JP2009144134A - Thermoplastic resin composition for expansion molding, expansion molded article, and multilayer article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for expansion molding, which is suitable for forming an expansion molded article excellent in mechanical strength, having low linear expansion coefficient, and excellent in dimensional stability, and an expansion molded article and a multilayer article. <P>SOLUTION: The thermoplastic resin composition for the expansion molding comprises: [A] a thermoplastic resin containing a styrene resin (A1) of 5-100 mass%, when the whole is 100 mass%; [B] a fibrous filler in which an aspect ratio is 5-50 and a mean particle diameter is 3-50 μm; and [C] an expanding agent containing a compound having boiling point of -10 to +55°C. In the thermoplastic resin composition for the expansion molding, content of the fibrous filler [B] is 5-150 pts.mass to the thermoplastic resin [A] of 100 pts.mass, and content of the expanding agent [C] is 0.1-5 pts.mass to the thermoplastic resin [A] of 100 pts.mass. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition for foam molding containing a thermoplastic resin, a fibrous filler, and a foaming agent, and a foam molded product and a laminate product using the composition. The present invention relates to a thermoplastic resin composition for foam molding, a foam molded product, and a laminate that are excellent in stability and suitable for forming a foam molded product having a high expansion ratio.

  In recent years, a resin composition mainly composed of a resin excellent in weight reduction, durability and the like has been used as a building material. In order to reduce the weight of products, in particular, foam molding using a resin composition containing a resin and a foaming agent has been widely applied (for example, Patent Document 1).

Japanese Patent Laid-Open No. 5-19476

While the foam molded product using the resin composition is lightweight, the strength, the deformation, and the like may be caused depending on the shape, application, and the like. In order to solve these problems, attempts have been made to blend a filler, but it has not been sufficient.
An object of the present invention is to provide a thermoplastic resin composition for foam molding, a foam molded product, and a laminate that are suitable for forming a foam molded product having excellent mechanical strength and excellent dimensional stability.

The present invention is shown below.
1. [A] a thermoplastic resin containing 5 to 100% by mass of a styrene resin (A1) when the total is 100% by mass; [B] an aspect ratio of 5 to 50 and an average particle size of 3 to 50 μm And a foaming agent containing a compound having a boiling point of −10 ° C. to 55 ° C., wherein the fibrous filler [B ] Is 5 to 150 parts by mass with respect to 100 parts by mass of the thermoplastic resin [A], and the content of the foaming agent [C] is 100 parts by mass of the thermoplastic resin [A]. The thermoplastic resin composition for foam molding, characterized by being 0.1 to 5 parts by mass with respect to parts.
2. 2. The thermoplastic resin composition for foam molding according to 1 above, wherein the fibrous filler [B] is wollastonite.
3. The thermoplastic resin corresponding to 5 to 50% by mass of the thermoplastic resin [A], the fibrous filler corresponding to 0 to 50% by mass of the fibrous filler [B], and the foam A composition [X] containing a foaming agent corresponding to 50 to 100% by mass of the agent [C], and a thermoplastic resin corresponding to 50 to 95% by mass of the thermoplastic resin [A]. And a fibrous filler corresponding to 50 to 100% by mass of the fibrous filler [B] and a foaming agent corresponding to 0 to 50% by mass of the foaming agent [C]. The thermoplastic resin composition for foam molding according to 1 or 2 above, which is a mixture of the composition [Y].
4). 4. The thermoplastic resin composition for foam molding according to 3 above, wherein the composition [X] is a foaming agent-containing master batch having an expansion ratio of 1.15 or less.
5). The thermoplastic resin composition for foam molding according to 3 or 4 above, wherein the composition [Y] is a melt-kneaded product containing no foaming agent [C].
6). When the acetone soluble component obtained by immersing the styrenic resin (A1) contained in the composition [X] in acetone is 100% by mass as a whole, it is a single unit composed of an aromatic vinyl compound. Body unit (monomer unit derived from aromatic vinyl compound) 75 to 95% by mass, monomer unit composed of vinyl cyanide compound (monomer unit derived from vinyl cyanide compound) 5 to 25% by mass, And the thermoplastic resin composition for foam molding according to any one of 3 to 5 above, comprising 0 to 20% by mass of a monomer unit comprising another compound (a monomer unit derived from another compound). object.
7). The styrenic resin (A1) is aromatic in the presence of a styrenic copolymer and / or a rubbery polymer using a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound. 7. The thermoplastic resin composition for foam molding according to any one of 1 to 6 above, comprising a rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing a vinyl compound and a vinyl cyanide compound.
8). A foam molded article obtained by using the thermoplastic resin composition for foam molding according to any one of 1 to 7 above.
9. 8. A foam molded article obtained by extrusion molding the thermoplastic resin composition for foam molding according to any one of 1 to 7 above.
10. The foamed molded article according to 8 or 9 above, wherein the foaming ratio is 2 to 25 times.
11. ^11. The foamed molded article according to any one of 8 to 10 above, having a linear expansion coefficient of 5.5 × 10 ⁻⁵ (1 / ° C.) or less.
12 The molded part (V) obtained by using the thermoplastic resin composition for foam molding according to any one of 1 to 7 above and a member (W) made of another material are laminated. Laminated product.

According to the thermoplastic resin composition for foam molding of the present invention, it is suitable for forming a foam molded product having excellent mechanical strength, a small linear expansion coefficient, and excellent dimensional stability and its stable production.
In the case where the fibrous filler [B] is wollastonite, the mechanical strength and the molded appearance are further improved. And the foaming molded product which is small in shrinkage | contraction and is further excellent in dimensional stability can be obtained.
The thermoplastic resin composition for foam molding of the present invention comprises a thermoplastic resin corresponding to 5 to 50% by mass of the thermoplastic resin [A] and 0 to 50 of the fibrous filler [B]. Of a composition [X] containing a fibrous filler corresponding to mass% and a foaming agent corresponding to 50 to 100 mass% of the foaming agent [C], and the thermoplastic resin [A]. Thermoplastic resin corresponding to 50 to 95% by mass of the fiber, fibrous filler corresponding to 50 to 100% by mass of the fibrous filler [B], and 0 of the foaming agent [C]. When it is a mixture of a composition [Y] containing a foaming agent corresponding to ˜50% by mass, it has excellent mechanical strength, a small coefficient of linear expansion, excellent dimensional stability, and surface appearance. It is suitable for the formation of an excellent foamed molded product and its stable production.
When the composition [X] is a foaming agent-containing masterbatch with an expansion ratio of 1.15 or less, it has excellent mechanical strength, a small coefficient of linear expansion, excellent dimensional stability, and surface appearance. It is suitable for forming an excellent foamed molded product.
When the composition [Y] is a molten mixture containing no foaming agent [C], the mechanical strength is excellent, the linear expansion coefficient is small, the dimensional stability is excellent, and the surface appearance is excellent. It is suitable for forming a foam molded product.
When the acetone-soluble component obtained by immersing the styrene-based resin (A1) contained in the composition [X] in acetone is 100% by mass as a whole, it is derived from an aromatic vinyl compound. When comprised of monomer units 75 to 95% by mass, monomer units 5 to 25% by mass derived from vinyl cyanide compounds, and monomer units 0 to 20% by mass derived from other compounds Is suitable for forming a foam molded article having excellent mechanical strength, a small linear expansion coefficient, excellent dimensional stability, and excellent surface appearance.

The foamed molded article of the present invention has uniform foamed cells, excellent mechanical strength, a small linear expansion coefficient, excellent dimensional stability, and excellent surface appearance.
The laminated product of the present invention is excellent in molding appearance and shape stability.

  The present invention will be described in detail below. In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acrylic and methacrylic.

1. Thermoplastic resin composition for foam molding The thermoplastic resin composition for foam molding of the present invention is a thermoplastic resin containing 5 to 100 mass% of a styrene resin (A1) when [A] is 100 mass% as a whole. (Hereinafter also referred to as “component [A]”), [B] fibrous filler (hereinafter also referred to as “component [B]”), and [C] boiling point of −10 ° C. to 55 ° C. A foaming thermoplastic resin composition containing a compound-containing foaming agent (hereinafter also referred to as “component [C]”), wherein the fibrous filler [B] It is 5 to 150 parts by mass with respect to 100 parts by mass of the plastic resin [A], and the content of the foaming agent [C] is 0.1 with respect to 100 parts by mass of the thermoplastic resin [A]. It is ˜5 parts by mass.

1-1. Thermoplastic resin [A]
This component [A] contains 5-100 mass% of styrene resin (A1) when the whole is 100 mass%. Therefore, the said component [A] consists of 1 or more types of the said styrene resin (A1) or 1 or more types of the said styrene resin (A1), and another thermoplastic resin.

1-1-1. Styrene resin (A1)
This styrene resin (A1) is a polymer containing a monomer unit derived from an aromatic vinyl compound. That is, the styrene resin (A1) is a monomer composed of one or more aromatic vinyl compounds, or one or more monomers copolymerizable with one or more aromatic vinyl compounds. A styrene-based (co) polymer obtained by (co) polymerizing monomers (hereinafter, both monomers are collectively referred to as “vinyl monomer (b1)”) ( A11) and / or other monomer capable of copolymerization with one or more monomers of an aromatic vinyl compound or one or more aromatic vinyl compounds in the presence of a rubbery polymer A rubber-reinforced styrene resin (hereinafter referred to as “vinyl monomer (b2)”) obtained by polymerizing monomers comprising at least one kind of body (hereinafter, both monomers are collectively referred to as “vinyl monomer (b2)”). A12). The rubber-reinforced styrene resin (A12) is usually composed of a grafted rubber polymer in which the vinyl monomer (b2) is graft-polymerized to a rubber polymer, and the vinyl polymer that is not grafted. It is a resin containing the (co) polymer of the monomer (b2).

  The aromatic vinyl compound constituting the vinyl monomer (b1) is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. . Examples thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

The styrenic (co) polymer (A11) as the styrenic resin (A1) may be either a homopolymer or a copolymer, or a combination thereof. A copolymer is preferred.
When the styrenic (co) polymer (A11) as the styrenic resin (A1) is a copolymer, other monomer units other than the monomer unit derived from the aromatic vinyl compound may be cyan. Vinyl compounds, (meth) acrylic acid ester compounds, maleimide compounds, acid anhydrides, vinyl compounds having functional groups such as hydroxyl groups, amino groups, epoxy groups, amide groups, carboxyl groups, oxazoline groups, etc. The monomer unit derived from is mentioned. These other monomer units may be included singly or in combination of two or more.

  Among the other monomers copolymerizable with the aromatic vinyl compound, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can be used alone or in combination of two or more. In addition, as another method of introducing a unit derived from a maleimide compound, for example, a method of copolymerizing maleic anhydride and then imidizing may be used.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

  Examples of the vinyl compound having a functional group such as hydroxyl group, amino group, epoxy group, amide group, carboxyl group, or oxazoline group include 2-hydroxyethyl (meth) acrylate, hydroxystyrene, and (meth) acrylic. Acid N, N-dimethylaminomethyl, N, N-diethyl-p-aminomethylstyrene, glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl Examples thereof include glycidyl ether, methacrylamide, acrylamide, (meth) acrylic acid, vinyl oxazoline and the like. These can be used alone or in combination of two or more.

  When the styrene-based (co) polymer (A11) is a copolymer, a preferable copolymer is a styrene-based polymer using a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound. A copolymer, and more specifically, a monomer unit derived from an aromatic vinyl compound, a monomer unit derived from a vinyl cyanide compound, and other monomer units contained as necessary. It is a copolymer consisting of. The content ratios of these monomer units are preferably 50 to 97% by mass, 3 to 50% by mass, and 0 to 47% by mass, respectively, when the total of all monomer units is 100% by mass. Preferably they are 55-95 mass%, 5-45 mass%, and 0-15 mass%. If it is the said content rate, it can be set as the foaming molded product which was excellent in chemical resistance and maintained the high foaming ratio with the thermoplastic resin composition for foam molding of this invention.

  When the styrene-based (co) polymer (A11) is a copolymer, acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, acrylonitrile / styrene -N-phenylmaleimide copolymer etc. are mentioned.

  Regarding the styrene-based (co) polymer (A11), the polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC) is preferably 100,000 to 300,000. More preferably, it is 100,000-270,000, More preferably, it is 120,000-250,000. When the Mw is within this range, the content of the foaming agent [C] in the thermoplastic resin composition for foam molding of the present invention is stable, and the change in the content over time can be reduced. In addition, a foam-molded product having excellent moldability and mechanical strength can be obtained.

  The styrene (co) polymer (A11) is produced by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound in the presence or absence of a polymerization initiator. be able to. When a polymerization initiator is used as the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. Moreover, when not using a polymerization initiator, it can be set as thermal polymerization.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b1) whole quantity.
In addition, the chain transfer agent, emulsifier, etc. which can be used at the time of manufacture of the rubber reinforcement | strengthening styrene-type resin (A12) mentioned later as needed can be used.

  In the production of the styrene-based (co) polymer (A11), the polymerization may be started in a state where the total amount of the vinyl-based monomer (b1) is accommodated in the reaction system, or a single amount selected arbitrarily. You may superpose | polymerize by adding a body component separately or continuously. Furthermore, when using the said polymerization initiator, it can add to a reaction system collectively or continuously.

  The rubber-reinforced styrene resin (A12) is a resin obtained by polymerizing the vinyl monomer (b2) in the presence of a rubber polymer (hereinafter referred to as “rubber polymer (a)”). It is.

  The rubbery polymer (a) may be a homopolymer or a copolymer as long as it is rubbery at room temperature, but a diene polymer and a non-diene polymer are preferred. . Furthermore, the rubbery polymer (a) may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

  Examples of the diene polymer include homopolymers such as polybutadiene and polyisoprene; styrene / butadiene copolymer rubbers; styrene / isoprene copolymer rubbers; natural rubbers and the like. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The said diene polymer can be used individually by 1 type or in combination of 2 or more types.

  Examples of the non-diene polymer include ethylene units and ethylene / α-olefin copolymer rubbers containing units derived from α-olefins having 3 or more carbon atoms; urethane rubbers; acrylic rubbers; silicone rubbers. A silicone-acrylic composite rubber; a polymer obtained by hydrogenating a (co) polymer containing a monomer unit derived from a conjugated diene compound (however, the hydrogenation rate is usually 50% or more), etc. Is mentioned. These copolymers may be block copolymers or random copolymers. The said non-diene polymer can be used individually by 1 type or in combination of 2 or more types.

  The rubbery polymer (a) is preferably a diene polymer and a hydrogenated product thereof, an acrylic rubber, and an ethylene / α-olefin copolymer rubber.

  The shape of the rubbery polymer (a) used for forming the rubber-reinforced styrene resin (A12) is not particularly limited, but when it is particulate, the weight average particle diameter is preferably 100 to 2,000 nm. More preferably, it is 200 to 1,000 nm. If the weight average particle diameter is in the above range, the foamed molded article obtained by using the thermoplastic resin composition for foam molding of the present invention is excellent in molding processability and impact resistance. Moreover, it is excellent also in impact resistance at the time of forming the laminated product of this invention. The weight average particle diameter can be measured by an image analysis method using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

  When the rubbery polymer (a) is in the form of particles, as long as the weight average particle diameter is within the above range, for example, JP-A-61-233010, JP-A-59-93701, JP The thing enlarged by the well-known method described in 56-167704 gazette etc. can also be used.

  As a method for producing the rubbery polymer (a), emulsion polymerization is preferable in consideration of adjustment of the average particle diameter and the like. In this case, the average particle size can be adjusted by selecting the production conditions such as the type of emulsifier and the amount used, the type and amount of initiator used, the polymerization time, the polymerization temperature, and the stirring conditions. Further, as another method for adjusting the average particle size (particle size distribution), a method of blending two or more of the rubbery polymers (a) having different particle sizes may be used.

  The vinyl monomer (b2) used for forming the rubber-reinforced styrene resin (A12) may be only an aromatic vinyl compound, and this aromatic vinyl compound, for example, a vinyl cyanide compound, ( A combination of a copolymerizable compound with an aromatic vinyl compound such as a (meth) acrylic acid ester compound, a maleimide compound, or an acid anhydride may also be used.

  As said aromatic vinyl compound, the compound illustrated as an aromatic vinyl compound used for formation of the said styrene-type (co) polymer (A11) can be used individually by 1 type or in combination of 2 or more types. Of these, styrene and α-methylstyrene are preferred.

  As said vinyl cyanide compound, the compound illustrated as a vinyl cyanide compound used for formation of the said styrene-type (co) polymer (A11) can be used individually by 1 type or in combination of 2 or more types. Of these, acrylonitrile is preferred.

  Moreover, also about said (meth) acrylic acid ester compound, a maleimide type compound, an acid anhydride, etc., the compound used for formation of the said styrene type (co) polymer (A11) is single 1 type, or 2 or more types. Can be used in combination.

  The vinyl monomer (b2) is preferably used in combination of one or more aromatic vinyl compounds and one or more compounds copolymerizable with the aromatic vinyl compounds. The mass ratio of the group vinyl compound and the other compounds is usually 45 to 97% by mass and 3 to 55% by mass, preferably 50 to 95% by mass, when the total of these is 100% by mass. It is 5-50 mass%. If the ratio of the aromatic vinyl compound is too small, the moldability tends to be inferior, and the shape stability of the resulting foam-molded product may be inferior. On the other hand, if the ratio is too large, the resulting foamed molded product may not have sufficient chemical resistance, heat resistance, and the like.

The vinyl monomer (b2) is preferably a combination of an aromatic vinyl compound and a vinyl cyanide compound, and an aromatic vinyl compound, a vinyl cyanide compound and other compounds ((meth) acrylic ester compounds Etc.). By using the vinyl cyanide compound, the physical properties balance such as chemical resistance and heat resistance is improved in the obtained foamed molded article.
In the vinyl monomer (b1) and the vinyl monomer (b2), the constituent components and the proportions thereof may be the same or different.

  The rubber-reinforced styrene resin (A12) can be produced by polymerizing the vinyl monomer (b2) in the presence of the rubber polymer (a). As the polymerization method, emulsion polymerization, solution polymerization, bulk polymerization, and bulk-suspension polymerization are preferable.

  In the production of the rubber-reinforced styrene resin (A12), the rubber polymer (a) and the vinyl monomer (b2) are added in the reaction system in the total amount of the rubber polymer (a). In the presence of, the vinyl monomer (b2) may be added all at once to initiate the polymerization, or the polymerization may be carried out in portions or continuously. Further, in the presence or absence of part of the rubber polymer (a), the vinyl monomer (b2) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, the remainder of the rubbery polymer (a) may be added in a batch, divided or continuously during the reaction.

  When producing 100 parts by mass of the rubber-reinforced styrene resin (A12), the amount of the rubbery polymer (a) used is usually 5 to 80 parts by mass. Moreover, the usage-amount of the said vinylic monomer (b2) is 25-1,900 mass parts normally with respect to 100 mass parts of said rubbery polymers (a).

  When the rubber-reinforced styrene resin (A12) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As said polymerization initiator, the compound illustrated by description of the manufacturing method of the said styrene-type (co) polymer (A11) can be used individually by 1 type or in combination of 2 or more types. The usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b2) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (b2).
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b2) whole quantity.

Emulsion polymerization can be carried out under known conditions according to the type of vinyl monomer (b2), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. As this coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.
In addition, when making the said styrene resin (A1) contain 2 or more types of rubber reinforcement | strengthening styrene resin (A12), after isolating resin from each latex, you may mix, but as another method There is a method of coagulating a latex mixture containing each resin.

  As a method for producing the rubber-reinforced styrene resin (A12) by solution polymerization, bulk polymerization, and bulk-suspension polymerization, known methods can be applied.

  The graft ratio of the rubber-reinforced styrene resin (A12) is usually 10 to 200% by mass, preferably 15 to 150% by mass. If it exists in the said range, it is excellent in the surface external appearance property and impact resistance of the foaming molding obtained.

Here, the graft ratio is insoluble when x-gram of rubbery polymer (a) in 1 gram of rubber-reinforced styrene resin (A12) and 1 gram of rubber-reinforced styrene resin (A12) are dissolved in acetone. It is a value obtained by the following equation when the minute is a y-gram. However, when the rubber polymer (a) is an acrylic rubber, acetonitrile is used instead of acetone.
Graft ratio (mass%) = {(y−x) / x} × 100

  In addition, the intrinsic viscosity [η] of a component soluble in acetone of the rubber-reinforced styrene resin (A12) (provided that acetonitrile is used when the rubbery polymer (a) is an acrylic rubber). (Measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g. When this intrinsic viscosity [η] is within the above range, the shape stability and impact resistance of the obtained foamed molded article are excellent.

  The graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiator, chain transfer agent, emulsifier, solvent, etc. used when producing the rubber-reinforced styrene resin (A12), and further the polymerization time, It can be easily controlled by adjusting the polymerization temperature and the like.

  The styrenic resin (A1) is preferably one or more of styrene-based (co) polymer (A11), one or more of rubber-reinforced styrene-based resin (A12), and styrenic (co) polymer ( A combination of one or more of A11) and one or more of rubber-reinforced styrene-based resin (A12).

  The content of the styrene resin (A1) in the component [A] is 5 to 100% by mass, preferably 30 to 100% by mass, more preferably 100% by mass when the component [A] is 100% by mass. 60-100 mass%, More preferably, it is 80-100 mass%, Most preferably, it is 90-100 mass%. When the content of the styrenic resin (A1) is in the above range, the foamed molded article having a high foaming ratio is excellent in foamability and fine dispersibility, the foamed cells are uniform, and the shape stability is excellent.

The said component [A] can contain another thermoplastic resin further as needed.
The amount of the other thermoplastic resin used is usually 0 to 95% by mass, preferably 0 to 70% by mass, more preferably 0 to 40% by mass, further preferably 100% by mass when the component [A] is 100% by mass. Is 0 to 20% by mass, particularly preferably 0 to 10% by mass.
The other thermoplastic resin is not particularly limited as long as it is a thermoplastic resin, and one or more of (meth) acrylic ester compounds such as polycarbonate resin (PC) and polymethyl methacrylate (PMMA) are used. Acrylic resins such as (co) polymers; vinyl chloride resins; polyamide resins (PA); polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; olefin resins; ionomers Ethylene copolymers such as ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer; polyacetal resin (POM); polyarylate resin; polyphenylene ether; polyphenylene sulfide; polytetrafluoroethylene, polyvinylidene fluoride, etc. Fluorine Fatty; Liquid crystal polymer; Imide resin; Ketone resin; Sulfone resin; Urethane resin; Polyvinyl acetate; Polyethylene oxide; Polyvinyl alcohol; Polyvinyl ether; Polyvinyl butyral; Phenoxy resin; It is done. These can be used alone or in combination of two or more. Of these, polycarbonate resins, polyester resins, thermoplastic elastomers, olefin resins, acrylic resins, vinyl chloride resins and bio-based polymers are preferred, and polycarbonate resins, polyester resins, acrylic resins and vinyl chloride polymers are preferred. A resin is more preferable.

Examples of the vinyl chloride resin include vinyl chloride homopolymer (polyvinyl chloride); polyvinylidene chloride; copolymers of vinyl chloride and other monomers copolymerizable therewith. Such other monomers include ethylene, propylene, butene, 1-pentene, butadiene, styrene, α-methylstyrene, acrylonitrile, vinylidene chloride, vinylidene cyanide, alkyl vinyl ethers, carboxylic acid vinyl esters, aryl ethers, dialkyl malees. Examples include acids, fumaric acid esters, N-vinyl pyrrolidone, vinyl pyridine, and vinyl silane.
The average degree of polymerization is usually 500 to 8,000.

  In the thermoplastic resin composition for foam molding of the present invention, when the component [A] is composed of the styrene resin (A1) and a vinyl chloride resin, the content of the vinyl chloride resin in the component [A] Is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 40% by mass, when the component [A] is 100% by mass. If the content of the vinyl chloride resin is in the above range, a foamed molded article having a high expansion ratio, uniform foamed cells and excellent molded appearance can be obtained.

1-2. Fibrous filler [B]
This component [B] is a fibrous filler having an aspect ratio of 5 to 50 and an average particle diameter of 3 to 50 μm. The aspect ratio is preferably 10-25. When the aspect ratio is in the range of 5 to 50, it is possible to easily obtain a foam molded product having excellent mechanical strength, a small linear expansion coefficient, and excellent dimensional stability. The average particle size is preferably 3 to 40 μm, more preferably 4 to 40 μm. When the average particle size is in the range of 3 to 50 μm, it is possible to obtain a foam molded article having excellent mechanical strength, a small linear expansion coefficient, and excellent dimensional stability.

As said component [B], glass fiber, PAN (polyacrylonitrile) type carbon fiber, pitch type carbon fiber, stainless steel, aluminum, titanium, copper, brass and other metal inorganic fibers, silica fiber, silica / alumina fiber, Zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, aluminum borate whisker, basic magnesium sulfate whisker, wollastonite, zonotolite, and organic materials such as polyamide, fluororesin and acrylic resin Examples thereof include fibrous fillers. Of these, wollastonite, carbon fiber, potassium titanate whisker and polyamide are preferable, and wollastonite is particularly preferable.
All of these are preferably in the form of chopped strands obtained by twisting a plurality of long fibers having a small diameter and converging them with a sizing agent.

  The glass fiber is obtained by spinning a general C glass or E glass.

Examples of the glass fiber sizing agent include epoxy resins, acrylic resins, and AS (acrylonitrile / styrene copolymer) resins. The coating amount of the sizing agent is preferably 0.5 to 10% by mass, more preferably 0.1 to 6% by mass, and particularly preferably 0.5 to 5% by mass in terms of solid content with respect to the glass fiber. It is. When the application amount of the sizing agent is too small, it is easy to defibrate and handling at the time of compounding is difficult. On the other hand, if it is too much, the heat resistance is lowered and molding defects such as silver are caused.
Moreover, in order to make the said glass fiber and these convergence agents adhere | attach efficiently, you may use a silane coupling agent together. This silane coupling agent also has a function of converging glass fibers. A known compound can be used as the silane coupling agent. The usage-amount of the said silane coupling agent is 0.01-20 mass% normally with respect to a sizing agent.

The PAN-based carbon fiber is a fiber obtained by baking polyacrylonitrile as a raw material. A preferable tensile elastic modulus is 100 to 700 GPa, more preferably 200 to 500 GPa.
The pitch-based carbon fiber is a fiber obtained by spinning a pitch as a raw material and heat-treating it. A preferred tensile modulus is 10 to 900 GPa, more preferably 30 to 600 GPa.
With respect to the PAN-based carbon fiber and the pitch-based carbon fiber, when the fiber diameter is in the above range, the effect of improving dimensional stability and rigidity is greatly preferable. When the fiber diameter is too small, the carbon fiber is easily broken at the time of compounding, and the above effect is reduced.
The PAN-based carbon fiber and the pitch-based carbon fiber are usually used after being converged by a sizing agent. The amount of the sizing agent used is preferably 0.5 to 10% by mass in terms of solid content with respect to the fiber. When the application amount of the sizing agent is too small, it is easy to defibrate and handling at the time of compounding is difficult. On the other hand, if it is too much, the heat resistance is lowered and molding defects such as silver are caused.
Furthermore, the surface of the PAN-based carbon fiber and the pitch-based carbon fiber may be coated with a metal or the like.

The wollastonite is a compound having a composition of CaSiO ₃ (CaO · SiO ₂ ), and either a natural product or a synthetic product may be used.
As this wollastonite, the one whose surface is surface-treated with a silane coupling agent, a titanate coupling agent or the like can be used.

  Content of the said component [B] contained in the composition of this invention is 5-150 mass parts when the quantity of the said thermoplastic resin [A] is 100 mass parts, Preferably it is 10-120. Part by mass, more preferably 10 to 80 parts by mass. When the content of the component [B] is in the above range, a foam molded article having excellent mechanical strength, a small linear expansion coefficient, and excellent dimensional stability can be obtained.

1-3. Foaming agent [C]
This component [C] is not particularly limited as long as it contains a compound having a boiling point (atmospheric pressure) of −10 ° C. to 55 ° C. Examples of the compound include aliphatic hydrocarbons having 3 to 6 carbon atoms, and n-butane, isobutane, n-pentane and isopentane are particularly preferable. These may be included singly or in combination of two or more. When these are used, it is excellent in foamability and the fine dispersibility of a foam cell. The content of the compound having a boiling point (atmospheric pressure) of −10 ° C. to 55 ° C. is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably with respect to 100% by mass of the component [C]. Is 95 to 100% by mass.
In addition, when the said component [C] contains a some component, it is preferable that the average value of a boiling point (atmospheric pressure) is -10 degreeC-55 degreeC.

When the above component [C] contains other components, hydrocarbon compounds such as ethane, cyclopentane, n-hexane, cyclohexane, etc .; methyl chloride, ethyl chloride, dichloroethane, chloroform, fluoromethane, difluoromethane, trifluoromethane, And halogenated hydrocarbons such as difluoroethane, trifluoroethane, fluorochloromethane, fluorochloroethane, dichlorodifluoromethane, and the like. These can be used alone or in combination of two or more.
The component [C] may also contain petroleum ether, carbon dioxide gas, nitrogen gas, etc., which are compounds containing oxygen atoms. The content of other components is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 0 to 5% by mass with respect to 100% by mass of the component [C].

  In the thermoplastic resin composition for foam molding of the present invention, the content of the component [C] is 0.1 to 5 parts by mass when the amount of the thermoplastic resin [A] is 100 parts by mass. , Preferably it is 0.2-4 mass parts, More preferably, it is 0.3-3 mass parts. By being in the said range, with the thermoplastic resin composition for foam molding of the present invention, a foam molded article having a high expansion ratio and a uniform cell diameter can be obtained.

1-4. Additive The thermoplastic resin composition for foam molding of the present invention may contain an additive depending on the purpose and application. These additives include foaming aids, fillers, heat stabilizers, antioxidants, UV absorbers, anti-aging agents, antistatic agents, plasticizers, lubricants, flame retardants, antibacterial agents, antifouling agents, and coloring agents. , Fluorescent brighteners, fluorescent dyes and the like.

Examples of the foaming aid include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons such as ethylene dichloride, trichloroethylene, and tetrachloroethylene; organic solvents such as esters such as ethyl acetate and butyl acetate. Can be mentioned. This foaming aid is used in combination with the above components [A] and [C] when n-propane, n-butane, isobutane, n-pentane, isopentane, cyclohexane or the like is used as the component [C]. Compatibility can be improved.
Content of the said foaming adjuvant is 0.1-2 mass parts normally with respect to 100 mass parts of said components [C].

Examples of the filler include talc, mica, clay, calcium carbonate, silica, alumina, glass beads, glass balloons, glass flakes, carbon flakes, carbon balun, carbon beads, carbon black, graphite, pulp, chaff, paper sludge, etc. Is mentioned. These can be used alone or in combination of two or more.
Content of the said filler is 0.1-5 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the heat stabilizer include phosphites, hindered phenols, thioethers, and the like. These can be used alone or in combination of two or more.
Content of the said heat stabilizer is 0.01-2 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
Content of the said antioxidant is 0.01-2 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more. Moreover, it may be preferable to use together with hindered amines.
Content of the said ultraviolet absorber is 0.05-2 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds. Thiobisphenol compound, hindered phenol compound, phosphite compound, imidazole compound, nickel dithiocarbamate salt compound, phosphate compound and the like. These can be used alone or in combination of two or more.
Content of the said anti-aging agent is 0.01-2 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the antistatic agent include a low molecular weight antistatic agent and a high molecular weight antistatic agent. Moreover, these may be an ion conduction type or an electron conduction type.
The low molecular weight antistatic agent includes an anionic antistatic agent; a cationic antistatic agent; a nonionic antistatic agent; an amphoteric antistatic agent; a complex compound; a metal alkoxide such as alkoxysilane, alkoxytitanium, alkoxyzirconium, and the like. Derivatives thereof: coated silica, phosphate, phosphate ester and the like. These can be used alone or in combination of two or more.
Examples of the polymer antistatic agent include vinyl copolymers having a sulfonic acid metal salt in the molecule, alkyl sulfonic acid metal salts, alkyl benzene sulfonic acid metal salts, and betaines. Furthermore, a polyamide elastomer, a polyester elastomer, etc. can also be used. These can be used alone or in combination of two or more.
The content of the antistatic agent is usually 0.1 to 5 parts by mass when the amount of the component [A] is 100 parts by mass.

Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; dimethyl adipate , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octy Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like. These can be used alone or in combination of two or more.
Content of the said plasticizer is 0.5-5 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the lubricant include fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, aliphatic Examples include alcohol, polyhydric alcohol, polyglycol, polyglycerol, metal soap, silicone, and modified silicone. These can be used alone or in combination of two or more.
Content of the said lubricant is 0.2-5 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.
Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tripentyl phosphate Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus flame retardants such as phosphazene derivatives containing phosphorus element and nitrogen element; polytetrafluoroethylene, guanidine salts, silicone compounds, phosphazene compounds, and the like. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate. These can be used alone or in combination of two or more.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used alone or in combination of two or more.

Content of the said flame retardant is 0.5-30 mass parts normally, when the quantity of the said component [A] is 100 mass parts.
In addition, when making the thermoplastic resin composition for foam molding of this invention contain a flame retardant, it is preferable to use a flame retardant adjuvant. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples thereof include ammonium polyphosphate, tin oxide, and iron oxide. These can be used alone or in combination of two or more.

Examples of the antibacterial agent include zeolite antibacterial agents such as silver zeolite and silver-zinc zeolite, silica gel antibacterial agents such as complexed silver-silica gel, glass antibacterial agents, calcium phosphate antibacterial agents, and zirconium phosphate antibacterial agents. Silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents, etc .; formaldehyde releasing agents, halogenated aromatic compounds, road Organic antibacterial agents such as propargyl derivatives, thiocyanato compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compounds; Organic hybrid antibacterial agent; natural Bacteria, and the like. These can be used alone or in combination of two or more.
Content of the said antibacterial agent is 0.1-5 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

As the colorant, any of inorganic pigments, organic pigments, and dyes may be used. Moreover, you may use combining these.
Content of the said coloring agent is 0.0005-10 mass parts normally, when the quantity of the said component [A] is 100 mass parts.

1-5. Thermoplastic resin composition for foam molding The thermoplastic resin composition for foam molding of the present invention contains the above-mentioned components [A], [B] and [C], but the form is not particularly limited. . For example, it may be in the form of a pellet or the like containing all of the above components [A], [B] and [C], or a pellet containing the above components [A] and [C], and the above components A mixture containing [B], a part of the above component [A], a pellet containing the above component [B], etc., the remainder of the above component [A], and a pellet containing the above component [C] It may be in the form of a mixture, etc.
In the present invention, the thermoplastic resin (hereinafter referred to as “resin (AX)”) corresponding to 5 to 50% by mass of the thermoplastic resin [A] and the fibrous filler [B]. The fibrous filler corresponding to 0 to 50% by mass (hereinafter referred to as “fibrous filler (BX)”) and the blowing agent corresponding to 50 to 100% by mass of the foaming agent [C] ( Hereinafter, a composition [X] containing “a foaming agent (CX)”) and a thermoplastic resin (hereinafter referred to as “resin”) corresponding to 50 to 95% by mass of the thermoplastic resin [A]. (AY) "), a fibrous filler corresponding to 50 to 100% by mass of the fibrous filler [B] (hereinafter referred to as" fibrous filler (BY) "), and the above. A foaming agent corresponding to 0 to 50% by mass of the foaming agent [C] (hereinafter referred to as “foaming agent (CY)”). .) And is preferably a mixture of a composition containing [Y] a. The thermoplastic resin [A] is composed of the resin (AX) and the resin (AY), and the fibrous filler [B] is composed of the fibrous filler (BX) and the fibrous filler (BY). The foaming agent [C] is composed of the foaming agent (CX) and the foaming agent (CY). Further, both the composition [X] and the composition [Y] can be composed of one or more kinds.

The resin (AX) contained in the composition [X] is preferably a styrene (co) polymer (A11) and / or a rubber-reinforced styrene resin (A12), more preferably a styrene. A (co) polymer (A11), and a mixture of a styrene-based (co) polymer (A11) and a rubber-reinforced styrene-based resin (A12), more preferably a styrene-based (co) polymer (A11). When the resin (AX) is composed of the above components, it is possible to obtain a foam-molded product having a high foaming ratio and further excellent foamability, fine dispersibility of foamed cells, and molded appearance.
When the resin (AX) is composed of a styrene-based (co) polymer (A11) and / or a rubber-reinforced styrene-based resin (A12), the polymer component excluding the rubbery polymer is When the total amount of monomer units constituting this polymer component is 100% by mass, the monomer units derived from the aromatic vinyl compound are 75 to 95% by mass, and the single unit derived from the vinyl cyanide compound It is preferable that a body unit is 5-25 mass%, and another monomer unit is 0-20 mass%. Further preferable ratios are 80 to 87 mass%, 13 to 20 mass%, and 0 to 12 mass%, respectively. When the content of each monomer unit is in the above range, it is possible to obtain a foam-molded product having a high expansion ratio, and having excellent foamability, fine dispersibility of foamed cells, and molded appearance. The polymer component excluding the rubber polymer can be an acetone-soluble component obtained by immersing the resin (AX) in acetone.
The content of the styrene-based (co) polymer (A11) contained in the resin (AX) and / or the styrene-based resin (A1) composed of the rubber-reinforced styrene-based resin (A12) is the same as that of the resin (AX). Is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass. Within this range, it is possible to obtain a foamed molded article having a high foaming ratio and having excellent foamability, fine dispersion of foamed cells, and molded appearance.
The content of the monomer unit constituting the styrene resin (A1) contained in the resin (AX) is the styrene (co) polymer (A11) in which the type and content ratio of the monomer unit are known. ) And / or the rubber-reinforced styrene-based resin (A12), and the amount of the monomer unit can be adjusted by appropriately adjusting the amount of use.
In addition, the structure of the acetone soluble component obtained by immersing the styrene resin contained in the composition [X] in acetone is derived from the aromatic vinyl compound when the whole is 100% by mass. The monomer unit, the monomer unit derived from the vinyl cyanide compound, and the monomer unit derived from another compound are preferably 75 to 95% by mass, 5 to 25% by mass, and 0 to 20%, respectively. It is 80 mass%, More preferably, it is 80-87 mass%, 13-20 mass%, and 0-12 mass%. When the composition of the acetone-soluble component is within the above range, it is suitable for forming a foam molded product having excellent mechanical strength, a small linear expansion coefficient, excellent dimensional stability, and excellent surface appearance.
When the styrene resin (A1) used for the composition [X] is only the styrene (co) polymer (A11), the composition [X] is obtained by immersing in acetone. The obtained acetone-soluble component is analyzed by a known method, and the monomer unit amount of the styrene-based (co) polymer (A11) can be verified based on the result.

The resin (AY) contained in the composition [Y] is preferably composed of a styrene resin (A1), or a styrene resin (A1) and another thermoplastic resin. The styrene resin (A1) is preferably the styrene (co) polymer (A11) and / or the rubber reinforced styrene resin (A12), more preferably the rubber reinforced styrene resin (A12). Or a mixture of a styrene-based (co) polymer (A11) and a rubber-reinforced styrene-based resin (A12).
As the other thermoplastic resin, a vinyl chloride resin is particularly preferable. In the case of using a vinyl chloride resin, the content ratio of the styrene resin (A1) and the vinyl chloride resin is preferably 0 when the total of these is 100% by mass in order to obtain the use effect. It is -80 mass% and 20-100 mass%, More preferably, it is 0-50 mass% and 50-100 mass%. In addition, the usage-amount of the said vinyl chloride-type resin is selected within the range of the prescribed amount of the other thermoplastic resin contained in the thermoplastic resin composition for foam molding of this invention.
In addition, the said description is applied as it is to the kind of monomer unit which originates in a vinyl-type monomer which comprises the said styrene-type (co) polymer (A11). In addition, each content of this vinyl monomer unit is a monomer unit derived from an aromatic vinyl compound, a monomer unit derived from a vinyl cyanide compound, and other monomers included as necessary. When the total content of all monomer units is 100% by mass, the units are preferably 50 to 97% by mass, 3 to 50% by mass, and 0 to 47% by mass, more preferably 55 to 95%, respectively. Mass%, 5-45 mass% and 0-15 mass%. Furthermore, the preferable Mw of the styrene-based (co) polymer (A11) is 100,000 to 300,000, more preferably 100,000 to 270,000, still more preferably 120,000 to 250,000. is there.
The rubber polymer (a) constituting the rubber-reinforced styrene resin (A12) is a diene polymer and / or a non-diene polymer, and the content thereof is a rubber-reinforced styrene resin (A12). ) It is usually 5 to 80% by mass with respect to 100% by mass. Furthermore, in the rubber-reinforced styrene resin (A12), the type of monomer unit derived from the vinyl monomer constituting the polymer component excluding the rubber polymer (a) is the vinyl monomer ( The explanation in b2) is applied as it is. And the content of these vinyl-type monomer units is the monomer unit derived from an aromatic vinyl compound, and the monomer unit derived from the compound other than that made the sum total 100 mass%. In this case, they are usually 45 to 97% by mass and 3 to 55% by mass, preferably 50 to 95% by mass and 5 to 50% by mass, respectively.

Moreover, the preferable structure for obtaining a foaming molded article with a high expansion ratio and excellent appearance is shown below. The mass ratio of the resin (AX) contained in the composition [X] and the resin (AY) contained in the composition [Y] is 5 to 50% by mass and 50%, respectively, as described above. It is -95 mass%, More preferably, it is 7-45 mass% and 55-93 mass%, More preferably, it is 10-40 mass% and 60-90 mass%.
The mass ratio of the fibrous filler (BX) contained in the composition [X] and the fibrous filler (BY) contained in the composition [Y] is 0 as described above. It is -50 mass% and 50-100 mass%, More preferably, it is 0-20 mass% and 80-100 mass%, More preferably, it is 0-10 mass% and 90-100 mass%.
Moreover, the mass ratio of the foaming agent (CX) contained in the said composition [X] and the foaming agent (CY) contained in the said composition [Y] is 50-100 respectively as mentioned above. They are mass% and 0-50 mass%, More preferably, they are 70-100 mass% and 0-30 mass%, More preferably, they are 90-100 mass% and 0-10 mass%.
By preparing compositions [X] and [Y] in the above range and mixing these compositions into a thermoplastic resin composition for foam molding, the expansion ratio is as high as 2 times or more, and the surface It is possible to easily obtain a foam molded product having excellent appearance.

A particularly preferred combination of the above compositions [X] and [Y] is that the composition [X] has the constitution of the acetone soluble component in the resin (AX), and the mass ratio of the fibrous filler (BX). Is a foaming agent-containing composition in which the mass ratio of the foaming agent (CX) is 0 to 10% by mass with respect to the entire fibrous filler, and the composition is 100% by mass with respect to the entire foaming agent. The product [Y] is made of the styrene resin (A1) or the styrene resin (A1) and other thermoplastic resin (vinyl chloride resin) in the resin (AY), and the fibrous filler (BY) A mass ratio is 90-100 mass% with respect to the whole fibrous filler, and it is an aspect which is a foaming agent-free composition which does not contain a foaming agent. The composition [X] is preferably a granular foaming agent-containing masterbatch melt-kneaded by heating, and the foaming ratio is preferably 1.15 or less, more preferably 1.10 or less. is there. On the other hand, the composition [Y] is preferably a molten mixture not containing the foaming agent [C]. When the resin (AY) contains another thermoplastic resin, preferably the total amount of the styrene-based resin (A1) constituting the resin (AY) and a part or the total amount of the fibrous filler (BY), It is also possible to use a mixture of a molten mixture made of the above and a composition comprising the other thermoplastic resin and the balance of the fibrous filler (BY) (if necessary) as the composition [Y].
The above compositions [X] and [Y] are exemplified by the foaming aids, fillers, heat stabilizers, antioxidants, UV inhibitors, antiaging agents, antistatic agents, plasticizers, Additives such as lubricants, flame retardants, antibacterial agents, antifouling agents, colorants, fluorescent brighteners, fluorescent dyes may be included.

  The shape and size of the foaming agent-containing masterbatch are not particularly limited, and the shape may be, for example, a flat shape (circular, rectangular, etc.), a columnar shape (cylinder, rectangular column, etc.), a linear shape, an indefinite shape, or the like. it can.

  The foaming agent-containing master batch as the composition [X] can be produced by blending and kneading the foaming agent [C] while keeping the resin (AX) in a molten state. (AX) is a step of melt-kneading (hereinafter referred to as “melting step”), the resin (AX) in the molten state obtained by the melting step, the component [C], or the component [C] and foaming A step of supplying an auxiliary agent and melt-kneading the mixture (hereinafter referred to as “kneading step”), a step of cooling the linear body immediately after making the kneaded product obtained by the kneading step into a linear body or the like , “Cooling step”) and a step of cutting the cooled linear body (hereinafter referred to as “cutting step”) can be manufactured by a manufacturing method that sequentially proceeds.

In the melting step, the resin (AX) is melt-kneaded at a melting temperature or higher using an extruder such as a single-screw extruder, a twin-screw extruder, or a tandem extruder.
Thereafter, in the kneading step, the extruder used in the melting step or the above-exemplified extruder prepared separately is used, and the component liquefied in the molten resin (AX) [ C] or the liquefied component [C] and the foaming aid are supplied and usually melt-kneaded at a temperature equal to or higher than the melting temperature of the resin (AX).

Next, in the cooling step, the kneaded product obtained in the kneading step is extruded from an extrusion hole having a diameter of 1 to 5 mm, for example, disposed at the exit of the extruder to form a continuous linear body or the like. To do. Then, the extruded linear body is introduced into a coolant such as water and cooled.
Then, the foamed agent containing masterbatch of a desired magnitude | size can be manufactured by cut | disconnecting the cooled linear body to suitable length.

On the other hand, the shape and size of the molten mixture are not particularly limited, and the shape is, for example, powdery, spherical, substantially spherical, flat (circular, square, etc.), columnar (cylinder, prism, etc.), linear, indefinite. It can be a shape or the like.
This molten mixture can be manufactured by applying a manufacturing method of pellets or the like using a known thermoplastic resin composition.

  The thermoplastic resin composition for foam molding of the present invention can produce foam-molded articles having various shapes by an extrusion molding method, an injection molding method, a vacuum molding method, a pressure molding method, or the like. In any case, it is possible to produce a foam molded article having a high expansion ratio of 2 to 25 times and excellent surface appearance.

2. Foam Molded Article The foam molded article of the present invention is obtained by using the above thermoplastic resin composition for foam molding of the present invention. The foam molded article of the present invention is obtained by extruding the thermoplastic resin composition for foam molding of the present invention. In extrusion molding, the foamed thermoplastic resin composition of the present invention is usually melted and extruded from a die to be foamed at the same time, plate-like (sheet-like), cylindrical, semi-cylindrical, linear, etc. The molded product is obtained.
The foamed molded article of the present invention has uniform foamed cells and is excellent in surface appearance. Further, the expansion ratio (by the calculation method shown in the examples) is preferably 2 to 25 times, more preferably 2 to 20 times. The density is preferably 40 to 500 kg / m ³ , more preferably 50 to 400 kg / m ³ . Further, the linear expansion coefficient in the temperature range of −20 ° C. to 60 ° C. is preferably 5.5 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 5.0 × 10 ⁻⁵ (1 / ° C.), and shrinkage The ratio is small and dimensional stability is excellent. In the foamed molded article of the present invention, the aspect ratio of the component [B] contained is preferably 5 to 50, more preferably 5 to 30. Since the aspect ratio is in the above range, the molding appearance, mechanical strength and dimensional stability are excellent.

In the above extrusion molding method, when the thermoplastic resin composition for foam molding of the present invention is heated and melted, an extruder equipped with a screw or the like is used. The heating condition is usually the above component [A]. It is selected according to the type.
The heating temperature is preferably 130 ° C to 260 ° C.
When the said component [A] consists of a styrene resin (A1) and a vinyl chloride resin, heating temperature becomes like this. Preferably it is 120 to 200 degreeC.

  The method for producing the foam molded article of the present invention is preferably a method using a thermoplastic resin composition for foam molding containing the above-mentioned compositions [X] and [Y]. According to this production method, the kneadability of the above compositions [X] and [Y] is improved, and the moldability is improved. Moreover, it is excellent in foamability and fine dispersibility, and in particular, a foam molded product having a high foaming ratio, uniform foamed cells, and excellent molded appearance without dusting can be obtained.

  After obtaining a kneaded product of the above compositions [X] and [Y], an extrusion molding method can be applied to produce a foam molded product. By this method, the foaming ratio can be as high as 2 to 25 times, and a foamed molded product having a dense skin layer that hardly ruptures and does not wipe off the surface is obtained, and the appearance is excellent. A similar molded product can be obtained by applying other molding methods such as injection molding, vacuum molding, and pressure molding.

  Foam molded products of the present invention include civil engineering and construction related materials such as display boards; interior and exterior materials for vehicles; electrical and electronic parts; sports equipment; walls, floors, frames, furniture (desk drawers, top plates, etc.), Cosmetic sheets, partitions, lattices, fences, gutters, sizing boards, carports, terraces, decks, bathroom components (counters, doors, apron, UB frames, window frames, shelves, etc.), kitchen components (doors, dividers, windows) It can be used as housing / office interior and exterior materials such as frames, shelves, etc .; toys; cushioning materials such as game machines, reinforcing materials, heat insulating materials, core materials, substitute plywood, and the like.

  Furthermore, the foamed molded product of the present invention can be used as an article formed by being integrated with another molded product, a member, or the like depending on applications, and can be applied to the above applications.

3. Laminated product The laminated product of the present invention comprises a molded part (V) (hereinafter referred to as "foamed molded part (V)") obtained by using the thermoplastic resin composition for foam molding of the present invention, and other parts. A member (W) made of a material is laminated.
The laminated product of the present invention is suitable for the same use as the foamed molded product of the present invention. The shape can be the same as that of the molded product of the present invention.

  The foam molded part (V) has uniform foam cells and is excellent in surface appearance. The expansion ratio of the foamed molded part (V) is preferably 2 to 25 times, more preferably 2 to 20 times.

The other material constituting the member (W) may be the thermoplastic resin composition for foam molding of the present invention as long as it is different from the constituent components, the expansion ratio, etc., and is not particularly limited, but is composed of a resin (composition). And those made of other organic materials and those made of inorganic materials.
The resin (composition) may be a thermoplastic resin (composition) or a cured resin (composition). The thermoplastic resin contained in the thermoplastic resin (composition) is selected depending on the use of the laminated product of the present invention, but the component [A] contained in the thermoplastic resin composition for foam molding of the present invention described above. May be the same or different. Moreover, this thermoplastic resin (composition) may contain the foaming agent, and does not need to contain it.
Examples of the inorganic material include metals, alloys, oxides, carbides, nitrides, and metal salts.
In the laminated product of the present invention, the number of layers of the member (W) may be one layer, two layers, or three or more layers. Moreover, the said member (W) may be provided on both surfaces of the said foaming molding part (V) (refer FIG. 3). Another preferable material is a thermoplastic resin (composition).

The laminated product 1a of FIG. 1 is a cross-sectional view showing that the foam molded part (V) 11 is laminated above the member (W) 12, and the thicknesses of both are the same. The thicknesses of the foam molded part (V) 11 and the member (W) 12 are selected depending on the purpose, application, and the like. The foam molded part (V) 11 may be thicker than the member (W) 12, or vice versa. Further, the foam molded part (V) 11 may be provided on the entire surface of the member (W) 12 or may be provided only on a part thereof. Preferable thicknesses of the foam molded part (V) 11 and the member (W) 12 are 1 to 25 mm and 0.1 to 5 mm, respectively.
As a method for producing the laminated product 1a, the foamed molded part (V) 11 is formed using the thermoplastic resin composition for foam molding of the present invention, and then the separately produced member (W) 12 is disposed. Method: A method of co-extrusion using the thermoplastic resin composition for foam molding of the present invention and a thermoplastic resin (composition) that forms the member (W) 12; The method of arrange | positioning the foaming molding part (V) 11 obtained using the thermoplastic resin composition for foam molding of the said invention on the surface of W) 12 is mentioned.

Moreover, the laminated product 1b of FIG. 2 is sectional drawing which shows that the member (W) 12 is laminated | stacked above the foaming molding part (V) 11. The member (W) 12 may be on the entire surface of the foam-molded part (V) or may be only partly. The thicknesses of the foam molded part (V) 11 and the member (W) 12 are selected depending on the purpose, application, and the like. The foam molded part (V) 11 may be thicker than the member (W) 12, or vice versa. Moreover, it may be the same as shown in FIG. Further, the laminated product may have a uniform thickness or a partially different thickness. For example, the preferred thicknesses of the foamed molded part (V) 11 and the member (W) 12 are 1 to 25 mm and 0.1 to 5 mm, respectively.
The manufacturing method of the laminated product 1b can be the same as the manufacturing method of the laminated product 1a.

Further, the laminated product of the present invention may be a laminated product 1c having a cross-sectional structure as shown in FIG. That is, the laminated product 1c in FIG. 3 includes foam molded portions (V) 11a and 11b on both surfaces of the member (W) 12. The thickness of each member is selected depending on the purpose, application, and the like, but preferably in the order of the foam-molded portions (V) 11a and 11b and the member (W) 12, preferably 1 to 25 mm, 1 to 25 mm, and 0. 1-5 mm.
As a manufacturing method of said laminated product 1c, using the thermoplastic resin composition for foam molding of the said invention and the thermoplastic resin (composition) which will form the said member (W) 12, it is common. Examples of the method include extrusion.

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

1. Raw material components Components used in the following Examples and Comparative Examples are shown.

1-1. Thermoplastic resin A
(1) Acrylonitrile / styrene copolymer (A-1)
It is a copolymer having a styrene unit amount of 79% and an acrylonitrile unit amount of 21%, and Mw is 160,000.
(2) Acrylonitrile / styrene copolymer (A-2)
It is a copolymer having a styrene unit amount of 84% and an acrylonitrile unit amount of 16%, and Mw is 150,000.
(3) Acrylonitrile / styrene copolymer (A-3)
The copolymer has a styrene unit amount of 70% and an acrylonitrile unit amount of 30%, and Mw is 200,000.
(4) ABS resin (A-4)
It is an ABS resin obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a polybutadiene rubber having a volume average particle diameter of 280 nm and a toluene insoluble content of 80%. The graft ratio of this ABS resin is 55%, the amount of polybutadiene rubber is 51%, the amount of styrene units is 35%, and the amount of acrylonitrile units is 14%.

(5) ASA resin (A-5)
This is a rubber-reinforced styrene resin obtained by emulsion polymerization of styrene and acrylonitrile in the presence of acrylic rubber which is a copolymer of 99% n-butyl acrylate and 1% allyl methacrylate. This rubber-reinforced styrene resin has a graft ratio of 60%, an acrylic rubber amount of 50.8%, a styrene unit amount of 36.4%, and an acrylonitrile unit amount of 12.8%.
(6) Vinyl chloride resin (A-6)
“Vinica PVC SG1300” (trade name) manufactured by Vitec Co., Ltd. was used.

1-2. Fibrous filler B
(1) Wollastonite (B-1)
Wollastonite “SH-800” (product number) manufactured by Kinsei Matech Co., Ltd. was used. The aspect ratio is 20, and the average particle size is 6.5 μm.
(2) Wollastonite (B-2)
Wollastonite having an aspect ratio of 3 and an average particle diameter of 2.5 μm was used.

1-3. Foaming agent C
Butane (boiling point at atmospheric pressure—0.5 ° C.) was used.

1-4. Chemical foaming agent D
An endothermic decomposition type foaming agent (trade name “SELBON SC-P”, manufactured by Eiwa Kasei Co., Ltd.) whose main component is sodium hydrogen carbonate was used.

1-5. Other raw materials (1) Extrudability improver (E-1)
An ultrahigh molecular weight acrylonitrile / styrene resin having an intrinsic viscosity [η] (30 ° C., dimethylformamide) of 2.4 dl / g, Mw / Mn of 6.8, and an acrylonitrile unit amount of 23% was used.
(2) Lubricant (E-2)
Magnesium stearate (trade name “MAGNIC-GR”, manufactured by NOF Corporation) was used.
(3) Lubricant (E-3)
Low molecular weight polyethylene wax (trade name “Sun Wax 171-P”, manufactured by Sanyo Chemical Industries, Ltd.) was used.

2. Manufacture of composition [X] (foaming agent-containing masterbatch) (1) Manufacture of composition X-1 Into a single screw extruder with a screw diameter of 40 mm and a cylinder temperature set to 170 ° C. to 250 ° C., acrylonitrile / styrene copolymer 100 parts of combined (A-1) was supplied and melted. Thereafter, 4.5 parts of the foaming agent C was supplied from the injection port at the rear of the extruder and melt-kneaded.
Next, the strand is extruded through a 5-hole (2.5 mmφ / hole) die disposed at the outlet of the extruder, cooled and then cut to form a cylindrical foam having an outer diameter of about 2 mm and a length of 3 mm. An agent-containing master batch (X-1) was obtained.

When the foaming agent content and the expansion ratio in the foaming agent-containing master batch (X-1) were measured by the following method, the composition of the foaming agent-containing master batch (X-1) was as shown in Table 1. Got.
[Butane content measurement method]
About 10 g of the foaming agent-containing master batch was placed on a 200 ° C. hot plate, heated for 5 minutes, the mass before and after heating was precisely weighed, and the difference was defined as the butane content.
[Foaming ratio]
The mass calculated value W1 was calculated from the bulk volume and the specific gravity of the resin obtained from the external dimensions of the foaming agent-containing masterbatch, and the ratio between the W1 and the actually measured mass value W2 was defined as the expansion ratio.
Foaming magnification (times) = W1 / W2
The density of the resin used for the calculation is acrylonitrile / styrene copolymer; 1.08 g / cm ³ .

Moreover, the shaping | molding external appearance property of the said foaming agent containing masterbatch (X-1) was observed visually, and the following reference | standard determined. The results are also shown in Table 1.
○: The surface was smooth.
X: The surface was like a sponge.

(2) Production of Compositions X-2 to X-4 Except that the thermoplastic resin A (A-2 to A-3) and the foaming agent C were used in the proportions shown in Table 1, respectively, the same as above. The foaming agent-containing master batches (X-2) to (X-3) were manufactured and subjected to various evaluations. The results are shown in Table 1.
Moreover, the masterbatch pellet (X-4) which consists only of styrene resin (A-1) which does not contain the foaming agent C was manufactured similarly (refer Table 1).

3. Production of Composition [Y] (Melted Mixture Pellet) (1) Production of Composition Y-1 According to the formulation shown in Table 2, 29 parts of acrylonitrile / styrene copolymer (A-3) and ABS resin (A- 4) 31 parts and 40 parts of wollastonite (B-1) are put into a Henschel mixer and mixed, and the cylinder temperature is set to 170 ° C. to 250 ° C. and supplied to a single screw extruder with a screw diameter of 40 mm. This was melt kneaded. Thereafter, the strand is extruded through a 5-hole (2.5 mmφ / hole) die disposed at the outlet of the extruder, cooled, and then cut to form a cylindrical melt having an outer diameter of about 2 mm and a length of 3 mm. A mixture pellet (Y-1) was obtained (see Table 2).

(2) Production of Composition Y-2 An outer diameter was obtained in the same manner as in the molten mixture pellet (Y-1) except that the ASA resin (A-5) was used instead of the ABS resin (A-4). A cylindrical molten mixture pellet (Y-2) having a length of about 2 mm and a length of 3 mm was obtained (see Table 2).

(3) Production of composition Y-3 Except for using wollastonite (B-2) instead of wollastonite (B-1), the same as the above molten mixture pellet (Y-1), A cylindrical molten mixture pellet (Y-3) having an outer diameter of about 2 mm and a length of 3 mm was obtained (see Table 2).

(4) Production of Composition Y-4 Except that the wollastonite (B-1) was not blended, a circle with an outer diameter of about 2 mm and a length of 3 mm was obtained in the same manner as the molten mixture pellet (Y-1). Columnar molten mixture pellets (Y-4) were obtained (see Table 2).

(5) Production of composition Y-5 37.5 parts of the above molten mixture pellet (Y-1) and 62.5 parts of vinyl chloride resin (A-6) were mixed at room temperature for 2 minutes with a Henschel mixer, A pellet mixture (Y-5) was obtained.

4). Production and Evaluation of Thermoplastic Resin Composition for Foam Molding and Foam Molded Product Example 1
25 parts of the foaming agent-containing master batch (X-1) and 75 parts of the molten mixture pellet (Y-1) were mixed for 2 minutes with a Henschel mixer to obtain a thermoplastic resin composition for foam molding. Then, it was put into an extruder equipped with a screw (“FS50-22 type”, manufactured by Ikekai Co., Ltd.) and melt-kneaded at 200 ° C. Next, the foam molded product having a width of 55 mm and a thickness of 5.0 mm was discharged from the outlet where the sizing die was disposed in the T die. The expansion ratio of the foamed molded product according to the following calculation method is 3.5 times. The foamed molded product has a length of 80 mm, a width of 55 mm, and a thickness of 5.0 mm (hereinafter referred to as “test piece”). Got.
[Foaming ratio calculation method]
The mass calculated value W1 was calculated from the bulk volume and the density of the resin and the fibrous filler obtained from the external dimensions of the foamed molded product, and the ratio between the W1 and the mass measured value W2 was defined as the expansion ratio.
Foaming magnification (times) = W1 / W2

Moreover, the following evaluation was performed about the obtained foaming molding. The results are shown in Table 3.
(1) Molding appearance property The appearance of the test piece was visually observed and judged according to the following criteria.
A: There was no distortion and the surface was smooth.
◯: Although there was no distortion, minute irregularities were observed on a part of the surface.
Δ: Slight distortion was obtained, and minute irregularities were observed on a part of the surface.
X: There was distortion, and minute irregularities were observed on almost the entire surface.

(2) Linear Expansion Coefficient In the above extrusion molding, a T-die was replaced with a die capable of forming a linear molded product having a square cross section (15 mm × 15 mm) to obtain a prismatic foam molded product. The length was cut to 100 mm, and this was used as a test piece for measuring the linear expansion coefficient.
The test piece was left for 60 minutes in a thermostat at -20 ° C., the length at -20 ° C. The _{(L 1),} was measured by a micrometer. Next, the same test piece was left in a constant temperature bath at 60 ° C. for 60 minutes, and the length (L ₂ ) at 60 ° C. was measured. The linear expansion coefficient was calculated by the following formula using the above length (L ₁ ) and length (L ₂ ).
Linear expansion coefficient (1 / ° C.) = (L ₂ −L ₁ ) / (L ₁ × 80)

Examples 2-5
According to the formulation shown in Table 3, a foamed molded article was produced and evaluated in the same manner as in Example 1 using a foaming agent-containing master batch and a molten mixture pellet. The results are shown in Table 3.

Example 6
According to the formulation shown in Table 3, a foamed molded product was produced and evaluated in the same manner as in Example 1 using 20 parts of the foaming agent-containing master batch (X-1) and 80 parts of the pellet mixture (Y-5). did. The results are shown in Table 3. In Table 3, instead of the pellet mixture (Y-5), the composition (Y-1) and the resin (A-6) constituting the mixture are shown.

Example 7
23 parts of acrylonitrile / styrene copolymer (A-1), 22 parts of acrylonitrile / styrene copolymer (A-3), 23 parts of ABS resin (A-4), and wollastonite (B-1) 30 Part, 1.2 parts of extrudability improver (E-1), 0.8 part of lubricant (E-2) and 0.4 part of lubricant (E-3) are mixed with a Henschel mixer, and the screw is It was put into an extruder (“FS50-22 type”, manufactured by Ikegai Co., Ltd.) and melt kneaded at 200 ° C. Thereafter, 2 parts of the foaming agent C was supplied from the injection port at the rear part of the extruder and melt-kneaded. Next, the foamed molded product having a width of 55 mm and a thickness of 5.0 mm was discharged from the outlet where the sizing die was disposed in the T die, and a foaming agent-containing thermoplastic resin body was obtained. Using this foaming agent-containing thermoplastic resin body, foamed molded articles were produced and evaluated in the same manner as in Example 1. The results are shown in Table 3.

Comparative Examples 1-2
According to the formulation shown in Table 3, a foamed molded article was produced and evaluated in the same manner as in Example 1 using a foaming agent-containing master batch and a molten mixture pellet. The results are shown in Table 3.

Comparative Example 3
According to the formulation shown in Table 3, the same procedure as in Example 1 except that 24 parts of the foaming agent-free master batch (X-4), 75 parts of the molten mixture pellet (Y-1) and 1 part of the foaming agent D were used. A foamed molded product was produced. In addition, since this foaming agent D foams during the production, the composition [X] cannot be produced in the same manner as the foaming agent C. Manufactured.
The evaluation results of the foam molded product are shown in Table 3.

As is clear from Table 3, Comparative Example 1 was an example using a resin composition that did not contain a fibrous filler, and had a large linear expansion coefficient. Comparative Example 2 was an example using a fibrous filler whose aspect ratio and average particle size were outside the scope of the present invention, and had a large linear expansion coefficient. Moreover, the comparative example 3 is an example using the resin composition containing the chemical foaming agent which is not the foaming agent which concerns on this invention, and the expansion ratio was low and the surface appearance property was inferior.
On the other hand, Examples 1-6 are examples of the foam-molded article obtained from the resin composition within the scope of the present invention, and had the target performance of the present invention.

5). Manufacture of laminated product Example 8
[1] The thermoplastic resin composition for foam molding obtained in Example 1 and [2] styrenic resin (A-4) are used as a surface material and a base material, respectively, and the following coextrusion Under the conditions, a laminated product having a thickness of 1.5 mm and 3.5 mm (the surface material was a foam molded part) was obtained.
<Extrusion conditions>
[1] Surface material layer: 20 mm extruder, 160 ° C. (extrusion temperature), 40 rpm (screw rotation speed), 0.8 m / min (take-off speed)
[2] Base material layer: 40 mm extruder, 190 ° C. (extrusion temperature), 20 rpm (screw rotation speed), 0.8 m / min (take-off speed)

  The thermoplastic resin composition for foam molding of the present invention comprises, by extrusion molding or the like, civil engineering / construction related materials such as display boards; interior / exterior materials for vehicles; daily miscellaneous goods such as containers and trays; electrical / electronic parts; Sporting goods; Walls, floors, frames, furniture, decorative sheets, partitions, lattices, fences, rain gutters, sizing boards, carports and other housing / office interior and exterior materials; Toys; It is suitable for forming a foam molded article suitable for a heat insulating material, a core material, a substitute plywood and the like.

It is the schematic which shows an example of the cross-section of the laminated product (laminated sheet etc.) of this invention. It is the schematic which shows the other example of the cross-section of the laminated product (laminated sheet etc.) of this invention. It is the schematic which shows the other example of the cross-section of the laminated product (laminated sheet etc.) of this invention.

Explanation of symbols

1a, 1b and 1c; Laminated products 11, 11a and 11b; Foam molded part (V)
12; Member (W)

Claims (12)

[A] a thermoplastic resin containing 5 to 100% by mass of a styrene resin (A1) when the total is 100% by mass; [B] an aspect ratio of 5 to 50 and an average particle size of 3 to 50 μm A foaming thermoplastic resin composition comprising: a fibrous filler that is [C], and a foaming agent comprising a compound having a boiling point of -10 ° C to 55 ° C.
The content of the fibrous filler [B] is 5 to 150 parts by mass with respect to 100 parts by mass of the thermoplastic resin [A], and
Content of the said foaming agent [C] is 0.1-5 mass parts with respect to 100 mass parts of said thermoplastic resins [A], The thermoplastic resin composition for foam molding characterized by the above-mentioned.   The thermoplastic resin composition for foam molding according to claim 1, wherein the fibrous filler [B] is wollastonite.   The thermoplastic resin corresponding to 5 to 50% by mass of the thermoplastic resin [A], the fibrous filler corresponding to 0 to 50% by mass of the fibrous filler [B], and the foam A composition [X] containing a foaming agent corresponding to 50 to 100% by mass of the agent [C], and a thermoplastic resin corresponding to 50 to 95% by mass of the thermoplastic resin [A]. And a fibrous filler corresponding to 50 to 100% by mass of the fibrous filler [B] and a foaming agent corresponding to 0 to 50% by mass of the foaming agent [C]. The thermoplastic resin composition for foam molding according to claim 1 or 2, which is a mixture of the composition [Y].   The thermoplastic resin composition for foam molding according to claim 3, wherein the composition [X] is a foaming agent-containing masterbatch having an expansion ratio of 1.15 or less.   The thermoplastic resin composition for foam molding according to claim 3 or 4, wherein the composition [Y] is a melt-kneaded product containing no foaming agent [C].   When the acetone-soluble component obtained by immersing the styrene-based resin (A1) contained in the composition [X] in acetone is 100% by mass as a whole, a single amount composed of an aromatic vinyl compound The body unit is composed of 75 to 95 mass%, the monomer unit composed of vinyl cyanide compound is 5 to 25 mass%, and the monomer unit composed of another compound is 0 to 20 mass%. The thermoplastic resin composition for foam molding according to any one of the above.   The styrenic resin (A1) is aromatic in the presence of a styrenic copolymer and / or a rubbery polymer using a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound. The thermoplastic resin composition for foam molding according to any one of claims 1 to 6, comprising a rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing a vinyl compound and a vinyl cyanide compound.   A foam molded article obtained by using the thermoplastic resin composition for foam molding according to any one of claims 1 to 7.   A foam-molded article obtained by extruding the thermoplastic resin composition for foam molding according to any one of claims 1 to 7.   The foamed molded product according to claim 8 or 9, wherein the expansion ratio is 2 to 25 times. The foamed molded product according to any one of claims 8 to 10, wherein the linear expansion coefficient is 5.5 x ^10-5 (1 / ° C) or less.   A molded part (V) obtained by using the thermoplastic resin composition for foam molding according to any one of claims 1 to 7 and a member (W) made of another material are laminated. Laminated product.

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