JP6510772B2 - Insert molding film - Google Patents

Description

  The present invention can suppress the generation of rubbing noise (hereinafter referred to as "squeaking noise") on the surface of a base made of a resin composition when it is in dynamic contact with other parts, and gives a good matte appearance. The present invention relates to a film for insert molding suitable for producing a laminate having a resin film portion (hereinafter, also referred to as an "insert molded product" or a "staining sound reduced composite").

  Conventionally, a film made of a thermoplastic resin composition is disposed inside an injection mold, the resin composition is injected into the cavity of the injection mold, and the film and the base made of the resin composition are joined. Insert molding methods are known for producing composites. Conventionally, this method uses, for example, a film (a decorative film consisting of a single layer or multiple layers) on which an image such as letters, numbers, patterns, designs, pictures, photographs, etc. is formed, and a decorated composite is used. It is widely applied as a method of manufacturing (for example, patent documents 1-3 etc.).

  By the way, the thermoplastic resin composition or the cured resin composition is used today as a raw material of parts having performance according to the purpose in all situations. However, in recent years, thermoplastic resin parts used in the fields of vehicles, OA (office automation) equipment, home electric appliances, electric / electronic equipment, construction materials, etc. (referred to as "parts made of thermoplastic resin composition Z") In particular, it is used in combination with other parts such as thermoplastic resin parts made of the same or different material as the thermoplastic resin composition Z, hardened resin parts, or inorganic material parts made of metal or inorganic compound. It is increasing. For example, a thermoplastic resin component and another component are disposed in contact with each other, or these components are disposed at a predetermined distance. In such an embodiment, thermoplastic resin components are mutually connected. Are adjacent to each other (only the two are in contact with each other or the adhesive part is in contact with each other, or both are arranged with a predetermined distance), vibration, rotation, twist, It is known that one or both of them move or deform due to sliding, impact or the like to be in dynamic contact and generate a stagnant noise (scrubbing noise). For example, when an air-conditioner or audio casing part disposed in a car and a fitting part disposed on the periphery or inside thereof rub against each other due to vibration or the like, an unpleasant sound (squealing noise) is emitted. is there. This stagnant sound is said to be a sound caused by the stick-slip phenomenon that occurs when two objects rub against each other. Incidentally, the stick-slip phenomenon is said to be a phenomenon different from the sliding phenomenon between objects as conventionally known.

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

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

  As a film having a matte appearance used for insert molding or in-mold molding, it is a matte acrylic resin film having a matte layer containing a matte material and a binder resin on an acrylic resin film substrate, and on the matte layer side Disclosed is a matte acrylic resin film in which the difference between the degree of yellowness of the matte acrylic resin film after heating to a surface temperature of 200 ° C. and the degree of 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 JP, 2013-001855, A Unexamined-Japanese-Patent No. 2007-062194

However, even if a composite is manufactured using the films as described in Patent Documents 1 to 4 described above, generation of rubbing noise can be suppressed when dynamically contacting with other parts, and a good matte appearance It was not possible to obtain a laminate provided with a resin film portion that gives.
The present invention is excellent in flexibility and vacuum moldability, suppresses generation of stagnant noise when dynamically contacting other parts on the surface of a 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 portion, and a method for producing a laminate (a humming noise reduced composite, an insert-molded product) including the base and the resin film portion thereof. .

The present invention is as follows.
1. Thermoplastic resin containing a thermoplastic resin including a portion (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 An insert molding film comprising the composition.
2. The film for insert molding as described in 1 above, wherein the rubbery polymer is ethylene / α-olefin rubber.
3. The film for insert molding as described in 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 insert molding film according to any one of 1 to 3, wherein the thermoplastic resin is a rubber-reinforced vinyl resin including the portion (a1) and a portion (a2) derived from a vinyl resin.
5. The insert molding film according to any one of the above 1 to 5, wherein the matte material (Y) is an inorganic matte material.
6. The insert molding film according to any one of the above 1 to 5, which has a thickness of 50 to 300 μm.
7. A step of disposing the insert molding film according to any one of the above 1 to 6 inside an injection molding die, and a step of injecting a resin composition into the cavity of the injection molding die A method for producing an insert-molded product, comprising:

In the present specification, “(meth) acrylic” refers to acrylic and methacrylic, “(meth) acrylate” refers to acrylate and methacrylate, and “(meth) acryloyl group” refers to acryloyl or methacryloyl group ” The term "polymer" refers to homopolymers and copolymers.
The melting point (hereinafter referred to as "Tm") according to JIS K 7121-1987 is obtained by measuring the endothermic change at a constant temperature rising rate of 20 ° C per minute using DSC (differential scanning calorimeter). It is a value obtained by reading the peak temperature of the 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 a mold for injection molding. In addition, the surface of the base made of the same or different thermoplastic resin composition or thermosetting resin composition as this composition suppresses generation of stagnant noise when it is in dynamic contact with other parts, and good. It is suitable for formation of the resin film part which has the matte appearance, ie, manufacture of the laminated body (squeezing sound reduction compound, insert-molded article) provided with these base and resin film parts. The resin film portion of the obtained laminate is adjacent to another component made of the same or other material as the thermoplastic resin composition constituting the insert molding film (only the both are in contact or bonded to each other) When forming a structure in which both are in contact with each other or arranged at a predetermined distance), one or both of them move or move due to vibration, rotation, twist, sliding, impact, etc. Even if deformation and dynamic contact (surface contact, line contact or point contact) occur, the generated stagnation noise is reduced or the generation of the stagnation noise is suppressed. In addition, the obtained laminate (the squealing sound reduction composite, the insert-molded article) is a member used for inserting the hole or the other part having the recess into the hole or the recess, and the hole Alternatively, since any generation of stagnant noise is suppressed in any of the members having the recessed portion itself, they can be suitably used in applications used in contact with other parts such as parts for automobile interiors.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing explaining an example of the method of manufacturing a laminated body (a stagnation sound reduction composite, an insert-molded article) using the film for insert molding of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the laminated | stacked product (a squeaking noise reduction compound, an insert-molded article) 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 (the stagnation sound reduction compound, the insert-molded article) obtained by the method of this invention, and other components. It is a schematic perspective view which shows the type | mold used for 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 stagnation sound evaluation in [Example]. It is explanatory drawing of the stick-slip phenomenon. (A), (b), (c), (d) are model diagrams of stick-slip.

The film for insert molding of the present invention is a thermoplastic resin (hereinafter referred to as “thermoplastic resin (X), which includes a portion (a1) derived from a rubbery polymer (hereinafter also referred to as“ rubbery polymer portion (a1) ”). And a matting material (Y), and having a Tm (melting point) of a thermoplastic resin composition in the range of 0 to 120 ° C., and having a matte appearance of matte tone , Flexible. In the film for insert molding of the present invention, the laminate obtained by the insert molding method is the same as or different from the thermoplastic resin composition which constitutes the film for insert molding, a cured resin composition, a rubber (additive Even if it is in dynamic contact with other parts including vulcanized rubber, fiber assembly, metal (including alloy), glass, ceramics, etc., the generation of stagnant noise is reduced or suppressed. Accordingly, using the insert molding film 1 of the present invention and the injection molding dies 11 and 12, the insert molding method is provided according to (A), (B), (C) and (D) in FIG. Thus, the resin film portion 4 (hereinafter sometimes referred to simply as the “resin film portion”) having the effect of reducing the generation of stagnant noise when being in dynamic contact with other components is joined to the surface of the resin molded portion 3 Can be suitably produced. Furthermore, after forming the film for insert molding 1 of the present invention into a film structure 1a which has been previously adjusted to a predetermined shape by another process, this laminate (staining sound reduction composite) 5 is It can also be manufactured by using an insert molding method according to (B), (C) and (D) in FIG.
As a result of subjecting the insert molding film of the present invention to insert molding, the thickness of the resin film portion in the resulting laminate may be thinner than the thickness of the insert molding film used. There is no loss, and the laminate is efficiently produced.

  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 reduction effect of the generation of stagnant noise in the resin film portion formed by the insert molding method and the mechanical strength. It is in the range of -90 ° C, more preferably 20-80 ° C. As described above, Tm (melting point) can be obtained according to JIS K 7121-1987, but the number of endothermic pattern peaks in the range of 0 to 120 ° C. is not limited to one, and two or more May be. Further, Tm (melting point) observed in the range of 0 to 120 ° C. may be derived from the thermoplastic resin (X), and other thermoplastic resins to be blended as necessary, weight average molecular weight May be derived from a low molecular weight polyolefin wax or the like such as 10,000 or less.

The thermoplastic resin (X) is a thermoplastic resin including a rubbery polymer portion (a1) derived from a rubbery polymer, and a rubbery polymer portion (a1) constituting the thermoplastic resin (X) is And may be only one kind, or 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 rubber polymer may be any of a diene polymer (hereinafter referred to as "diene rubber") and a non-diene polymer (hereinafter referred to as "non diene rubber"). Moreover, these polymers may be crosslinked polymers or non-crosslinked polymers.

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

  Further, as the non-diene rubber, ethylene / α-olefin copolymer rubber (hereinafter referred to as “ethylene / α-olefin rubber”); urethane rubber; acrylic rubber; silicone rubber; silicone acrylic An IPN rubber; a hydrogenated polymer formed by hydrogenating a (co) polymer containing a structural unit derived from a conjugated diene compound can be mentioned. The hydrogenated polymer may be a block copolymer or a random copolymer. Moreover, these copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more).

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

The ethylene / α-olefin rubber is a copolymer rubber including a structural unit derived from ethylene and a structural unit derived from α-olefin.
As an α-olefin, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-hexene Eikosen etc. are mentioned. These α-olefins can be used alone or in combination of two or more. The carbon atom number of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8 from the viewpoint of impact resistance.

  The 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 reduction effect of generation of stagnant sound 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, further preferably Is 60 to 95% by mass and 40 to 5% by mass.

  In the present invention, preferred ethylene / α-olefin rubbers are ethylene / α-olefin copolymers having a Tm (melting point) in the range of 0 to 120 ° C., and in that respect, they are derived from other monomers May have a structural unit. Other monomers include non-conjugated diene compounds such as alkenyl norbornenes, cyclic dienes and aliphatic dienes. These nonconjugated 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 nonconjugated diene compound is preferably 10% by mass, more preferably 5 when the total amount of 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 reduction effect of generation of stagnant noise in the resin film portion formed by the insert molding method and the impact resistance. It is 20-80 ° C. The fact that the Tm (melting point) of the ethylene / α-olefin rubber is in the range of 0 to 120 ° C. means that this rubber has crystallinity. When the ethylene / α-olefin rubber has a crystalline portion, the occurrence of the stick-slip phenomenon is suppressed, so even if the resin film portion containing this dynamically contacts other parts, the stagnant noise is generated. Is considered to be 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 reduction effect of generation of stagnant noise in the resin film portion formed by the insert molding method Ethylene / α-olefin copolymer is preferable, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-octene copolymer are more preferable, and ethylene / propylene copolymer Particular preference is given to coalescing.

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

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

In the case where the rubbery polymer portion (a1) is derived from both ethylene / α-olefin rubber and other rubbers, the content ratio of both is the generation of stagnant noise in the resin film portion formed by the insert molding method From the viewpoint of reducing 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. % By mass, more preferably 35 to 90% by mass and 10 to 65% by mass.
In the above embodiment, the ratio of the total amount of the part derived from the ethylene / α-olefin rubber and the part derived from other rubber to the thermoplastic resin (X), ie, the rubber polymer part (a1) Is preferably 20 to 90 from the viewpoint of 100% by mass of the thermoplastic resin (X) from the viewpoint of reducing the generation of stagnant noise in the resin film portion formed by the insert molding method and impact resistance. It is mass%, 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, preferably, the thermoplastic resin (X) is preferably the rubbery polymer portion (a1) and a portion (a2) derived from a vinyl resin (hereinafter also referred to as "resin portion (a2)") And are chemically bonded rubber-reinforced vinyl resins. The resin portion (a2) constituting the one molecule of the thermoplastic resin (X) may be only one kind or two or more kinds.
The vinyl-based resin is a vinyl-based (co) polymer including a structural unit derived from a vinyl-based monomer, and preferably, a vinyl-based (co) polymer portion including a structural unit derived from an aromatic vinyl compound It is. That is, in a preferred embodiment, the resin portion (a2) may be a vinyl (co) polymer portion comprising one or two or more structural units derived from an aromatic vinyl compound, or an aromatic vinyl compound It may be a vinyl-based (co) polymer part comprising one or two or more types of structural units derived from the resin and one or more types of structural units derived from other vinyl-based monomers.
The lower limit of the content of the structural unit derived from the aromatic vinyl compound contained in the vinyl-based resin constituting the resin portion (a2) is the resin portion (a2) from the viewpoint of film rigidity and appearance. When the whole is 100 mass%, it is preferably 50 mass%, more preferably 60 mass%, and still more preferably 65 mass%.

  The above 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, vinyl toluene, vinyl xylene, vinyl naphthalene and the like. These compounds can be used alone or in combination of two or more. Moreover, among these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Further, as other vinyl monomers, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, amides A group containing unsaturated compound, a hydroxyl group containing unsaturated compound, an oxazoline group containing unsaturated compound etc. are mentioned. These compounds may be used alone or in combination of two or more.

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

  As said (meth) acrylic acid ester compound, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylic acid isobutyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate. These compounds can be used alone or in combination of two or more. Moreover, among these, methyl (meth) acrylate and n-butyl (meth) acrylate are preferable.

  As the above maleimide compound, maleimide, N-methyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-dodecyl maleimide, N-phenyl maleimide, N- (2-methylphenyl) maleimide, N- (4-methyl) Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N- benzyl maleimide, N- (4-hydroxyphenyl) And maleimide), N-naphthyl maleimide, N-cyclohexyl maleimide and the like. These compounds can be used alone or in combination of two or more. Moreover, among these, N-phenyl maleimide is preferable. In addition, as another method of introducing a structural unit derived from a maleimide compound into a polymer chain, for example, a method of copolymerizing unsaturated dicarboxylic acid anhydride of maleic anhydride and then imidizing may be used.

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.

As the amino group-containing unsaturated compound, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylamine, methacrylamine, N- Methyl acryl amine etc. are mentioned. These compounds can be used alone or in combination of two or more.
Examples of the amide group-containing unsaturated compound include acrylamide, N-methyl acrylamide, methacrylamide, N-methyl methacrylamide 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 ) A hydroxyl group such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate ( Meta) acrylic acid ester; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2- Hydroxy Ethyl-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- 1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene and the like. 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, methallyl glycidyl ether and the like. These compounds can be used alone or in combination of two or more.
Examples of the above oxazoline group-containing unsaturated compounds 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-based 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-based monomer, as another vinyl-based monomer In view of the rigidity and appearance of the film, 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-based resin constituting the resin portion (a2) is a vinyl-based copolymer including 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 the mechanical strength and chemical resistance of the film. %, More preferably 95 to 100% by mass. In addition, the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound is 100% by mass from the viewpoint of mechanical strength and chemical resistance, respectively. Preferably it is 55-95 mass% and 5-45 mass%, More preferably, it is 60-90 mass% and 10-40 mass%, More preferably, it is 65-80 mass% and 20-35 mass%.

  When the thermoplastic resin (X) is a rubber-reinforced vinyl-based resin, the content ratio of the rubber-like polymer portion (a1) and the resin portion (a2) constituting this rubber-reinforced vinyl-based resin is the insert molding method When the total of these is 100% by mass, preferably from 10 to 90% by mass and 10 to 90% by mass, respectively, from the viewpoint of the reduction effect of the generation of stagnant noise in the resin film portion formed by Preferably it is 20-80 mass% and 20-80 mass%, More preferably, it is 30-75 mass% and 25-70 mass%.

The thermoplastic resin (X) contained in the said thermoplastic resin composition can consist of 1 type, or 2 or more types of resin.
As described above, the thermoplastic resin (X) according to the present invention is preferably a rubber-reinforced vinyl-based resin, and in particular, a polymer part derived from an ethylene / α-olefin-based rubber (hereinafter referred to as “ethylene · α Ethylene / α-olefin rubbery polymer reinforced vinyl resin having an olefin rubbery polymer portion and a vinylic resin portion comprising a vinylic (co) polymer portion derived from an aromatic vinyl compound It is preferred to contain a resin.
Further, 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 used in combination with a diene-based rubbery polymer-reinforced vinyl-based resin having a vinyl-based resin portion composed of a system (co) polymer portion, the impact resistance of the film for insert molding, and the lamination formed by the insert molding method Impact resistance in the resin film portion of the body can be further improved.

  The content ratio of the ethylene / α-olefin rubber polymer portion and the vinyl resin portion constituting the ethylene / α-olefin rubber polymer reinforced vinyl resin is the resin of the laminate formed by the insert molding method From the viewpoint of reducing the generation of stagnant noise in the film portion and impact resistance, when the total of both is 100% by mass, each is preferably 10 to 90% by mass and 10 to 90% by mass, more preferably 20 to 20% by mass. It is 80% by mass and 20 to 80% by mass, more preferably 30 to 75% by mass and 25 to 70% by mass.

  The content ratio of the diene-based polymer portion and the vinyl-based resin portion constituting the diene-based rubbery polymer reinforced vinyl-based resin is the effect of reducing generation of stagnant sound in the resin film portion 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, respectively. More preferably, they are 30-70 mass% and 30-70 mass%.

  The above-mentioned ethylene / α-olefin rubber polymer reinforced vinyl resin or diene rubber polymer reinforced vinyl resin is preferably vinyl resin in the presence of ethylene / α-olefin rubber or diene rubber. Contained in a rubber-reinforced resin obtained by polymerizing a monomer, preferably a vinyl-based monomer containing an aromatic vinyl compound, particularly preferably a vinyl-based monomer containing an aromatic vinyl compound and a vinyl cyanide compound It is a graft resin. The ethylene / α-olefin rubber preferably has a Tm (melting point) in the range of 0 to 120 ° C., and a structural unit derived from ethylene and a carbon atom number of preferably 3 to 20, more preferably 3 to 3. 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-olefins. The aromatic vinyl compound is preferably styrene and α-methylstyrene, and the vinyl cyanide compound is preferably acrylonitrile.

  As a method of polymerizing (grafting polymerization) a vinyl monomer in the presence of an ethylene / α-olefin rubber or a diene rubber to produce the above-mentioned rubber-reinforced vinyl resin, emulsion polymerization, suspension polymerization Solution polymerization, bulk polymerization, or a polymerization method combining these.

  When the above-mentioned emulsion polymerization is carried out, a polymerization initiator, a chain transfer agent (molecular weight modifier), an emulsifier, water and the like are used.

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

  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) ) 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-dihydroper Oxide, 1,3-bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl Luperoxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy laurate, tert-butylperoxymonocarbonate, bis (tert-butylcyclohexyl) peroxy Dicarbonate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and the like can be mentioned.

  As the above-mentioned azo compounds, 2,2'-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis (2-methylbutyronitrile) 2,2'-azobisdimethylvaleronitrile, 4,4'-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2'-azobis (2,4, -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.
Further, as the above-mentioned redox type polymerization initiator, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate and the like as a reducing agent, potassium peroxodisulfate, hydrogen peroxide, cumene hydroperoxide The thing which used the tert- butyl hydroperoxide etc. 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 and tert-tetradecyl mercaptan; terpinolenes; The dimer of alpha-methylstyrene etc. are mentioned. These can be used singly or in combination of two or more.

  As said emulsifier, anionic surfactant and nonionic surfactant are mentioned. As anionic surfactants, sulfuric acid esters of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Can be mentioned. Further, examples of the nonionic surfactant include alkyl ester type compounds of polyethylene glycol, alkyl ether type compounds and the like. These can be used singly or in combination of two or more.

The production conditions in the case of emulsion polymerization are not particularly limited. The polymerization initiator or chain transfer agent can be supplied collectively or continuously to the reaction system.
With respect to the latex obtained by the emulsion polymerization, the resin component is usually coagulated by a coagulant to be a powder or the like. Thereafter, it is purified by washing with water and the like, dried and recovered. 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; and organic acids such as acetic acid and lactic acid.

  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, an ethylene / α-olefin resin It includes a rubber or diene rubber itself, and a vinyl (co) polymer including a structural unit derived from a vinyl monomer which is not chemically bonded to a rubbery polymer portion derived from these rubbers. There is a case. The latter vinyl-based (co) polymer does not contain the rubbery polymer portion (a1), and therefore, is contained in the rubber-reinforced resin as “other thermoplastic resin” described later.

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

The graft ratio can be determined by the following equation.
Graft ratio (%) = {(S−T) / T} × 100
In the above formula, S is charged with 1 gram of a rubber-reinforced resin in 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then centrifuged (rotational temperature condition of 5 ° C. Mass (g) of insolubles obtained by centrifuging at 23,000 rpm) for 1 hour and separating insolubles and solubles, T is ethylene · α− contained in 1 gram of rubber reinforced resin It is mass (g) of rubbery polymers, such as olefin system rubber and diene system rubber. The mass of the rubbery polymer can be obtained by a method of calculating from the polymerization formulation and the polymerization conversion, infrared spectroscopy, pyrolysis gas chromatography, CHN elemental analysis or the like.

  Although the content ratio of the rubbery polymer part (a1) and the resin part (a2) in the rubber reinforced vinyl resin is as described above, the ratio of these is determined by the rubber reinforcement obtained from the rubber reinforced resin It can also be calculated from the result of the grafting rate in a vinyl resin.

In the rubber reinforced resin containing a rubber reinforced vinyl resin manufactured by the above graft polymerization, an acetone-soluble component (hereinafter, also referred to as "acetone soluble component") is a non-grafted polymer produced by graft polymerization as a by-product It is a (co) polymer having a structural unit derived from a vinyl monomer. The intrinsic viscosity [η] (measured at 30 ° C. in methyl ethyl ketone) of the acetone soluble component is preferably 0.05 to 0.90 dl / g, from the viewpoint of the extrudability of the thermoplastic resin composition, molding processability, etc. More preferably, it is 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.
For example, 1 g of a rubber-reinforced resin is added to 20 ml of acetone, and the acetone solubles are shaken at 25 ° C. for 2 hours using a shaker or the like to form insolubles and It can be obtained by separating solubles.

The intrinsic viscosity [η] can be determined in the following manner.
A rubber-reinforced resin containing a rubber-reinforced vinyl-based resin is charged into acetone, acetone-soluble components recovered after centrifugation are dissolved in methyl ethyl ketone, five different concentrations are prepared, and 30 ° C. from Ubbelohde viscosity tube Measure the reduced viscosity of the solution at each concentration to determine the limiting viscosity [η].

  The graft ratio and the intrinsic viscosity [η] are the types and amounts of polymerization initiators, chain transfer agents, emulsifiers, etc., types and amounts of solvents, etc. used when producing rubber-reinforced vinyl resins, and further, the charging time 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 made of a thermoplastic resin (X), or may be made 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, a polyvinylidene chloride Examples thereof include resins, fluorine resins, polyolefin resins, polyester resins, polyamide resins and polyimide resins.
The other thermoplastic resins may be used singly or in combination of two or more.
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 article having a matte tone (matt appearance) on the surface. In the present invention, those comprising an inorganic material (metal or inorganic compound) (hereinafter referred to as “inorganic matting material”) and those comprising an organic material (polymer) (hereinafter “organic matting” Or any combination of these.
The shape of the matting material (Y) is not particularly limited, and examples thereof include a spherical shape, an oval spherical shape, a linear shape, a plate shape, a polyhedron, an irregular shape and the like, and a hollow portion may be provided. In addition, the size of the matte material (Y) is also not particularly limited.

  Examples of inorganic matting materials include, as powdery and granular materials, calcium carbonate, magnesium carbonate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, calcium oxide, silicon oxide, silicon oxide, magnesium hydroxide, magnesium sulfate , Barium sulfate, silicates, talc, mica, kaolin, glass flakes, etc. in the form of microballoons, glass balloons, phenolic resin balloons etc., in the form of fibers, glass fibers, carbon fibers, metal fibers, Examples of the whisker-like carbon fibers include ceramic whiskers and titanium whiskers.

  Examples of organic matting agents include crosslinked resins (crosslinked acrylic resins, etc.) polymerized using unsaturated carboxylic acid alkyl ester monomers and a crosslinking agent, unsaturated nitrile monomers and aromatic vinyl monomers. A crosslinked resin (crosslinked acrylonitrile styrene resin, etc.) polymerized using a monomer and a crosslinking agent can be mentioned.

  As the above-mentioned matting material (Y), an inorganic type matting material is preferable. When an inorganic matte material is used as the matte material (Y), the matte appearance of the obtained laminate and the other parts and the like while maintaining the flexibility and vacuum formability of the film for insert molding The effect of suppressing the generation of a stagnant sound upon contact is further excellent and preferred.

  The proportion of the matting material (Y) contained in the thermoplastic resin composition is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, based on 100 parts by mass of the thermoplastic resin. More preferably, it is 3 to 12 parts by mass. If the matting material (Y) contained in the film for insert molding of the present invention falls within the above range, the matte appearance of the obtained laminate and the other while maintaining the flexibility and vacuum formability of the film, and the like The effect of suppressing the generation of stagnant noise when contacting with parts is further excellent and preferred.

  The above-mentioned thermoplastic resin composition is, according to the purpose, use and the like, further excluding the above-mentioned matting material (Y), a filler, a plasticizer, an antioxidant, an ultraviolet absorber, an antiaging agent, a flame retardant, a lubricant , Stabilizers, weathering agents, light stabilizers, heat stabilizers, antistatic agents, mold release agents, antibacterial agents, antiseptics, colorants (pigments, dyes, etc.), fluorescent whitening agents, conductivity imparting agents, etc. It can be done.

  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 Molecular type plasticizers, chlorinated paraffin and the like can be mentioned. These can be used alone or in combination of two or more.

  Examples of the above-mentioned antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, phosphorus-containing compounds and the like. 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.

  As the above-mentioned anti-aging agent, naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thio compounds Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, dithiocarbamic acid nickel salt compounds, and phosphoric acid compounds. 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, silicone compounds and the like. These can be used alone or in combination of two or more.
In addition, aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compounds, molybdenum compounds, zinc stannate and the like can be used.

  Examples of the mold release agent include olefin waxes, silicone oils, higher fatty acids, higher fatty acid esters of monohydric or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, and natural waxes such as paraffin wax Examples include petroleum-based waxes, natural coal-based waxes such as montan wax, and the like. These can be used alone or in combination of two or more.

The above-mentioned olefin wax is usually a (co) polymer containing a structural unit derived from an olefin. In addition, the structure of the olefin wax is not particularly limited, and may be linear or branched.
Examples of the above-mentioned olefin wax include polyethylene wax, polypropylene wax, olefin copolymer wax (for example, ethylene copolymer wax) and the like, and these may be partial oxides. When the above-mentioned olefin wax is a copolymer, for example, olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-decene, 4-methyl-1-butene, 4-methyl-1-pentene Copolymers containing two or more structural units derived from: at least one of structural units derived from olefins and monomers copolymerizable with olefins (unsaturated carboxylic acids or their acid anhydrides, (meth) acrylic acid The copolymer etc. which consist of a structural unit derived from an alkyl ester etc. are mentioned. 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 is preferably one having a polyorganosiloxane structure, and may be, for example, unmodified silicone oil such as dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, etc., or polyorganosiloxane structure The modified silicone oil etc. in which various organic groups were introduce | transduced into a part of side chain in the inside and / or the one terminal part of a polyorganosiloxane structure, or the both terminal part of a polyorganosiloxane structure are mentioned.
As the above-mentioned modified silicone oil, 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, methyl chlorine Phenyl silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, acrylic modified silicone oil, methacrylic modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, carbinol modified silicone 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, particularly preferably 20 from the viewpoint of releasability. ~ 30,000 cSt. In addition, the said kinematic viscosity can be measured by the Ubbelode viscometer by ASTMD445-46T (it is also JIS 8803 good).

  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 or whole ester of a C1-C20 monohydric or polyhydric alcohol and a C10-C30 saturated fatty acid, for example, stearic acid monoglyceride, stearic acid Diglycerides, stearic acid triglyceride, monosorbate stearate, stearyl stearate, monoglyceride behenate, behenyl behenate, 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.

  Although the Tm (melting point) of the thermoplastic resin composition according to the present invention is in the range of 0 to 120 ° C., 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 ethylene-.alpha.-olefin rubber-polymer-reinforced vinyl-based resin is preferably composed of 10 to 90.degree. C., more preferably 20 to 80.degree. C., as Tm (melting point).

  The resin component contained in the above-mentioned thermoplastic resin composition may consist of thermoplastic resin (X) as mentioned above, and consists of this thermoplastic resin (X) and other thermoplastic resin. In any case, when the thermoplastic resin (X) is made of a rubber-reinforced vinyl-based resin, the content ratio of the rubber-like polymer portion (a1) constituting the rubber-reinforced vinyl-based resin is , Film processability, followability (flexibility) of the film to the concave portion, convex portion, etc. of the surface of the injection molding die, and further, from the viewpoint of the impact resistance of the resin film portion formed by the insert molding method The amount is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass, based on the whole of the thermoplastic resin composition. In addition, a vinyl-based resin in which the thermoplastic resin (X) comprises a polymer portion derived from the ethylene / α-olefin rubber (r1) and a vinyl-based (co) polymer portion derived from an aromatic vinyl compound In the case of an ethylene / α-olefin rubber polymer reinforced vinyl resin consisting of parts, the content ratio of the polymer part derived from the ethylene / α-olefin rubber (r1) is film processability, and From the viewpoint of the impact resistance of the resin film portion formed by the insert molding method, preferably 5 to 50% by mass, more preferably 10 to 45% by mass, still more preferably to the whole of the thermoplastic resin composition. It is 15 to 35% by mass.

  The said thermoplastic resin composition contains the resin component which consists of a thermoplastic resin (X) and another thermoplastic resin, The other thermoplastic resin is a vinyl type which has a structural unit derived from a vinyl-type monomer. When it is a (co) polymer, the limiting viscosity [η] (measured in methyl ethyl ketone, at 30 ° C.) of the acetone-soluble component of the thermoplastic resin composition is preferably 0 in view of extrudability, molding processability, etc. It is preferably from 0.05 to 0.90 dl / g, more preferably from 0.07 to 0.81 dl / g, still more preferably from 0.09 to 0.65 dl / g, particularly preferably from 0.12 to 0.55 dl / g.

  The film for insert molding of the present invention is a known molding apparatus such as a calendar molding apparatus, a T-die extrusion molding apparatus, an inflation molding apparatus, etc., of the above-mentioned thermoplastic resin composition or the raw material component to form its components. It can manufacture by processing with.

  The thickness of the film for insert molding of the present invention can be easily handled, and the insert molding excellent in matt noise appearance reduction effect, etc. in the resin film portion of the laminate formed by the insert molding method It is preferably 50 to 400 μm, more preferably 70 to 350 μm, and still more preferably 90 to 280 μm, because the product can be manufactured smoothly.

The film for insert molding of the present invention is subjected to an insert molding method using an injection molding die to reduce the generation of stagnant noise when dynamically contacting other parts with the surface of the resin molded portion 3. It is possible to preferably manufacture a laminate (a squealing sound reduction composite, an insert-molded article) 5 formed by bonding the resin film portion 4 having the resin film portion 4 (see FIG. 1 (D), FIG. 2 etc.). The resin molding part 3 can be made of a thermoplastic resin composition or a cured resin composition.
The above-mentioned laminate (staining sound reduction composite, insert-molded article) 5 is a step of disposing a film for insert molding inside an injection molding die (hereinafter referred to as “first step”), and It can manufacture by the method provided with the process (henceforth a "2nd process") which injects a resin composition to the cavity of a metal mold (refer FIG. 1). The first step may be a step using the film not processed into a specific shape as it is (the film 1 for insert molding) as shown in FIG. 1 (A), or 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 used by placing it in an injection mold. It may be a process.

  Hereinafter, with respect to a method of manufacturing the laminate (the squealing sound reduction composite, the insert-molded article) 5 using the film 1 for insert molding and the injection mold including the male die 11 and the female die 12 as shown in FIG. It illustrates and demonstrates by. In addition, when manufacturing the laminate 5, a concave portion, a convex portion, a groove portion, etc. 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. Depending on the raw material component of the thermoplastic resin composition which comprises the part 3, or a cured resin composition, you may surface-treat.

  First, as shown in FIG. 1A, the insert molding film 1 is placed 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 die 12 by using suction means such as the suction holes 13 arranged in the female die 12. Since the film 1 for insert molding has flexibility, it can be easily adhered along the inner surface of the female die 12 to form a film structure 1a having a predetermined shape (see FIG. 1 (B)). . Although not shown in FIG. 1A, the insert molding film 1 may be fixed by, for example, a frame-like sheet clamp.

  Next, as shown in FIG. 1C, the male mold 11 and the female mold 12 are clamped, and in the cavity formed by both molds, they are in a heated and melted state from the inlet 14 formed in the male mold 11 The raw material 2 for resin molded part formation which consists of a thermoplastic resin composition or room temperature curing or thermosetting resin composition is supplied (2nd process). When the raw material 2 for resin molding part formation consists of a thermoplastic resin composition or a thermosetting resin composition, the film 1 (film structure 1a) for insert molding may be preheated. Thereafter, the raw material 2 for forming a resin molded part is solidified by cooling or the like, and the mold is opened to take out the integrated laminate (the stagnant sound reduction composite, insert molded article) 5. At this time, if there is an unnecessary portion of the insert molding film, it is trimmed appropriately. By 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 molding portion 3 made of the thermoplastic resin composition or the cured resin composition. (See FIG. 1 (D)).

  Although the manufacturing method using FIG. 1 demonstrated trimming the unnecessary part in the film for insert moldings, this invention is not limited to this. For example, in the case of producing a laminate 5 as shown in FIG. 2, the insert molding film is cut to a predetermined size and placed at a predetermined position inside the injection molding die. Resin compositions 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 of manufacturing such a laminate 5, the second step is performed only once. 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 resin film portions 4 can be used.

  When the raw material 2 for forming a resin molded part 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 ( (Co) polymer obtained by polymerizing a polymerizable unsaturated monomer containing an aromatic vinyl compound in the absence of an ABS resin, an AES resin, an ASA resin, an MBS resin, etc., and 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 naf Such as polycarbonate resin, polyarylate resin, polyacetal resin, polyamide resin, fluorocarbon resin, polyphenylene ether, polyphenylene sulfide, imide resin, polyether ketone, ketone resin such as polyether ether ketone, polysulfone, polyether sulfone etc. It can be set as the composition etc. which contain at least 1 sort (s) of thermoplastic resin chosen from sulfone-type resin of the above, a biodegradable plastic, etc.

  When the raw material 2 for forming a resin molded part used in the second step is a curable resin composition, it is cured of an acrylic resin, a phenol resin, a furan resin, an acrylic silicone resin, a urethane resin, a melamine resin, an epoxy resin, etc. It can be set as the unhardened curable composition etc. which contain resin resin (prepolymer etc.), a curing agent (polymerization initiator etc.), etc.

In the laminate (the stagnation sound reduced composite, insert molded article) 5 obtained by the present invention, the resin film portion 4 is the same as or different from the thermoplastic resin composition constituting the insert molding film of the present invention Dynamic 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 portion 4 in the laminate 5 is brought into contact with other parts to obtain a composite structure, the effect of suppressing generation of stagnant noise due to vibration, twist, impact or the like, the laminate 5 and the like Noise is generated when parts are placed with a predetermined gap and one or both of them move or deform due to vibration, twist, impact, etc. to make dynamic contact (surface contact, line contact or point contact). It is suitable for obtaining the suppression effect of
FIG. 3 has two concave portions or groove portions as the laminate 5, and the resin film portion 4 is formed on the surface on the side having these, and the resin connection member 7 is used as another component. The composite structure 15 is shown. In FIG. 3, since the connecting member 7 made of resin is fitted to be in contact with the resin film portion 4 of the concave portion or the groove portion in the laminate 5, it is possible to suppress generation of stagnant noise due to vibration, torsion, impact or the like. You can get the effect.

  A laminate (a squealing sound reduction composite, an insert molded article) 5 obtained by the present invention is a composite product that constitutes a vehicle, an office automation (OA) device, a home appliance, an electric / electronic device, a building material, etc. It is suitable as one member.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples unless the gist of the present invention is exceeded. In the following, parts and% are based on mass unless otherwise specified.

1. Manufacturing raw material of film for insert molding The manufacture of the film for insert molding was performed by T-die extrusion molding of the thermoplastic resin composition prepared using the following raw material. In addition, the measurement of the graft ratio of a resin component etc., an intrinsic viscosity [eta], etc. was performed according to the method of the said description.

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

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

Synthesis example 2 (synthesis of raw material P2)
Ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C, glass transition temperature: in a stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc. 10 parts of Mooney viscosity (ML _{1 + 4} , 100 ° C.): 20), 13.2 parts of styrene, 4.8 parts of acrylonitrile, 0.7 parts of tert-dodecyl mercaptan and 100 parts of toluene were charged, and the temperature was raised. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.11 part of tert-butylperoxyisopropyl monocarbonate was added, and the temperature was further raised. While maintaining the internal temperature at 100 ° C., polymerization was started at a stirring rotational speed of 100 rpm. After polymerization for 70 minutes, 52.8 parts of styrene, 19.2 parts of acrylonitrile and 0.42 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 3 hours and 30 minutes. After 4 hours and 30 minutes of initiation of the polymerization, the internal temperature was raised to 120 ° C., and the reaction was further carried out for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion was 97%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, and a portion made of ethylene-propylene copolymer rubber, and a vinyl cyanide compound ( Ethylene / α-olefin rubber polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion consisting 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 composed of an ungrafted vinyl copolymer (acrylonitrile / styrene copolymer). The graft ratio of the graft resin (acetone insoluble matter) contained in this raw material P2 was 52%. The content of acetone soluble matter contained in the raw material P2 is 85% when the whole raw material P2 is 100%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone soluble matter is It was 0.25 dl / g. Then, when Tm of the raw material P2 was measured using this pellet, it was 40 degreeC.

Synthesis example 3 (synthesis of raw material P3)
Ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C, glass transition temperature: in a stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc. 50 parts of Mooney viscosity (ML _{1 + 4} , 100 degrees C.): 20), 7.3 parts of styrene, 2.7 parts of acrylonitrile, 0.1 parts of tert-dodecyl mercaptan and 220 parts of toluene were charged, and the temperature was raised. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.07 part of tert-butylperoxyisopropyl monocarbonate was added, and the temperature was further raised. While maintaining the internal temperature at 100 ° C., polymerization was started at a stirring rotational speed of 100 rpm. After polymerization for 60 minutes, 29.3 parts of styrene, 10.7 parts of acrylonitrile and 0.25 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 2 hours and 30 minutes. After 3 hours and 30 minutes of initiation of the polymerization, the internal temperature was raised to 120 ° C., and the reaction was further carried out for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, and a portion made of ethylene-propylene copolymer rubber, and a vinyl cyanide compound ( Ethylene / α-olefin rubber polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion consisting 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 composed 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 acetone soluble matter contained in the raw material P3 is 30% when the whole raw material P3 is 100%, and the limiting viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone soluble matter is It was 0.40 dl / g. Then, when Tm of the raw material P3 was measured using this pellet, it was 40 degreeC.

Synthesis Example 4 (Synthesis of Raw Material P4)
Ethylene / propylene copolymer rubber (ethylene / propylene = 78/22 (%), Tm: 40 ° C, glass transition temperature: in a stainless steel autoclave equipped with a ribbon stirrer blade, auxiliary additive continuous addition device, thermometer, etc. 50 parts of Mooney viscosity (ML _{1 + 4} , 100 degrees C.): 20), 7.3 parts of styrene, 2.7 parts of acrylonitrile, 0.3 parts of tert-dodecyl mercaptan and 220 parts of toluene were charged, and the temperature was raised. When the internal temperature reached 75 ° C., the contents of the autoclave were stirred for 1 hour to make a homogeneous solution. Thereafter, 0.07 part of tert-butylperoxyisopropyl monocarbonate was added, and the temperature was further raised. While maintaining the internal temperature at 100 ° C., polymerization was started at a stirring rotational speed of 100 rpm. After polymerization for 60 minutes, 29.3 parts of styrene, 10.7 parts of acrylonitrile and 0.25 parts of tert-butylperoxyisopropyl monocarbonate were continuously added over 2 hours and 30 minutes. After 3 hours and 30 minutes of initiation of the polymerization, the internal temperature was raised to 120 ° C., and the reaction was further carried out for 2 hours while maintaining this temperature to complete the polymerization. The polymerization conversion was 98%. Thereafter, the internal temperature was cooled to 100 ° C., and 0.2 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. Then, the reaction solution was withdrawn from the autoclave, and the unreacted material and the solvent were distilled off by steam distillation. Thereafter, the volatile components are substantially degassed using a 40 mm φ vented extruder (cylinder temperature 220 ° C., vacuum degree 760 mmHg), pelletized, and a portion made of ethylene-propylene copolymer rubber, and a vinyl cyanide compound ( Ethylene / α-olefin rubber polymer reinforced vinyl resin (graft resin) comprising a structural unit derived from acrylonitrile) and a portion consisting 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 composed 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 acetone soluble matter contained in the raw material P4 is 38% when the whole raw material P4 is 100%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of this acetone soluble matter is It was 0.35 dl / g. Then, when Tm of the 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 parts of potassium rosinate, 0.2 parts of tert-dodecyl mercaptan, polybutadiene rubber with an average particle size of 300 nm (gel content 80% Containing 80 parts of a latex containing 32 parts, 19 parts of a latex containing 8 parts of a styrene-butadiene copolymer rubber (30% styrene unit weight) having an average particle diameter of 600 nm, 14 parts of styrene and 6 parts of acrylonitrile while stirring The temperature rose. When the internal temperature reached 40 ° C, a solution of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.3 parts of glucose in 8 parts of ion-exchanged water was added . Thereafter, 0.07 parts of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 30 minutes, 45 parts of ion exchanged water, 0.7 parts of potassium rosin acid, 30 parts of styrene, 10 parts of acrylonitrile, 0.13 parts of tert-dodecyl mercaptan and 0.1 parts of cumene hydroperoxide for 3 hours Was added continuously. Thereafter, the polymerization was continued for an additional hour, and 0.2 parts of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) was added to the reaction system to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and washed with water. Thereafter, the resultant is washed, neutralized, washed with water, and dried using a potassium hydroxide aqueous solution, and a portion made of a styrene-butadiene copolymer rubber, a structural unit derived from a vinyl cyanide compound (acrylonitrile), Diene rubbery polymer reinforced vinyl resin (graft resin) containing a vinyl copolymer containing a structural unit derived from an aromatic vinyl compound (styrene), and an ungrafted vinyl copolymer A rubber reinforced resin (raw material P5) which is a resin mixture composed of (acrylonitrile-styrene copolymer) was obtained. The graft ratio of the diene rubber 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 of this acetone-soluble portion [[ (In methyl ethyl ketone, 30 ° C.) was 0.45 dl / g. In addition, Tm of this raw material P5 was not observed.

1-2. Raw material [Q]
The following raw materials Q1 to Q4 were used as thermoplastic resins not containing a portion derived from a rubbery polymer.
(1) Raw material Q1
An acrylonitrile styrene copolymer (2) raw material having an acrylonitrile unit and a styrene unit ratio of 27% and 73%, respectively, and an intrinsic viscosity [[] (in methyl ethyl ketone, 30 ° C.) of 0.30 dl / g Q2
An acrylonitrile styrene copolymer (3) raw material having an acrylonitrile unit and a styrene unit ratio of 27% and 73%, respectively, and an intrinsic viscosity [[] (in methyl ethyl ketone, 30 ° C.) of 0.45 dl / g Q3
An acrylonitrile styrene copolymer (4) raw material having an acrylonitrile unit and a styrene unit ratio of 27% and 73%, respectively, and an intrinsic viscosity [[] (in methyl ethyl ketone, 30 ° C.) of 1.20 dl / g Q4
A methacrylic resin “ACRYPET VH-5” (trade name, a copolymer of methyl methacrylate and methyl acrylate) manufactured by Mitsubishi Rayon Co., Ltd. was used.

1-3. Raw material [R]
A polycarbonate "NOVAREX 7022 PJ" (trade name) manufactured by Mitsubishi Engineering Plastics, Inc. 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 agent (Y).
(1) Raw material S1
As an inorganic type matting material, granular glass flakes made by Nippon Sheet Glass Co., Ltd. "Micrograss Freca REFG-101" (trade name) were used. The glass flakes are scaly, the average thickness of the base glass is 5 μm, and the average particle size of the base glass is 600 μm.
(2) Raw material S2
A partially crosslinked acrylic additive "Metabrene F-410" (commercial item, crosslinked methyl methacrylate-alkyl acrylate-styrene copolymer) manufactured by Mitsubishi Rayon Co., Ltd. was used as the organic matting agent.

2. Production and Evaluation of Insert Molding Film Examples 1 to 19 and Comparative Examples 1 to 3
Using the raw materials [P], [Q], [R] and [S] and mixing the raw materials with the Henschel mixer at the mixing ratio shown in Table 1 and Table 2, the obtained mixture is The mixture was supplied to a twin-screw extruder "TEX 44 α II" (model name) and melt-kneaded (cylinder set temperature: 200 ° C to 250 ° C) to obtain pellets composed of a thermoplastic resin composition.
Then, this pellet is supplied to an extruder with a screw diameter of 115 mm disposed in a film forming machine equipped with a T die (die width: 1600 mm, lip distance 1 mm), and melting from the T die is performed at a resin temperature of 240 ° C. The resin was discharged to form a soft film. Thereafter, the soft film is brought into intimate contact with a cast roll (surface temperature of the roll; 90 ° C.) by an air knife, and is operated so as to obtain the thickness shown in Tables 1 and 2. Obtained.
The temperature of the molten resin was measured using a thermocouple thermometer. In addition, the thickness of the film for insert molding is obtained by using a thickness gauge (type “ID-C1112C”, manufactured by Mitutoyo Corp.), cutting off the film after 1 hour from the start of film production, the center in the film width direction, and the center The thickness was measured at intervals of 10 mm toward both ends, and the average value was taken. The values of the measuring points in the range of 20 mm from the end of the film were removed from the calculation of the average value.

The obtained insert molding film was subjected to the following evaluation, and the results are shown in Tables 1 and 2.
2-1. Film Formability The film formability was determined from the difference in thickness at each point of the film measured as described above. The smaller the difference in height, the more uniform the thickness of the obtained film, and the better the film forming property.
○: The difference is less than 30 μm and the film forming property is excellent.
Δ: The difference is 30 μm or more and less than 40 μm, and the film forming property is good.
X: The difference is 40 μm or more and the film forming property is inferior

2-2. Adhesion to resin moldings The insert molding film is cut into a size of 70 mm (MD) × 25 mm (TD), fixed in a mold of an injection molding machine, and then the mold is closed and melted at 240 ° C. The heat resistant ABS resin "Techno MUH E1500" (made by Techno Polymer Co., Ltd.) was injected, and the laminate was molded. Next, the laminate is taken out of the mold, conditioned at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and then subjected to a 90 ° peel test (film tensile speed in the MD direction: 1 mm / sec). The adhesion between the part and the injection resin molded part was evaluated according to the following criteria.
Good: The portion of the film for insert molding does not separate from the resin molded portion and the film is broken. Δ: The portion of the film for insert molding slightly separates at the resin molded portion and the adhesive surface, but the film is broken halfway: X: insert molding Part of the film for peeling off at the resin molding part and the adhesive surface, the film did not break

2-3. The film for flexible 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 this folded state is reciprocated twice on each crease at a speed of 5 mm / sec using a manual pressure bonding roll (2,000 g) according to JIS Z0237, and then the crease is expanded. It returned to the original state, the crease was observed visually, and it judged by the following standard. The one in which the crease is not broken is excellent in flexibility.
○: The crease was not broken, and the crease was not broken even if it was folded and spread again △: The crease was not broken but the crease was broken when it was folded and spread again ×: the crack was broken

2-4. Vacuum Formability The insert molding film is cut into a size of 300 mm (MD) × 210 mm (TD), and the molded article shown in FIG. 5 (IV) is provided with a vacuum forming mold 8 shown in FIG. It manufactured using small-sized vacuum forming machine "300X". The vacuum forming mold 8 shown in FIG. 4 has a height of 45 mm, a bottom size of 150 mm × 150 mm, an upper surface size of 140 m × 140 mm, and a central area of 100 mm × 100 mm on the upper surface. A recess of 20 mm in depth is formed and has fine through holes throughout.
An insert molding film of the above-mentioned size was fixed at a distance of 40 mm above the upper surface of the vacuum forming mold 8 (FIG. 5 (I)). Then, the film for insert moldings was heated from the peripheral side using the heater (not shown) previously heated at 450 degreeC. Next, the vacuum forming mold 8 was moved upward to bring the upper surface into contact with the insert forming film (FIG. 5 (II)). Thereafter, the pressure was reduced from the bottom side of the vacuum forming mold 8, the insert forming film was brought into close contact with the inner surface of the recess of the vacuum forming mold 8, and the vacuum forming was performed (FIG. 5 (III)). Next, the vacuum forming mold 8 was released to obtain a molded article shown in FIG. 5 (IV). The followability of the film for insert molding to the recess of the vacuum forming mold 8 was visually observed and evaluated according to the following criteria.
:: The ability to follow the recesses of the vacuum forming mold 8 is good, and no wrinkles are observed on the film surface of the molded article shown in FIG. 5 (IV): the ability to follow the recesses of the vacuum forming die 8 is Although it was good, wrinkles were observed on the film surface of the molded article shown in FIG. 5 (IV) x: The ability to follow the recess of the vacuum forming mold 8 was poor, and the film of the molded article shown in FIG. Wrinkles were observed on the surface

  In the following stick-slip test, in order to evaluate the ease or difficulty of generation of a stagnant sound when an insert-molded product is manufactured using a film for insert molding, as in item 2-2 above The resin film portion 4 which is the obtained laminate and is made of the insert molding film (50 mm × 25 mm) manufactured using each pellet is made of the 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 x 25 mm x 4 mm) was used (refer FIG. 6).

2-5. A resin film portion 4 which is a composite obtained as described in item 2-2 above and which is made of a film for insert molding (50 mm × 25 mm) manufactured using each pellet is a heat-resistant ABS resin “ Test body 18 joined to a support (resin molded part) 16 (50 mm × 25 mm × 4 mm) made of “Techno MUH E1500” (made by Techno Polymer Co., Ltd.) in a 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., which is disposed directly on the ceiling of a dark room, which is directly above the test body 18 and has a distance of 2 m to the resin film portion 4. It was made to light-emit and five panelists visually observed the matting property in the resin film part 4, and the following reference | standard evaluated.
:: All five panelists judged that the film surface had no reflection or reflection of fluorescent light, and a good matte appearance was obtained.
Fair: 1 to 4 of 5 panelists judged that the film surface had reflections or reflections of fluorescent light, and that a good matte appearance was not obtained.
X: All five panelists judged that the film surface had reflection and reflection of fluorescent light, and did not have a good matte appearance.

2-6. Stick-slip test (noise noise risk index)
In the stick-slip test, a stick-slip tester “SSP-02” (model name) manufactured by Ziegler (ZIEGLER), the above-mentioned test body 18, an AES resin “Techo AESW210” (made by Techno Polymer) or an ABS / PC alloy “ Test piece 20 (60 mm × 100 mm × 4 mm) made of EXCELOY CK 20 (made by Techno Polymer Co., Ltd.), PMMA “Acriprene” (Mitsubishi Rayon Co., 60 mm × 100 mm × 80 μm) or PET “Teijin Tetron Film” (Teijin DuPont Film Co., Ltd.) A film of 60 mm × 100 mm × 50 μm) was set as shown in FIG. 7, and both were rubbed three times to measure an abnormal noise risk index. The measurement conditions are temperature: 23 ° C., humidity: 50% RH, load: 40 N, speed: 10 mm / sec, amplitude: 20 mm. The smaller the allophone risk index, the lower the risk of itching. In each table, a place indicated by "-" indicates that the experiment was not conducted.

2-7. Melting point (Tm)
The melting point was measured by a differential scanning calorimeter “DSC 2910” (model name) manufactured by TA Instruments in accordance with JIS K 7121-1987. In the measurement, the endothermic change was observed at a constant temperature rising rate of 20 ° C. per minute, and the melting point was read from the peak temperature of the obtained endothermic pattern.

The following is apparent from Tables 1 and 2. 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 including the portion derived from the rubbery polymer, but the noise risk index in the stick-slip test Became high. Although the comparative example 2 is an example using the thermoplastic resin composition which does not contain the part originating in a rubbery polymer, and Tm does not exist in the range of 0-120 degreeC, film forming property and a resin molded article In addition to inferiority in adhesion, flexibility and vacuum formability, in the stick-slip test, the noise risk index increased. Comparative Example 3 is an example containing no matting material, but was inferior in matting property.
On the other hand, it is clear that Examples 1 to 19 using the composition having the constitution of the present invention are excellent in the matting performance, excellent in the flexibility and the vacuum formability, and less likely to generate stagnant noise. is there.

  When the film for insert molding of the present invention is used together with a mold for injection molding, generation of stagnant noise when dynamic contact with other parts is suppressed, and a resin film portion having a good matte appearance and It is possible to efficiently manufacture a laminate (a squealing sound reduction composite, an insert-molded article) in which a base made of a resin composition is joined. And, the obtained laminate (smudge noise reduction composite, insert molded article) is suitable as a member of products constituting vehicles, office automation (OA) equipment, home electric appliances, electric / electronic equipment, building materials, etc. is there.

1: film for insert molding 1a: film structure of a predetermined shape 2: raw material for forming a resin molded portion 3: resin molded portion 4: resin film portion 5: laminate (insert molded product or stagnant sound reduced composite)
7: Connection parts 11: Injection mold (male)
12: Injection molding mold (female mold)
13: Suction hole 14: Inlet of raw material for forming resin molded part 15: Composite 16: Support 18: Test body for evaluation of squeak noise 20: Stage for squeak noise evaluation

Claims (5)

Thermoplastic resin containing a thermoplastic resin containing a portion (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 to 1987 Consisting of a resin composition,
The rubbery polymer is an ethylene / α-olefin rubber,
The ethylene / α-olefin rubber has a melting point in the range of 0 to 120 ° C. according to JIS K 7121-1987,
The content of the portion (a1) is 6.25 to 90% by mass, based on 100% by mass of the thermoplastic resin,
A film for insert molding having a thickness of 50 to 400 μm. Wherein the thermoplastic resin is, the a portion (a1), insert molding film according to claim 1 is a rubber-reinforced vinyl-based resin containing a portion (a2) derived from a vinyl resin. The matting material (Y) is, insert molding film according to claim 1 or 2 is a matting material inorganic. The film for insert molding according to any one of claims 1 to 3 , which has a thickness of 50 to 300 μm. A step of disposing the insert molding film according to any one of claims 1 to 4 inside an injection molding die, and a step of injecting a resin composition into a cavity of the injection molding die, A method of manufacturing an insert-molded product, comprising:

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