α-olefin rubber and other rubbers. As the other rubber, for example, a diene rubber made of a (co) polymer having a structural unit derived from 1,3-butadiene or isoprene can be used from the viewpoint of further improving impact resistance.

When the rubbery polymer part (a1) is derived from both ethylene / α-olefin rubber and other rubbers, the content ratio of both is the occurrence of squeaking noise in the resin film part formed by the insert molding method. From the viewpoint of reduction effect and impact resistance, when the total of both is 100% by mass, preferably 15 to 98% by mass and 2 to 85% by mass, more preferably 25 to 95% by mass and 5 to 75%, respectively. It is 35 mass%, More preferably, it is 35-90 mass% and 10-65 mass%.
In the above aspect, the ratio of the total amount of the part derived from the ethylene / α-olefin-based rubber and the part derived from other rubber to the thermoplastic resin (X), that is, the rubbery polymer part (a1) The ratio is preferably 20 to 90 when the thermoplastic resin (X) is 100% by mass from the viewpoint of reducing the occurrence of squeaking noise in the resin film portion formed by the insert molding method and impact resistance. The mass% is more preferably 40 to 85 mass%, still more preferably 55 to 80 mass%.

Since the thermoplastic resin (X) is a thermoplastic resin containing a rubbery polymer part (a1), it is usually a resin comprising this rubbery polymer part (a1) and other structural parts. . In the present invention, the thermoplastic resin (X) is preferably the rubber polymer part (a1) and a part derived from a vinyl resin (a2) (hereinafter also referred to as “resin part (a2)”). Is a rubber-reinforced vinyl resin chemically bonded. The resin part (a2) which comprises single molecule thermoplastic resin (X) may be only 1 type, and 2 or more types may be sufficient as it.
The vinyl resin is a vinyl (co) polymer containing a structural unit derived from a vinyl monomer, preferably a vinyl (co) polymer part containing a structural unit derived from an aromatic vinyl compound. It is. That is, in a preferred embodiment, the resin part (a2) may be a vinyl (co) polymer part composed of one or more structural units derived from an aromatic vinyl compound. The vinyl-type (co) polymer part which consists of 1 type or 2 types or more of the derived structural unit and 1 type or 2 types or more of the structural unit derived from another vinyl-type monomer may be sufficient.
In addition, the minimum of content of the structural unit derived from an aromatic vinyl compound contained in the vinyl resin which comprises the said resin part (a2) is the said resin part (a2) from a viewpoint of the rigidity of a film, and an external appearance property. When the total is 100% by mass, it is preferably 50% by mass, more preferably 60% by mass, and still more preferably 65% by mass.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. However, it shall not have a substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Other vinyl monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, amides. Examples thereof include a group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound. These compounds may be used alone or in combination of two or more.

  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.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include 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 (meth) acrylate and n-butyl (meth) acrylate are preferred.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) ) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more. Of these, N-phenylmaleimide is preferred. In addition, as another method for introducing a structural unit derived from a maleimide compound into a polymer chain, for example, an unsaturated dicarboxylic anhydride of maleic anhydride is copolymerized and then imidized.

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.
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.

Examples of the amino group-containing unsaturated compound include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, and propylaminoethyl methacrylate. , Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, methacrylamine, N- Examples include methylacrylamine. These compounds can be used alone or in combination of two or more.
Examples of the amide group-containing unsaturated compound include acrylamide, N-methylacrylamide, methacrylamide, N-methylmethacrylamide and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) Having hydroxyl groups such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate ( (Meth) acrylic acid ester; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2- Hydroxy Cyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxy Methyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy- Examples include 1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2-methyl-1-propene. These compounds can be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These compounds can be used alone or in combination of two or more.
Examples of the unsaturated compound containing an oxazoline group include vinyl oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline. 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Etc.

When the vinyl resin constituting the resin part (a2) is composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from another vinyl monomer, the other vinyl monomer From the viewpoint of film rigidity and appearance, it is preferable to contain a vinyl cyanide compound, a (meth) acrylic acid ester compound, and the like.
In the present invention, when the vinyl resin constituting the resin part (a2) is a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound, The total amount of these structural units is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl copolymer, from the viewpoint of mechanical strength and chemical resistance of the film. %, More preferably 95 to 100% by mass. Moreover, the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound is, from the viewpoint of mechanical strength and chemical resistance, when these are 100% by mass, Preferably they are 55-95 mass% and 5-45 mass%, More preferably, they are 60-90 mass% and 10-40 mass%, More preferably, they are 65-80 mass% and 20-35 mass%.

  When the thermoplastic resin (X) is a rubber reinforced vinyl resin, the content ratio of the rubber polymer part (a1) and the resin part (a2) constituting the rubber reinforced vinyl resin is determined by an insert molding method. From the viewpoint of the effect of reducing the occurrence of stagnation noise in the resin film portion formed by the above and the impact resistance, when these are 100% by mass, preferably 10 to 90% by mass and 10 to 90% by mass, respectively. Preferably they are 20-80 mass% and 20-80 mass%, More preferably, they are 30-75 mass% and 25-70 mass%.

The thermoplastic resin (X) contained in the thermoplastic resin composition can be composed of one or more resins.
As described above, the thermoplastic resin (X) according to the present invention is preferably a rubber-reinforced vinyl resin, and in particular, a polymer part derived from ethylene / α-olefin rubber (hereinafter referred to as “ethylene • α”). -Olefinic rubbery polymer part ") and an ethylene / α-olefinic rubbery polymer reinforced vinyl type having a vinylic resin part composed of a vinylic (co) polymer part derived from an aromatic vinyl compound It is preferable that resin is included.
The ethylene / α-olefin rubber polymer-reinforced vinyl resin, a polymer part derived from a diene rubber (hereinafter referred to as “diene polymer part”), and a vinyl derived from an aromatic vinyl compound. When a diene rubbery polymer reinforced vinyl resin having a vinyl resin part composed of a system (co) polymer part is used in combination, the impact resistance of the film for insert molding and the laminate formed by the insert molding method The impact resistance in the resin film part of the body can be further improved.

  The content ratio of the ethylene / α-olefin rubber polymer part and the vinyl resin part constituting the ethylene / α-olefin rubber polymer reinforced vinyl resin is a resin of a laminate formed by an insert molding method. From the viewpoint of reducing the occurrence of squeaking noise in the film part and impact resistance, when the total of both is 100% by mass, preferably 10 to 90% by mass and 10 to 90% by mass, more preferably 20 to 20%, respectively. 80 mass% and 20-80 mass%, More preferably, they are 30-75 mass% and 25-70 mass%.

  The content ratio of the diene polymer part and the vinyl resin part constituting the diene rubber polymer reinforced vinyl resin is the effect of reducing the occurrence of squeaking noise in the resin film part of the laminate formed by the insert molding method, and From the viewpoint of impact resistance, when the total of both is 100% by mass, preferably 10 to 90% by mass and 10 to 90% by mass, more preferably 25 to 80% by mass and 20 to 75% by mass, More preferably, they are 30-70 mass% and 30-70 mass%.

  The ethylene / α-olefin rubber polymer reinforced vinyl resin or diene rubber polymer reinforced vinyl resin is preferably a vinyl resin in the presence of ethylene / α-olefin rubber or diene rubber. Included in rubber reinforced resins obtained by polymerizing monomers, preferably vinyl monomers containing aromatic vinyl compounds, particularly preferably vinyl monomers containing aromatic vinyl compounds and vinyl cyanide compounds It is a graft resin. The ethylene / α-olefin rubber preferably has a structural unit derived from ethylene having a Tm (melting point) in the range of 0 to 120 ° C., and preferably 3 to 20, more preferably 3 to carbon atoms. 12, more preferably an ethylene / α-olefin copolymer (hereinafter referred to as “ethylene / α-olefin rubber (r1)”) composed of structural units derived from 3 to 8 α-olefin. The aromatic vinyl compound is preferably styrene and α-methylstyrene, and the vinyl cyanide compound is preferably acrylonitrile.

  In order to produce the rubber-reinforced vinyl resin, the polymerization method (graft polymerization) of the vinyl monomer in the presence of ethylene / α-olefin rubber or diene rubber includes emulsion polymerization and suspension polymerization. , Solution polymerization, bulk polymerization, or a polymerization method combining these.

  When performing the above emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

  Examples of the polymerization initiator include organic peroxides, azo compounds, inorganic peroxides, and redox polymerization initiators.

  Examples of the organic peroxide include tert-butyl hydroperoxide, tert-amyl-tert-butyl peroxide, tert-butyl-tert-hexyl peroxide, tert-amyl-tert-hexyl peroxide, di (tert-hexyl). ) Peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydropa Oxide, 1,3-bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butyl kumi Ruperoxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxylaurate, tert-butylperoxymonocarbonate, bis (tert-butylcyclohexyl) peroxy Examples include dicarbonate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, and the like.

  Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, and 2,2′-azobis (2-methylbutyronitrile). 2,2'-azobisdimethylvaleronitrile, 4,4'-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2'-azobis (2,4,4) 4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate) and the like.

Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
The redox polymerization initiator includes sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, etc. as a reducing agent, potassium peroxodisulfate, hydrogen peroxide, cumene hydroperoxide. , Tert-butyl hydroperoxide or the like as an oxidizing agent can be used.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used individually by 1 type or in combination of 2 or more types.

The production conditions for the emulsion polymerization are not particularly limited. The polymerization initiator or the chain transfer agent can be supplied to the reaction system all at once or continuously.
For the latex obtained by emulsion polymerization, the resin component is usually coagulated with a coagulant to form a powder or the like. Thereafter, it is purified by washing with water, etc., dried and collected. For coagulation, conventionally known coagulants are used, and inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.

  The rubber reinforced resin produced by the graft polymerization mainly includes an ethylene / α-olefin rubber polymer reinforced vinyl resin or a diene rubber polymer reinforced vinyl resin, and further includes an ethylene / α-olefin resin. Includes rubber or diene rubber itself, and vinyl (co) polymers that contain structural units derived from vinyl monomers that are not chemically bonded to the rubbery polymer portion derived from these rubbers. There is a case. The latter vinyl-based (co) polymer does not include the rubbery polymer part (a1), and therefore is included as “other thermoplastic resin” described later in the rubber-reinforced resin.

  The graft ratio of the rubber-reinforced vinyl resin is preferably 10 to 150%, more preferably 20 to 120%, still more preferably 30 to 80%, from the viewpoint of film formability and impact resistance. .

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the above formula, 1 g of rubber reinforced resin is added to 20 ml of acetone and shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then a centrifuge (rotation) is performed under a temperature condition of 5 ° C. Number; 23,000 rpm) for 1 hour, and the mass (g) of the insoluble matter obtained by separating the insoluble matter and the soluble matter, and T is ethylene · α- contained in 1 gram of rubber reinforced resin. It is the mass (g) of rubbery polymers such as olefin rubber and diene rubber. The mass of the rubbery polymer can be obtained by a method of calculating from the polymerization prescription and the polymerization conversion rate, infrared spectroscopic analysis, pyrolysis gas chromatography, CHN elemental analysis and the like.

  The content ratio of the rubber-like polymer part (a1) and the resin part (a2) in the rubber-reinforced vinyl resin is as described above, and these ratios are the rubber reinforcement obtained from the rubber-reinforced resin. It can also be calculated from the result of the graft ratio in the vinyl resin.

In the rubber reinforced resin including the rubber reinforced vinyl resin produced by the graft polymerization, an acetone-soluble component (hereinafter also referred to as “acetone soluble component”) is an ungrafted polymer by-produced by the graft polymerization. And a (co) polymer having a structural unit derived from a vinyl monomer. The intrinsic viscosity [η] of acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) is preferably 0.05 to 0.90 dl / g from the viewpoint of extrudability, moldability, etc. of the thermoplastic resin composition. More preferably, it is 0.07-0.81 dl / g, More preferably, it is 0.09-0.65 dl / g, Most preferably, it is 0.12-0.55 dl / g.
The acetone-soluble component is, for example, by adding 1 gram of rubber reinforced resin to 20 ml of acetone, and shaking for 2 hours at 25 ° C. using a shaker or the like. It can be obtained by separating the soluble component.

The intrinsic viscosity [η] can be determined as follows.
A rubber reinforced resin containing a rubber reinforced vinyl resin is put into acetone, and acetone-soluble components recovered after centrifugation are dissolved in methyl ethyl ketone, and five different concentrations are prepared. Measure the reduced viscosity of the solution at each concentration to determine the intrinsic viscosity [η].

  The graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiators, chain transfer agents, emulsifiers, and the like, types and amounts of solvents, etc., used when producing rubber-reinforced vinyl resins. It can be controlled by adjusting the charging time, polymerization temperature, polymerization time and the like.

  The resin component contained in the thermoplastic resin composition according to the present invention may be composed of the thermoplastic resin (X), or composed of this thermoplastic resin (X) and another thermoplastic resin. It may be.

When the thermoplastic resin composition contains another thermoplastic resin, for example, a vinyl (co) polymer containing a structural unit derived from a vinyl monomer, a polycarbonate resin, a polyvinyl chloride resin, or polyvinylidene chloride. Resins, fluororesins, polyolefin resins, polyester resins, polyamide resins, polyimide resins, and the like can be given.
Said other thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.
When the thermoplastic resin composition contains another thermoplastic resin, the upper limit of the content is preferably 80 parts by mass, more preferably 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin (X). It is.

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 other parts are maintained while maintaining the flexibility and vacuum formability of the insert molding film. The effect of suppressing the generation of stagnation noise upon contact 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 2 to 15 parts by mass, when the thermoplastic resin is 100 parts by mass. More preferably, it is 3-12 mass parts. If the matting material (Y) contained in the film for insert molding of the present invention is in the above range, the matte appearance of the resulting laminate, while maintaining the flexibility and vacuum formability of the film, and other The effect of suppressing the generation of stagnation noise when coming into contact with a component is further excellent and preferable.

  The thermoplastic resin composition may further comprise a filler, a plasticizer, an antioxidant, an ultraviolet absorber, an anti-aging agent, a flame retardant, a lubricant, excluding the matting material (Y), depending on the purpose and application. Contains stabilizers, weathering agents, light stabilizers, heat stabilizers, antistatic agents, mold release agents, antibacterial agents, preservatives, colorants (pigments, dyes, etc.), fluorescent brighteners, conductivity enhancers, etc. Can be.

  Examples of the plasticizer include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, polyhydric alcohol ester, epoxy plasticizer, high Examples include molecular plasticizers and chlorinated paraffins. These can be used alone or in combination of two or more.

  Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.

  Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.

Examples of the flame retardant include halogen-containing compounds, phosphorus-containing compounds, guanidine compounds, and silicone compounds. These can be used alone or in combination of two or more.
In addition, aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based compound, molybdenum-based compound, zinc stannate, and the like can be used.

  Examples of the release agent include olefinic wax, silicone oil, higher fatty acid, higher fatty acid ester of monohydric or polyhydric alcohol, natural animal wax such as beeswax, natural plant wax such as carnauba wax, and natural oil such as paraffin wax. Examples thereof include natural coal-based waxes such as petroleum wax and montan wax. These can be used alone or in combination of two or more.

The olefin wax is usually a (co) polymer containing structural units derived from olefins. The structure of the olefin wax is not particularly limited, and may be linear or branched.
Examples of the olefin wax include polyethylene wax, polypropylene wax, and olefin copolymer wax (for example, ethylene copolymer wax), and these may be partial oxides. When the olefin wax is a copolymer, for example, olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-decene, 4-methyl-1-butene, 4-methyl-1-pentene, etc. A copolymer containing two or more structural units derived from olefin; at least one of structural units derived from olefin and a monomer copolymerizable with olefin (unsaturated carboxylic acid or acid anhydride thereof, (meth) acrylic acid) And a copolymer composed of a structural unit derived from an alkyl ester or the like). These copolymers may be any of random copolymers, block copolymers, and graft copolymers.

The number average molecular weight of the olefin wax is preferably 100 to 10,000, more preferably 1,000 to 6,000, and still more preferably 1,200 to 5,500 from the viewpoint of releasability.
The viscosity (140 ° C.) of the olefin wax is preferably 100 to 10,000 cps, more preferably 100 to 5,000 cps from the viewpoint of releasability.

The silicone oil preferably has a polyorganosiloxane structure, and may be, for example, a non-modified silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, or the polyorganosiloxane structure. Examples thereof include a modified silicone oil in which various organic groups are introduced into a part of the side chain and / or one terminal part of the polyorganosiloxane structure, or both terminal parts of the polyorganosiloxane structure.
Examples of the modified silicone oil include alkyl-modified silicone oil, alkyl-aralkyl-modified silicone oil, polyether-modified silicone oil, fluorine-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acid-modified silicone oil, methylstyryl-modified silicone oil, and methylchlorine. Phenyl silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone An oil etc. are mentioned.

  The kinematic viscosity (25 ° C.) of the silicone oil is preferably 10 to 100,000 cSt, more preferably 10 to 50,000 cSt, still more preferably 15 to 50,000 cSt, and particularly preferably 20 from the viewpoint of releasability. ~ 30,000 cSt. The kinematic viscosity can be measured by an Ubbelohde viscometer according to ASTM D445-46T (JIS 8803 is acceptable).

  The higher fatty acid is preferably a compound having 10 to 30 carbon atoms, and examples thereof include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

  The higher fatty acid ester is preferably a partial ester or total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms, such as stearic acid monoglyceride or stearic acid. Diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, behenic acid behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate Rate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2 Ethylhexyl stearate and the like.

  The Tm (melting point) of the thermoplastic resin composition according to the present invention is in the range of 0 to 120 ° C, but the Tm (melting point) of the thermoplastic resin (X) is preferably in the range of 0 to 120 ° C. Such a thermoplastic resin (X) is a vinyl resin comprising a polymer part derived from the ethylene / α-olefin rubber (r1) and a vinyl (co) polymer part derived from an aromatic vinyl compound. The Tm (melting point) is more preferably in the range of 10 to 90 ° C, still more preferably in the range of 20 to 80 ° C.

  As described above, the resin component contained in the thermoplastic resin composition may be composed of the thermoplastic resin (X), or is composed of this thermoplastic resin (X) and another thermoplastic resin. In any case, when the thermoplastic resin (X) is made of a rubber reinforced vinyl resin, the content of the rubbery polymer part (a1) constituting the rubber reinforced vinyl resin is From the viewpoint of film processability, followability (flexibility) of the film to the concave and convex portions on the surface of the injection mold, and impact resistance in the resin film portion formed by the insert molding method The total amount of the thermoplastic resin composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass. The thermoplastic resin (X) is a vinyl resin comprising a polymer part derived from the ethylene / α-olefin rubber (r1) and a vinyl (co) polymer part derived from an aromatic vinyl compound. When the ethylene / α-olefin rubbery polymer reinforced vinyl resin is composed of a part, the content ratio of the polymer part derived from the ethylene / α-olefin rubber (r1) is film processability, and From the viewpoint of impact resistance in the resin film part formed by the insert molding method, the total amount of the thermoplastic resin composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably. It is 15-35 mass%.

  The thermoplastic resin composition includes a resin component comprising a thermoplastic resin (X) and another thermoplastic resin, and the other thermoplastic resin has a structural unit derived from a vinyl monomer. In the case of a (co) polymer, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component of the thermoplastic resin composition is preferably 0 from the viewpoint of extrudability, moldability, and the like. 0.05 to 0.90 dl / g, more preferably 0.07 to 0.81 dl / g, still more preferably 0.09 to 0.65 dl / g, and particularly preferably 0.12 to 0.55 dl / g.

  The film for insert molding of the present invention is a known molding device such as a calender molding device, a T-die extrusion molding device, an inflation molding device, or the like as the thermoplastic resin composition or a raw material component that forms the constituent components thereof. It can manufacture by processing with.

  The thickness of the insert molding film of the present invention can be easily handled, and the insert molding is excellent in the effect of reducing the squeaking noise in the resin film portion of the laminate formed by the insert molding method, the matte appearance, etc. Since a product can be manufactured smoothly, it is preferably 50 to 400 μm, more preferably 70 to 350 μm, and still more preferably 90 to 280 μm.

The film for insert molding of the present invention has an effect of reducing the generation of squeaking noise when it is in dynamic contact with other parts on the surface of the resin molding part 3 by being subjected to an insert molding method using an injection mold. A laminate (smear noise-reducing composite, insert-molded product) 5 formed by bonding the resin film portions 4 having the resin film portion 4 can be suitably manufactured (see FIG. 1D, FIG. 2, and the like). The resin molding part 3 can consist of a thermoplastic resin composition or a cured resin composition.
The laminate (smear noise-reducing composite, insert molded product) 5 includes a step of placing an insert molding film inside an injection mold (hereinafter referred to as “first step”) and the injection molding. It can be manufactured by a method including a step (hereinafter referred to as “second step”) of injecting a resin composition into a cavity of a metal mold (see FIG. 1). In addition, a 1st process may be a process of using the film which is not processed into a specific shape as it is as shown in FIG. 1 (A) (the film 1 for insert molding) as it is, FIG. 1 (B). As shown in Fig. 1, after the raw insert molding film 1 is subjected to another process in advance to form a film structure 1a having a predetermined shape, this is placed in an injection mold and used. It may be a process.

  Hereinafter, a manufacturing method of a laminate (smudge noise reducing composite, insert molded product) 5 using an insert molding film 1 and an injection molding die including a male mold 11 and a female mold 12 will be described with reference to FIG. An example will be described. When manufacturing the laminate 5, a concave portion, a convex portion, a groove portion, or the like may be formed in advance on the surface of the insert molding film 1 on the side where the resin molded portion 3 is formed. Surface treatment may be performed according to the raw material components of the thermoplastic resin composition or the cured resin composition constituting the part 3.

  First, as shown in FIG. 1A, the insert molding film 1 is disposed between the male mold 11 and the female mold 12. Thereafter, the insert molding film 1 is brought into close contact with the inner surface of the female mold 12 using suction means such as the suction holes 13 arranged in the female mold 12. Since the insert molding 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 insert molding film 1 may be fixed by, for example, a frame-shaped sheet clamp.

  Next, as shown in FIG. 1C, the male mold 11 and the female mold 12 are clamped, and the cavity formed by both molds is heated and melted from the inlet 14 formed in the male mold 11. A resin molded part forming raw material 2 made of a thermoplastic resin composition or a room temperature curable or thermosetting resin composition is supplied (second step). When the resin molding part forming raw material 2 is made of a thermoplastic resin composition or a thermosetting resin composition, the insert molding film 1 (film structure 1a) may be preheated. After that, the resin molded part forming raw material 2 is solidified by cooling or the like, and then the mold is opened, and an integrated laminate (smack noise reducing composite, insert molded product) 5 is taken out. At this time, if there is an unnecessary portion of the insert molding film, it is appropriately trimmed. Through the above steps, a laminate 5 is obtained in which the resin film portion 4 formed using the insert molding film 1 is bonded to the surface of the resin molded portion 3 made of the thermoplastic resin composition or the cured resin composition. (See FIG. 1D).

  In the manufacturing method using FIG. 1, it has been explained that unnecessary portions of the insert molding film are trimmed, but the present invention is not limited to this. For example, when manufacturing the laminate 5 as shown in FIG. 2, the insert molding film is cut into a predetermined size and placed in a predetermined position inside the injection mold. A resin composition can be introduced. FIG. 2 shows a laminate 5 in which two resin film portions 4 are formed on the surface of the resin molded portion 3. As a method for manufacturing such a laminate 5, the second step is performed only once. Alternatively, a method of forming a plurality of resin film portions 4 or a method of forming the resin film portions 4 one by one by performing the second step by the number of the resin film portions 4 can be employed.

  When the resin molded part forming raw material 2 used in the second step is a thermoplastic resin composition, a rubber reinforced resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of a rubbery polymer ( (ABS resin, AES resin, ASA resin, MBS resin, etc.) and a (co) polymer obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound in the absence of a rubbery polymer ( Polystyrene, styrene / acrylonitrile copolymer, styrene / acrylonitrile / methyl methacrylate copolymer, styrene / acrylonitrile / N-phenylmaleimide copolymer, etc.), acrylic resin (polymethyl methacrylate, etc.), polyolefin resin, polyvinyl chloride Resin, polyvinylidene chloride resin, polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphtha Etc.), polycarbonate resins, polyarylate resins, polyacetal resins, polyamide resins, fluororesins, polyphenylene ethers, polyphenylene sulfides, imide resins, polyether ketones, polyether ether ketones and other ketone resins, polysulfones, polyether sulfones, etc. And a composition containing at least one thermoplastic resin selected from sulfone resins, biodegradable plastics, and the like.

  Moreover, when the resin molding part forming raw material 2 used in the second step is a curable resin composition, curing comprising an acrylic resin, a phenol resin, a furan resin, an acrylic silicon resin, a urethane resin, a melamine resin, an epoxy resin, or the like. An uncured curable composition containing a curable resin (such as a prepolymer) and a curing agent (such as a polymerization initiator).

The laminate (smear noise-reducing composite, insert molded product) 5 obtained by the present invention has a resin film portion 4 having the same or different heat as the thermoplastic resin composition constituting the insert molding film of the present invention. When it comes into contact with other parts including plastic resin composition, cured resin composition, crosslinked rubber (including vulcanized rubber), fiber assembly, metal (including alloy), glass, ceramics, etc. It has the performance that generation is suppressed. Therefore, when the resin film part 4 in the laminate 5 and other parts are brought into contact with each other as a composite structure, an effect of suppressing the generation of squeaking noise due to vibration, twist, impact, etc. is obtained, or the laminate 5 and other components Generation of a squeaking noise when a part is placed with a certain gap and one or both of them move or deform due to vibration, twist, impact, etc. and dynamically contact (surface contact, line contact, or point contact) It is suitable for obtaining the suppression effect.
FIG. 3 shows a laminate 5 having two concave portions or groove portions, a resin film portion 4 formed on the surface having these concave portions, and a resin connection member 7 as another component. A composite structure 15 is shown. In FIG. 3, since the resin connection member 7 is fitted so as to come into contact with the resin film portion 4 of the concave portion or groove portion in the laminate 5, the generation of squeaking noise due to vibration, twist, impact, etc. is suppressed. An effect can be obtained.

  The laminate (smear noise-reducing composite, insert molded product) 5 obtained by the present invention is a composite product that constitutes vehicles, OA (office automation) equipment, home electrical appliances, electrical / electronic equipment, building materials, and the like. It is suitable as one member.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Production Raw Material for Insert Molding Film Production of the insert molding film was performed by T-die extrusion molding of a thermoplastic resin composition prepared using the following raw materials. The measurement of the graft ratio of the resin component, the intrinsic viscosity [η] and the like was performed according to the method described above.

1-1. Raw material [P]
As a thermoplastic resin containing a portion derived from a rubbery polymer, the ethylene / α-olefin rubbery polymer reinforced vinyl resin (raw materials P1 to P4) obtained in Synthesis Examples 1 to 4 below, The diene rubbery polymer reinforced vinyl resin (raw material P5) obtained in Synthesis Example 5 was used.

Synthesis Example 1 (Synthesis of raw material P1)
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 (ML _{1 + 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 ( Ethylene / α-olefin rubbery polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion made of a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene) And a rubber-reinforced resin (raw material P1) which is a resin mixture made of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer). The graft ratio of the graft resin (acetone insoluble matter) contained in the raw material P1 was 48%. 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.

Synthesis Example 2 (Synthesis of raw material P2)
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 (ML _{1 + 4} , 100 ° C.): 20) 10 parts, 13.2 parts of styrene, 4.8 parts of acrylonitrile, 0.7 part of tert-dodecyl mercaptan and 100 parts of toluene were heated. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to obtain a uniform solution. Thereafter, 0.11 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 70 minutes, 52.8 parts of styrene, 19.2 parts of acrylonitrile and 0.42 part of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours and 30 minutes. After 4 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 97%. 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 ( Ethylene / α-olefin rubbery polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion made of a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene) And a rubber-reinforced resin (raw material P2) which is a resin mixture made of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer). The graft ratio of the graft resin (acetone insoluble matter) contained in the raw material P2 was 52%. The content of the acetone-soluble component contained in the raw material P2 is 85% when the entire raw material P2 is 100%, and the intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of this acetone-soluble component is It was 0.25 dl / g. Then, when Tm of raw material P2 was measured using this pellet, it was 40 degreeC.

Synthesis example 3 (synthesis of raw material P3)
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 (ML _{1 + 4} , 100 ° C.): 20), 7.3 parts of styrene, 2.7 parts of acrylonitrile, 0.1 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 ( Ethylene / α-olefin rubbery polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion made of a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene) And a rubber reinforced resin (raw material P3) which is a resin mixture made of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer). The graft ratio of the graft resin (acetone insoluble matter) contained in this raw material P3 was 40%. The content of the acetone-soluble component contained in the raw material P3 is 30% when the entire raw material P3 is 100%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone-soluble component is: It was 0.40 dl / g. Then, when Tm of raw material P3 was measured using this pellet, it was 40 degreeC.

Synthesis Example 4 (Synthesis of raw material P4)
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 (ML _{1 + 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 ( Ethylene / α-olefin rubbery polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion made of a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene) And a rubber-reinforced resin (raw material P4) which is a resin mixture made of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer). The graft ratio of the graft resin (acetone insoluble matter) contained in the raw material P4 was 25%. The content of the acetone-soluble component contained in the raw material P4 is 38% when the total amount of the raw material P4 is 100%, and the intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of this acetone-soluble component is It was 0.35 dl / g. Then, when Tm of raw material P4 was measured using this pellet, it was 40 degreeC.

Synthesis Example 5 (Synthesis of raw material P5)
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 Diene rubbery polymer reinforced vinyl resin (graft resin) containing a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene), and ungrafted vinyl copolymer A rubber reinforced resin (raw material P5) which is a resin mixture made of (acrylonitrile / styrene copolymer) was obtained. The graft ratio of the diene rubbery polymer reinforced vinyl resin (graft resin, acetone insoluble matter) contained in this raw material P5 was 55%. 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.

1-2. 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.
(1) Raw material Q1
Acrylonitrile / styrene copolymer (2) raw material having ratios of acrylonitrile unit and styrene unit of 27% and 73%, respectively, and intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.30 dl / g Q2
Acrylonitrile / styrene copolymer (3) raw material having ratios of acrylonitrile units and styrene units of 27% and 73%, respectively, and intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.45 dl / g Q3
Acrylonitrile / styrene copolymer (4) raw material having ratios of acrylonitrile units and styrene units of 27% and 73%, respectively, and intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 1.20 dl / g Q4
A methacrylic resin “Acrypet VH-5” (trade name, copolymer of methyl methacrylate and methyl acrylate) manufactured by Mitsubishi Rayon Co., Ltd. was used.

1-3. Raw material [R]
A polycarbonate “NOVAREX7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The viscosity average molecular weight (Mv) is 18,700, and the MFR (temperature 240 ° C., load 10 kg) is 18 g / 10 min.

1-4. Raw material [S]
The following raw materials S1 and S2 were used as the matting material (Y).
(1) Raw material S1
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.
(2) Raw material S2
As an organic matting material, a partially cross-linked acrylic additive “methabrene F-410” (commercial product, cross-linked methyl methacrylate-alkyl acrylate-styrene copolymer) manufactured by Mitsubishi Rayon Co., Ltd. was used.

2. Production and evaluation of insert molding films Examples 1 to 19 and Comparative Examples 1 to 3
The raw materials [P], [Q], [R] and [S] were used, and the raw materials were mixed with a Henschel mixer at the blending ratios shown in Tables 1 and 2, and the resulting mixture was mixed with Nippon Steel Corporation. The product was supplied to a twin screw extruder “TEX44αII” (model name) and melt kneaded (cylinder setting temperature: 200 ° C. to 250 ° C.) to obtain pellets made of a thermoplastic resin composition.
Then, this pellet is supplied to an extruder having a screw diameter of 115 mm arranged in a film forming machine equipped with a T die (die width: 1600 mm, lip interval 1 mm), and melted at a resin temperature of 240 ° C. from the T die. Resin was discharged and it was set as the soft film. Then, this soft film is surface-adhered to a cast roll (roll surface temperature: 90 ° C.) with an air knife, and is operated so as to have the wall thickness shown in Tables 1 and 2, to cool and solidify the insert molding film. Obtained.
The temperature of the molten resin was measured using a thermocouple thermometer. In addition, the thickness of the insert molding film was measured by using a thickness gauge (model “ID-C1112C”, manufactured by Mitutoyo Corporation), cutting the film after 1 hour from the start of film production, The thickness was measured at 10 mm intervals toward both ends, and the average value was obtained. Measurement point values in the range of 20 mm from the edge of the film were removed from the average calculation.

The obtained film for insert molding was subjected to the following evaluation, and the results are shown in Tables 1 and 2.
2-1. Film forming property The film forming property was determined from the difference in thickness at each point of the film measured as described above. The smaller the height difference, the more uniform the thickness of the obtained film and the better the film-forming property.
A: The difference is less than 30 μm, and the film forming property is excellent.
(Triangle | delta): A difference is 30 micrometers or more and less than 40 micrometers, and film forming property is favorable.
X: The difference is 40 μm or more and the film-forming property is inferior

2-2. Adhesiveness with resin molding Insert insert film is cut into a size of 70mm (MD) x 25mm (TD), fixed in the mold of the injection molding machine, then closed and melted at 240 ° C The heat resistant ABS resin “Techno MUH E1500” (manufactured by Techno Polymer Co., Ltd.) was injected to form a laminate. Next, after taking out the laminate from the mold and adjusting the condition at a temperature of 23 ° C. and a humidity of 50% for 24 hours, a 90-degree peel test (MD film pulling speed: 1 mm / second) was performed. The adhesion between the part and the injection resin molded part was evaluated according to the following criteria.
○: The part of the film for insert molding was not peeled off from the resin molded part and the film was broken. Δ: The part of the film for insert molding was slightly peeled off from the resin molded part on the adhesive surface, but the film was broken halfway. The film part was peeled off from the resin molded part and the adhesive surface, and the film did not break

2-3. Flexibility A film for insert molding was cut into a size of 100 mm (MD) × 100 mm (TD), bent along the symmetry axis in the MD direction, and then bent along the symmetry axis 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 it was folded and expanded again. △: The crease was not cracked, but the crease was cracked when folded and expanded again. ×: The crease was cracked.

2-4. Vacuum forming property The film for insert molding is cut into a size of 300 mm (MD) × 210 mm (TD), and the molded product shown in FIG. 5 (IV) is provided with the vacuum forming die 8 shown in FIG. It was produced using a small vacuum forming machine “300X”. 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 film for insert molding having the above size was fixed upward from the upper surface of the vacuum forming die 8 with an interval of 40 mm (FIG. 5 (I)). Then, the film for insert molding was heated from the peripheral side using the heater (not shown) heated beforehand at 450 degreeC. Next, the vacuum mold 8 was moved upward to bring the upper surface into contact with the insert molding film (FIG. 5 (II)). Thereafter, the pressure was reduced from the bottom surface side of the vacuum forming die 8, the insert forming film was brought into close contact with the inner surface of the concave portion of the vacuum forming die 8, and vacuum forming was performed (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 insert molding film to the recess of the vacuum molding die 8 was visually observed and evaluated according to the following criteria.
◯: Good conformability to the recess of the vacuum forming die 8 and no wrinkle was observed on the film surface of the molded product shown in FIG. 5 (IV) Δ: Followability to the recess of the vacuum forming die 8 Although it was good, wrinkles were observed on the film surface of the molded product shown in FIG. 5 (IV). X: poor conformability to the recess of the vacuum forming die 8, and the film of the molded product shown in FIG. 5 (IV) Wrinkles were observed on the surface

  In the following stick-slip test, in order to evaluate the ease or difficulty of generating a squeaking noise when an insert-molded product is manufactured using an insert-molding film, A resin film portion 4 made of an insert molding film (50 mm × 25 mm), which is the obtained laminate and made using each pellet, is made of a heat-resistant ABS resin “Techno MUH E1500” (manufactured by Techno Polymer Co., Ltd.). The test body 18 joined to the support part (resin molding part) 16 (50 mm × 25 mm × 4 mm) was used (see FIG. 6).

2-5. Matte property The composite film obtained as described in the above section 2-2, and the resin film part 4 made of insert molding films (50 mm × 25 mm) produced by using each pellet is a heat-resistant ABS resin “ The test body 18 joined to the support part (resin molding part) 16 (50 mm × 25 mm × 4 mm) made of “Techno MUH E1500” (manufactured by Techno Polymer Co., Ltd.) is placed in the dark room so that the resin film part 4 faces upward. installed. Thereafter, a fluorescent lamp “FLR40SW / M / 36” (trade name) manufactured by Mitsubishi Electric Lighting Co., Ltd., disposed on the ceiling of the dark room, which is directly above the test body 18 and is 2 m from the resin film portion 4. The panel was made to emit light, and the matte property in the resin film part 4 was visually observed by five panelists and evaluated according to the following criteria.
○: 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.

2-6. Stick-slip test (abnormal noise risk index)
The stick-slip test was conducted by using a stick-slip tester “SSP-02” (model name) manufactured by ZIEGLER, the test specimen 18 and an AES resin “Techno AESW 210” (manufactured by Techno Polymer) or ABS / PC alloy “ Test piece 20 (60 mm × 100 mm × 4 mm) made of Excelloy CK20 ”(manufactured by Techno Polymer Co., Ltd.), PMMA“ Acryprene ”(manufactured by Mitsubishi Rayon Co., Ltd., 60 mm × 100 mm × 80 μm) or PET“ Teijin Tetron Film ”(Teijin DuPont Films Ltd.) A film made of 60 mm × 100 mm × 50 μm) was set as shown in FIG. 7, and both were rubbed three times to measure the noise risk index. 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 each table, “-” indicates that no experiment was performed.

2-7. Melting point (Tm)
According to JIS K 7121-1987, the melting point was measured with a differential scanning calorimeter “DSC2910” (model name) manufactured by TA Instruments. In the measurement, the endothermic change was observed at a constant temperature increase rate of 20 ° C. per minute, and the melting point was read from the peak temperature of the obtained endothermic pattern.

From Tables 1 and 2, the following is clear. That is, Comparative Example 1 is an example in which the Tm of the thermoplastic resin composition is not found in the range of 0 to 120 ° C. while containing a portion derived from the rubbery polymer. Became high. Comparative Example 2 is an example using a thermoplastic resin composition that does not include a portion derived from a rubbery polymer and does not have Tm in the range of 0 to 120 ° C. In addition to being inferior in adhesion, flexibility and vacuum formability, the noise risk index increased in the stick-slip test. Although the comparative example 3 is an example which does not contain a matte material, it was inferior in the matte property.
On the other hand, it is clear that Examples 1 to 19 using the composition having the configuration of the present invention have an excellent matting performance, an excellent flexibility and vacuum formability, and a configuration in which it is difficult to generate a squeaking noise. is there.

  When the film for insert molding of the present invention is used together with a mold for injection molding, a resin film part that suppresses generation of squeaking noise when dynamically contacting with other parts and has a good matte appearance; In addition, it is possible to efficiently produce a laminate (smudge noise-reducing composite, insert molded product) in which a base made of a resin composition is joined. The obtained laminate (smear noise-reducing composite, insert-molded product) is suitable as a member of products constituting vehicles, OA (office automation) equipment, home electrical appliances, electrical / electronic equipment, building materials and the like. is there.

1: Film for insert molding 1a: Film structure having a predetermined shape 2: Raw material for forming a resin molded part 3: Resin molded part 4: Resin film part 5: Laminate (insert molded product or squeaking noise reducing composite)
7: Connection part 11: Mold for injection molding (male)
12: Injection mold (female)
13: Suction hole 14: Introducing port for raw material for forming resin molding 15: Composite 16: Support 18: Test body for evaluating squeaking sound 20: Stage for evaluating squeaking sound

Claims (7)

  Thermoplastic containing thermoplastic resin containing part (a1) derived from rubber polymer and matting material (Y) and having a melting point in the range of 0 to 120 ° C. according to JIS K 7121-1987 An insert molding film comprising a resin composition.   The insert molding film according to claim 1, wherein the rubbery polymer is ethylene / α-olefin rubber.   The film for insert molding according to claim 2, wherein the ethylene / α-olefin rubber is a copolymer having a melting point in the range of 0 to 120 ° C. according to JIS K 7121-1987.   The film for insert molding according to any one of claims 1 to 3, wherein the thermoplastic resin is a rubber-reinforced vinyl resin including the part (a1) and a part (a2) derived from a vinyl resin. .   The insert molding film according to any one of claims 1 to 4, wherein the matting material (Y) is an inorganic matting material.   The film for insert molding according to any one of claims 1 to 5, wherein the film has a thickness of 50 to 300 µm.   A step of placing the insert molding film according to any one of claims 1 to 6 in an injection mold, and a step of injecting a resin composition into a cavity of the injection mold; A method for producing an insert-molded product, comprising:

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