JP2008150476A - Thermoplastic resin composition for expansion molding, expansion-molded article and laminated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for expansion molding, suitable for molding an expansion-molded article having a high foaming magnitude and excellent in molded appearance, the expansion-molded article and a laminated article. <P>SOLUTION: This thermoplastic resin composition for expansion molding comprises [A] in the case of setting the total of the whole monomer units as 100 mass%, a thermoplastic resin consisting of 75 to 95 mass% unit consisting of an aromatic vinyl compound, 5 to 25 mass% unit consisting of a vinyl cyanide-based compound and 0 to 20 mass% unit consisting of another vinyl-based compound, and also containing a styrene-based resin having 100,000 to 300,000 weight-average molecular weight, and [B] a blowing agent. The content of [B] the blowing agent is 2.5 to 10 pts.mass based on the 100 pts.mass styrene-based resin, and the content of the styrene-based resin is 5 to 100 mass% based on the 100 mass% [A] thermoplastic resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic resin composition for foam molding containing a thermoplastic resin and a foaming agent, a foam molded article and a laminated article using the composition, and more specifically, formation of a foam molded article having a high expansion ratio. The present invention relates to a thermoplastic resin composition for foam molding, a foam molded product, and a laminate.

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, particularly, foam molding using a resin composition containing a resin and a foaming agent has been widely applied.
As resins for compositions used for foam molding, Patent Documents 1 to 5 include rubber-reinforced styrene resins such as ABS resin and ASA resin, polystyrene, styrene / methacrylic acid copolymer, acrylonitrile / styrene copolymer. Further, styrene resins such as high impact polystyrene, olefin resins, polyester resins and the like are disclosed.

  Patent Documents 6 to 8 disclose compositions containing a rubber-reinforced styrene resin such as an ABS resin and a chemical foaming agent. Furthermore, Patent Document 9 discloses a composition containing a masterbatch composed of an ethylene / (meth) acrylic acid (ester) copolymer and a chemical foaming agent, and a thermoplastic resin such as an olefin resin. .

JP 59-221340 JP-A-6-32932 JP-A-6-298893 JP-A-7-314438 JP-A-9-221562 JP 2000-212355 A JP 2004-18686 JP 2004-51875 A JP 2004-285345 A

According to the compositions disclosed in the above Patent Documents 6 to 9, the foaming ratio is high and the molding is caused by the decomposition residue of the foaming agent, the contamination of the die, the die disposed in the extruder, etc. In some cases, a foam-molded product having excellent appearance cannot be obtained.
An object of the present invention is to provide a thermoplastic resin composition for foam molding, a foam molded product, and a laminated product suitable for forming a foam molded product having a high expansion ratio and excellent molded appearance.

The present invention is shown below.
1. [A] When the total of all the monomer units is 100% by mass, the monomer unit composed of an aromatic vinyl compound is 75 to 95% by mass, and the monomer unit composed of a vinyl cyanide compound is 5 to 25% by mass. And a thermoplastic resin containing a styrene resin (A1) comprising 0 to 20% by mass of monomer units composed of other vinyl compounds and having a weight average molecular weight of 100,000 to 300,000, and [B A foaming thermoplastic resin composition containing a foaming agent, wherein the content of the foaming agent [B] is 2.5 to 10 parts per 100 parts by mass of the styrenic resin (A1). The thermoplastic resin for foam molding, characterized in that the content of the styrene resin (A1) is 5 to 100% by mass with respect to 100% by mass of the thermoplastic resin [A]. Resin composition.
2. The thermoplastic resin [A] is at least one selected from a styrene resin (A3) excluding the styrene resin (A1), a polycarbonate resin, an acrylic resin, and a vinyl chloride resin, and the styrene resin ( The thermoplastic resin composition for foam molding as described in 1 above, comprising A1).
3. The thermoplastic resin composition for foam molding as described in 1 above, wherein [D] monomer units of an aromatic vinyl compound are 75 to 95 masses when the total of all monomer units is 100 mass%. %, 5 to 25% by weight of monomer units composed of vinyl cyanide compound and 0 to 20% by weight of monomer units composed of other vinyl compounds, and has a weight average molecular weight of 100,000 to 300,000. Styrene-based resin (A1) and a foaming agent [B], and the content of the foaming agent [B] is 2.5 to 10 parts by mass with respect to 100 parts by mass of the styrene-based resin (A1). And (E) a thermoplastic resin [C] (excluding the styrene resin (A1)) and a thermoplastic resin body containing no foaming agent. Heatable for foam molding characterized by RESIN composition.
4). 4. The thermoplastic resin composition for foam molding according to any one of 1 to 3, wherein the foaming agent [B] contains a compound having an average boiling point of −10 ° C. to 55 ° C.
5. The thermoplastic resin composition for foam molding according to 3 or 4 above, wherein the thermoplastic resin [C] includes at least one selected from the group consisting of a styrene resin (A3), a polycarbonate resin, an acrylic resin, and a vinyl chloride resin. object.
6). 6. The thermoplastic resin composition for foam molding as described in 2 or 5 above, wherein the styrene resin (A3) contains a styrene rubber reinforced resin.
7). The styrene rubber reinforced resin is a resin obtained by polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, and the styrene rubber reinforced resin is acetone. When the sum of the total amount of the monomer units constituting the soluble component or the acetonitrile-soluble component is 100% by mass, the ratio of the total amount of the monomer units made of the vinyl cyanide compound is 25 to 35 mass. The thermoplastic resin composition for foam molding according to the above 6, which is%.
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. A molded part (X) obtained by using the thermoplastic resin composition for foam molding according to any one of 1 to 7 above and a member (Y) made of another material are laminated. Laminated product.

The thermoplastic resin composition for foam molding according to the present invention is suitable for forming a foam molded product having a high expansion ratio and excellent molded appearance. When the average value of the boiling point of the foaming agent [B] is −10 ° C. to 55 ° C., the foaming property and the fine dispersibility are excellent, especially the foaming ratio is high, the foamed cells are uniform, and the molded appearance It is suitable for forming a foamed molded product having excellent properties.
When the thermoplastic resin [A] contains at least one selected from styrene resin (A3), polycarbonate resin, acrylic resin and vinyl chloride resin, and styrene resin (A1), foaming is performed. It is suitable for forming a foamed molded article having a high magnification and excellent molded appearance.
The styrene resin (A3) is a styrene rubber reinforced resin, and the styrene rubber reinforced resin polymerizes a monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. When the sum of the total amount of monomer units constituting the acetone-soluble component or the acetonitrile-soluble component of the styrene rubber-reinforced resin is 100% by mass, the vinyl cyanide compound is obtained. When the ratio of the total amount of the monomer units is 25 to 35% by mass, the foamed cell is further uniform, has excellent shape stability, and has excellent chemical resistance. be able to.
The foamed molded article of the present invention has uniform foamed cells, excellent shape stability, and excellent shape stability even when the expansion ratio is as high as 2 times or more.
The laminated product of the present invention is excellent in shape stability, and is excellent in shape stability even if it has a molded part (X) having a high expansion ratio of 2 times or more.

  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] a monomer unit comprising an aromatic vinyl compound when the total of all monomer units is 100% by mass. 75 to 95% by mass, 5 to 25% by mass of monomer units made of vinyl cyanide compound, and 0 to 20% by mass of monomer units made of other vinyl compounds, and has a weight average molecular weight of 100,000. A thermoplastic resin (hereinafter also referred to as “component [A]”) containing styrene resin (A1) of ˜300,000, and [B] a foaming agent (hereinafter also referred to as “component [B]”). And the content of the foaming agent [B] is 2.5 to 10 parts by mass with respect to 100 parts by mass of the styrenic resin (A1). And content of the styrenic resin (A1) Is 5 to 100% by mass with respect to 100% by mass of the thermoplastic resin [A].

1-1. Thermoplastic resin [A]
This component [A] is composed of 75 to 95% by mass of a monomer unit made of an aromatic vinyl compound and 5% of a monomer unit made of a vinyl cyanide compound when the total of all monomer units is 100% by mass. Styrenic resin (A1) which consists of 0-20 mass% of monomer units consisting of ˜25 mass% and other vinyl compounds and has a weight average molecular weight of 100,000-300,000 is included. The content of the styrene resin (A1) is usually 5 to 100% by mass, preferably 10 to 90% by mass, and more preferably 15 to 80% by mass with respect to the component [A]. Therefore, the component [A] preferably contains a styrene resin (A1) and another thermoplastic resin (hereinafter also referred to as “thermoplastic resin (A2)”).

1-1-1. Styrene resin (A1)
The styrene resin (A1) is a monomer unit made of an aromatic vinyl compound (hereinafter referred to as “unit (a1)”) 75 to 95 when the total of all monomer units is 100% by mass. 5% to 25% by mass of a monomer unit composed of a vinyl cyanide compound (hereinafter referred to as “unit (a2)”) and a monomer unit composed of another vinyl compound (hereinafter referred to as “unit (a3)”) It is a resin comprising 0 to 20% by mass and having a weight average molecular weight of 100,000 to 300,000.

  The aromatic vinyl compound that forms the unit (a1) 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.

  Examples of the vinyl cyanide compound that forms the unit (a2) 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 other vinyl compounds that form the unit (a3) include (meth) acrylic acid ester compounds, maleimide compounds, and acid anhydrides. Other than these, a vinyl compound having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used.

  Examples of the (meth) acrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate. Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl 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 for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized 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 methacrylate, 2-hydroxyethyl acrylate, hydroxystyrene, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N-diethyl-p-aminomethylstyrene, glycidyl methacrylate, glycidyl acrylate, 3,4-oxycyclohexyl methacrylate, acrylic Examples include acid 3,4-oxycyclohexyl, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide, acrylamide, methacrylic acid, acrylic acid, and vinyl oxazoline. These can be used alone or in combination of two or more.

  Specific examples of the styrenic resin (A1) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, and acrylonitrile / styrene / N-phenylmaleimide copolymer. A polymer etc. are mentioned. These can be used alone or in combination of two or more.

  The proportions of the units (a1), (a2) and (a3) constituting the styrene resin (A1) are 75 to 95% by mass, 5 to 25% by mass and 0 to 20% by mass, respectively. Yes, preferably 78-90 mass%, 10-22 mass% and 0-15 mass%, more preferably 80-87 mass%, 13-20 mass% and 0-12 mass%. When the styrenic resin (A1) has the above-described configuration, a foamed molded article having excellent chemical resistance and a high foaming ratio can be obtained from the thermoplastic resin composition for foam molding of the present invention.

  The styrene resin (A1) can be produced by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and other vinyl compounds in the presence or absence of a polymerization initiator. 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 and the like, and a reducing agent such as a sugar-containing pyrophosphate formulation and 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 monomer whole quantity.

  In the production of the styrenic resin (A1), the polymerization may be started in a state where the whole amount of the monomer is accommodated in the reaction system, and arbitrarily selected monomer components are added in portions or continuously. Polymerization may be performed by adding. Furthermore, when using the said polymerization initiator, it can add to a reaction system collectively or continuously.

  The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC) of the styrenic resin (A1) is 100,000 to 300,000, preferably 100,000 to 270,000, more preferably 120,000-250,000. When the Mw is within this range, the content of the foaming agent [B] 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.

  In the thermoplastic resin composition for foam molding of the present invention, the content of the styrene resin (A1) in the component [A] is as described above, and when the component [A] is 100% by mass, It is 5-100 mass%, Preferably it is 10-90 mass%, More preferably, it is 15-80 mass%. If the content of the styrenic resin (A1) is in the above range, it is excellent in foamability and fine dispersibility, in particular, the formation of a foam-molded product having a high foaming ratio, uniform foamed cells and excellent molded appearance. It is suitable for.

1-1-2. Other thermoplastic resins (A2)
The thermoplastic resin (A2) has thermoplasticity and is not particularly limited as long as it is a thermoplastic resin excluding the styrene resin (A1). The styrene resin (A3) excluding the styrene resin (A1). ); Polycarbonate resin (PC); acrylic resin such as (co) polymer using one or more of (meth) acrylic acid ester compounds such as polymethyl methacrylate (PMMA); polyvinyl chloride, ethylene / vinyl chloride Polymers, vinyl chloride resins such as polyvinylidene chloride; polyamide resins (PA); polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate; olefin resins; ionomers, ethylene Ethylene-based copolymers such as vinyl acetate copolymer and ethylene / vinyl alcohol copolymer Polyacetal resin (POM); Polyarylate resin; Polyphenylene ether; Polyphenylene sulfide; Fluorine resin such as polytetrafluoroethylene and polyvinylidene fluoride; Liquid crystal polymer; Imide resin; Ketone resin; Sulfone resin; Urethane resin Polyvinyl acetate, polyethylene oxide, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, phenoxy resin, photosensitive resin, biodegradable plastic, and the like. These can be used alone or in combination of two or more. Of these, styrene resin (A3), polycarbonate resin, acrylic resin, and vinyl chloride resin are preferable.

  Examples of the styrenic resin (A3) include polystyrene, styrene / maleic anhydride copolymer, styrene / (meth) acrylic acid ester copolymer, and the like other than the styrenic resin (A1). Styrene (co) polymers such as acrylonitrile copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, acrylonitrile / styrene / N-phenylmaleimide copolymer (hereinafter “ Styrene (co) polymer (A31) ")); styrene rubber obtained by polymerizing aromatic vinyl compound in the presence of rubber polymer such as ABS resin, AES resin, ASA resin, etc. Examples thereof include reinforced resins (hereinafter referred to as “styrene-based resin (A32)”). Among these, it is preferable that a styrene rubber reinforced resin (styrene resin (A32)) is included. You may combine said styrene-type (co) polymer (A31) and styrene-type resin (A32).

The styrene resin (A32) is an aromatic vinyl compound or the like (hereinafter referred to as “vinyl monomer (q1)” in the presence of a rubber polymer (hereinafter referred to as “rubber polymer (p)”). Is a resin containing a rubber-reinforced vinyl resin obtained by polymerizing.
The styrene resin (A32) may be the rubber-reinforced vinyl resin, or the styrene / acrylonitrile copolymer, acrylonitrile / α-excluding the rubber-reinforced vinyl resin and the styrene resin (A1). It may be a mixture with a styrene (co) polymer (A21) such as a methylstyrene copolymer, an acrylonitrile / styrene / methyl methacrylate copolymer, an acrylonitrile / styrene / N-phenylmaleimide copolymer.

  The rubber polymer (p) may be a homopolymer or a copolymer as long as it is rubbery at room temperature, but it may be a diene polymer (diene rubber polymer). And non-diene polymers (non-diene rubber polymers) are preferred. Furthermore, the rubbery polymer (p) 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 (diene rubber 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.

  The non-diene polymer (non-diene rubber polymer) is an ethylene / α-olefin copolymer rubber containing an ethylene unit and a unit comprising an α-olefin having 3 or more carbon atoms; Examples include rubbers, acrylic rubbers, silicone rubbers, silicone / acrylic IPN rubbers, and polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The said non-diene polymer can be used individually by 1 type or in combination of 2 or more types.

  The rubber-reinforced vinyl resin obtained when a diene polymer is used as the rubber polymer (p) is a diene rubber-reinforced vinyl resin, and is generally referred to as “ABS resin”. The rubber-reinforced vinyl resin obtained when ethylene / α-olefin and / or ethylene / α-olefin / non-conjugated diene copolymer is used as the rubbery polymer (p) is generally “AES”. It is said to be “resin”. Furthermore, the rubber-reinforced vinyl resin obtained when acrylic rubber is used as the rubbery polymer (p) is an acrylic rubber-reinforced vinyl resin and is generally referred to as “ASA resin”.

  The shape of the rubbery polymer (p) used for forming the rubber-reinforced vinyl resin is not particularly limited, but when it is particulate, the weight average particle diameter is preferably 100 to 2,000 nm, more preferably. 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. 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 (p) 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 (p), emulsion polymerization is preferred 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. Moreover, as another adjustment method of the said average particle diameter (particle diameter distribution), the method of blending 2 or more types of the said rubber-like polymer (p) which has a different particle diameter may be sufficient.

The vinyl monomer (q1) used for the formation of the vinyl rubber polymer contains an aromatic vinyl compound. The vinyl monomer (q1) may be only an aromatic vinyl compound, and the aromatic vinyl compound and, for example, a vinyl cyanide compound, a (meth) acrylic acid ester compound, a maleimide compound, an acid anhydride It may be a combination of a compound copolymerizable with an aromatic vinyl compound such as a product. The compounds copolymerizable with the above aromatic vinyl compound can be used singly or in combination of two or more.
Accordingly, as the vinyl monomer (q1), the monomer (q11) comprising at least one aromatic vinyl compound, or at least one aromatic vinyl compound, and the aromatic vinyl compound and A monomer (q12) obtained by combining at least one copolymerizable compound can be used.

  As said aromatic vinyl compound, the compound illustrated as an aromatic vinyl compound used for formation of the said styrene resin (A1) 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 resin (A1) 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 resin (A1) is used individually by 1 type or in combination of 2 or more types. be able to.

  The vinyl monomer (q1) includes one or more aromatic vinyl compounds and a combination of one or more compounds copolymerizable with the aromatic vinyl compound, that is, the monomer (q12). In this case, the mass ratio between the aromatic vinyl compound and the other compound is usually (2-95) mass% / (98-5), assuming that the total of these is 100 mass%. ) Mass%, preferably (10 to 90) mass% / (90 to 10) mass%. If the ratio of the aromatic vinyl compound is too small, molding processability tends to be inferior. If it is too large, the resulting molded article may not have sufficient chemical resistance, heat resistance, and the like.

  The monomer (q12) is preferably a combination of an aromatic vinyl compound and a vinyl cyanide compound (hereinafter referred to as “monomer (q121)”), an aromatic vinyl compound, and a vinyl cyanide compound. And other compounds (such as (meth) acrylic acid ester compounds) (hereinafter referred to as “monomer (q122)”). By using a vinyl cyanide compound, the balance of physical properties such as chemical resistance and heat resistance is improved.

The rubber-reinforced vinyl resin is obtained by polymerizing the vinyl monomer (q1) in the presence of the rubber polymer (p), and is exemplified below.
[1] One or more rubber-reinforced vinyl resins obtained using only the monomer (q11) as the vinyl monomer (q1).
[2] One or more rubber-reinforced vinyl resins obtained by using only the monomer (q121) as the vinyl monomer (q1).
[3] One or more rubber-reinforced vinyl resins obtained using only the monomer (q122) as the vinyl monomer (q1).
As the rubber-reinforced vinyl resin, the above embodiments [2] and [3] are preferable. Further, two or three of these modes [1], [2] and [3] may be used.

  The rubber-reinforced vinyl resin can be produced by polymerizing the vinyl monomer (q1) in the presence of the rubber polymer (p). As the polymerization method, emulsion polymerization, solution polymerization, bulk polymerization, and bulk-suspension polymerization are preferable.

  In the production of the rubber-reinforced vinyl resin, the rubber polymer (p) and the vinyl monomer (q1) are present in the reaction system in the presence of the total amount of the rubber polymer (p). In addition, the above-mentioned vinyl monomer (q1) may be added all at once to initiate the polymerization, or the polymerization may be carried out while being divided or continuously added. Further, in the presence or absence of a part of the rubber polymer (p), the vinyl monomer (q1) 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 rubber polymer (p) may be added in a batch, divided or continuously during the reaction.

  When producing 100 parts by mass of the rubber-reinforced vinyl resin, the amount of the rubbery polymer (p) used is usually 5 to 80 parts by mass. Moreover, the usage-amount of the said vinylic monomer (q1) is 25-1,900 mass parts normally with respect to 100 mass parts of said rubber-like polymers (p).

  In the case of producing a rubber-reinforced vinyl resin 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 resin (A1) 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 (q1) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, and other mercaptans; 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 (q1).
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 (q1) whole quantity.

Emulsion polymerization can be performed on well-known conditions according to kinds, such as a vinyl-type monomer (q1) and a polymerization initiator. 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. Examples of the coagulant include 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.
In addition, when making the rubber reinforced resin containing two or more kinds of the above rubber reinforced vinyl resins, the resins may be mixed after being isolated from each latex. There are methods such as coagulating a mixture of latex.

  A known method can be applied to the method for producing the rubber-reinforced vinyl resin by solution polymerization, bulk polymerization, and bulk-suspension polymerization.

  The graft ratio of the rubber-reinforced vinyl resin is usually 10 to 200% by mass, preferably 15 to 150% by mass. If the graft ratio is less than 10% by mass, the foamability of the thermoplastic resin composition for foam molding of the present invention is excellent in workability, and the surface appearance and impact resistance of the resulting foam-molded product are excellent.

Here, the graft ratio means x grams of the rubbery polymer (p) in 1 gram of the rubber reinforced vinyl resin, and y is an insoluble content when 1 gram of the rubber reinforced vinyl resin is dissolved in acetone. It is a value obtained by the following formula when expressed in grams. However, when the rubbery polymer (p) is an acrylic rubber, acetonitrile is used instead of acetone.
Graft ratio (mass%) = {(y−x) / x} × 100

  In addition, the intrinsic viscosity [η] (in methyl ethyl ketone) of a component soluble in acetone of the rubber-reinforced vinyl resin (however, acetonitrile is used when the rubber polymer (p) is an acrylic rubber). , Measured at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g. When the intrinsic viscosity [η] is within the above range, the molding processability is excellent, and the resulting molded article is excellent in impact resistance.

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

  The rubber-reinforced vinyl resin obtained by polymerizing the vinyl monomer (q1) in the presence of the rubbery polymer (p) by applying the above method is usually a vinyl monomer (q1). ) Includes a grafted rubbery polymer that is graft-polymerized to the rubbery polymer (p), but depending on the production conditions, a free, vinyl-based monomer that is not grafted to the rubbery polymer (p) It may further contain a (co) polymer of the body (q1). The weight average molecular weight of this (co) polymer is usually from 50,000 to 400,000, but a part or all of the weight average molecular weight is “when the total of all monomer units is 100% by mass. It consists of 75 to 95% by mass of monomer units composed of a vinyl group compound, 5 to 25% by mass of monomer units composed of a vinyl cyanide compound, and 0 to 20% by mass of monomer units composed of other vinyl compounds, And if it has a property that a weight average molecular weight is 100,000-300,000, the mass part shall be contained in the said styrene resin (A1).

  In the thermoplastic resin composition for foam molding of the present invention, when the thermoplastic resin (A2) is a styrenic resin (A32), that is, the component [A] is the styrenic resin (A1) and ( When it consists of A32), content of the styrene resin (A32) in the said component [A] is 10-90 mass% when the said component [A] is 100 mass%, Preferably it is 30-87. It is 50 mass%, More preferably, it is 50-85 mass%. If the content of the styrenic resin (A1) is in the above range, the foaming ratio is high, the foamed cells are uniform, and it is suitable for forming a foamed molded product having excellent molded appearance.

  The polycarbonate resin is not particularly limited as long as it has a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). This polycarbonate resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the aromatic polycarbonate include those obtained by melting a transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and pyridine and phosgene. What was obtained by the pyridine method using a reaction product etc. can be used.

  The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as dihydroxybenzene such as hydroquinone and resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxy) Phenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydroxy) Phenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used alone or in combination of two or more.

  Of the aromatic dihydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. Of these, bisphenol A is particularly preferable.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin is preferably 12,000 to 40,000, more preferably 14,000 to 30,000 when converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent. It is. When this viscosity average molecular weight is too high, the fluidity is not sufficient, and the moldability may be lowered. On the other hand, if it is too low, impact resistance, toughness and chemical resistance may not be sufficient.
The polycarbonate resin may be used by mixing two or more polycarbonate resins having different viscosity average molecular weights as long as the overall viscosity average molecular weight falls within the above range.

  In the thermoplastic resin composition for foam molding of the present invention, when the thermoplastic resin (A2) is a polycarbonate resin, that is, the component [A] is composed of the styrene resin (A1) and a polycarbonate resin. The content of the polycarbonate resin in the component [A] is 50 to 95% by mass, preferably 60 to 95% by mass, more preferably 70 to 90%, when the component [A] is 100% by mass. % By mass. If the content of the styrenic resin (A1) is in the above range, the foaming ratio is high, the foamed cells are uniform, and it is suitable for forming a foamed molded product having excellent molded appearance.

  As the acrylic resin, a (co) polymer using at least one (meth) acrylic ester compound excluding the styrene resins (A1), (A31) and (A32) is used. The content of monomer units comprising the (meth) acrylic acid ester compound constituting this acrylic resin is usually 50% by mass or more when the total of all monomer units is 100% by mass. . Examples of other monomer units include aromatic vinyl compounds, maleimide compounds, acid anhydrides having an unsaturated bond, unsaturated acids, and the like.

  In the thermoplastic resin composition for foam molding of the present invention, when the thermoplastic resin (A2) is an acrylic resin, that is, the component [A] is composed of the styrene resin (A1) and the acrylic resin. In this case, the content of the acrylic resin in the component [A] is 30 to 90% by mass, preferably 45 to 90% by mass, more preferably 100% by mass when the component [A] is 100% by mass. It is 55-85 mass%. If the content of the styrenic resin (A1) is in the above range, the foaming ratio is high, the foamed cells are uniform, and it is suitable for forming a foamed molded product having excellent molded appearance.

Examples of the vinyl chloride resin include vinyl chloride homopolymers; 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 thermoplastic resin (A2) is a vinyl chloride resin, that is, the component [A] is the styrene resin (A1) and the vinyl chloride resin. When it consists of resin, content of the vinyl chloride resin in the component [A] is 50 to 95% by mass, preferably 60 to 90% by mass, when the component [A] is 100% by mass. More preferably, it is 70-90 mass%. If the content of the styrenic resin (A1) is in the above range, the foaming ratio is high, the foamed cells are uniform, and it is suitable for forming a foamed molded product having excellent molded appearance.

  In the thermoplastic resin composition for foam molding of the present invention, when the sum of the total amount of monomer units constituting the acetone-soluble component or the acetonitrile-soluble component of the thermoplastic resin [A] is 100% by mass The total amount of the monomer units (a2) composed of the vinyl cyanide compound is preferably 20 to 40% by mass, more preferably 25 to 35% by mass. When it is within this range, it is possible to obtain a foam-molded article having excellent chemical resistance.

1-2. Foaming agent [B]
This component [B] is not particularly limited as long as it is used as a foaming agent for resin. Usually, hydrocarbon compounds including hydrocarbons and halogenated hydrocarbons, carbon dioxide gas, nitrogen gas and the like are used. These can be used alone or in combination of two or more.

Among the hydrocarbon compounds, hydrocarbons include ethane, n-propane, isopropane, propylene, n-butane, isobutane, isobutylene, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, cyclohexane and the like. Can be mentioned. These can be used alone or in combination of two or more.
Examples of the halogenated hydrocarbon include methyl chloride, ethyl chloride, dichloroethane, chloroform, fluoromethane, difluoromethane, trifluoromethane, difluoroethane, trifluoroethane, fluorochloromethane, fluorochloroethane, dichlorodifluoromethane, and the like. These can be used alone or in combination of two or more.
In addition, petroleum ether, which is a compound containing an oxygen atom, can also be used.

  The component [B] is a compound having an average boiling point (atmospheric pressure) of −10 ° C. to 55 ° C. when used alone or in combination of two or more. Is preferably 80 to 100% (mass% or volume%), more preferably 90 to 100% (mass% or volume%). Examples of such a compound include aliphatic hydrocarbons having 3 to 6 carbon atoms, and it is particularly preferable to include one or more selected from n-butane, isobutane, n-pentane and isopentane. When these are used, it is excellent in foamability and fine dispersibility.

  In the thermoplastic resin composition for foam molding of the present invention, the content ratio of the component [B] is 2.5 to 10 parts by mass, preferably 2 with respect to 100 parts by mass of the styrenic resin (A1). 5-8 parts by mass, more preferably 3-7 parts by mass. 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.

1-3. 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 inhibitors, 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-mentioned components [A] and [B] when n-propane, n-butane, isobutane, n-pentane, isopentane, cyclohexane or the like is used as the component [B]. 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 [B].

Examples of the filler include talc, mica, clay, wollastonite, calcium carbonate, silica, alumina, glass fiber, glass beads, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon balun, charcoal powder, Examples thereof include carbon beads, carbon milled fibers, carbon black, graphite, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, various whiskers, wood flour, pulp, chaff, and paper sludge. 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 antiaging 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.
The content of the lubricant is usually 0.5 to 5 parts by mass when the amount of the component [A] is 100 parts by mass.

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, toki 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 a foaming agent containing masterbatch 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 agents 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, thiocyanate compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compounds; inorganic and organic Hybrid antibacterial agent; natural anti Agent, 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.

  The thermoplastic resin composition for foam molding of the present invention has [D] 75 to 95% by mass of monomer units composed of an aromatic vinyl compound when the total of all monomer units is 100% by mass, cyanide. A styrenic monomer comprising 5 to 25% by weight of a monomer unit made of a vinyl compound and 0 to 20% by weight of a monomer unit made of another vinyl compound and having a weight average molecular weight of 100,000 to 300,000. A foaming agent containing a resin (A1) and a foaming agent [B], and the content ratio of the foaming agent [B] is 2.5 to 10 parts by mass with respect to 100 parts by mass of the styrenic resin (A1). Containing master batch (hereinafter also referred to as “component [D]”) and [E] thermoplastic resin [C] (excluding the styrene-based resin (A1); hereinafter also referred to as “component [E]”) .) And no foaming agent When, it is preferable that is formed by mixing.

The foaming agent-containing master batch [D] contains a styrene resin (A1) and a foaming agent [B]. In the foaming agent-containing masterbatch, the content of the component [B] is 2.5 to 10 parts by mass, preferably 2.5 to 8 parts by mass, with respect to 100 parts by mass of the styrene resin (A1). Part, more preferably 3 to 7 parts by mass. By being in the said range, a foaming molded article with a high expansion ratio can be manufactured efficiently.
In addition, the said foaming agent containing masterbatch [D] may contain 20 mass parts or less thermoplastic resins [C] with respect to 100 mass parts of said styrene-type resins (A1).

  The component [D] is exemplified by the foaming aid, filler, heat stabilizer, antioxidant, ultraviolet ray inhibitor, anti-aging agent, antistatic agent, plasticizer, lubricant, flame retardant, antibacterial agent exemplified above. Additives such as an agent, an antifouling agent, a colorant, a fluorescent brightener, and a fluorescent dye may be included.

  The shape and size of the component [D] are not particularly limited, and the shape may be, for example, a flat plate shape (circular, square, etc.), a column shape (cylinder, prism, etc.), a linear shape, or the like.

  The said component [D] can be manufactured by mix | blending and knead | mixing the said foaming agent [B], making the said styrene resin (A1) into a molten state, for example, the said styrene resin (A1). In the melt-kneading step (hereinafter referred to as “melting step”), the component [B], or the component [B] and the foaming aid are added to the molten styrene-based resin (A1) obtained by the melting step. And the step of melt-kneading the mixture (hereinafter referred to as “kneading step”), the kneaded product obtained by the kneading step as a linear body and the like, and immediately cooling the linear body (hereinafter referred to as “ It can be manufactured by a manufacturing method in which the cooling process ”and the process of cutting the cooled linear body (hereinafter referred to as“ cutting process ”) are sequentially performed.

In the melting step, the styrene resin (A1) 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 liquefied styrene resin (A1) is liquefied. The component [B] or the liquefied component [B] and the foaming aid are supplied and usually melt-kneaded at a temperature equal to or higher than the melting temperature of the styrenic resin (A1).

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.

Next, the thermoplastic resin body [E] is an object containing the thermoplastic resin [C] excluding the styrenic resin (A1) and containing no foaming agent.
As the thermoplastic resin [C], the thermoplastic resin (A2) can be applied as it is. Preferred thermoplastic resins [C] are styrene resin (A3), polycarbonate resin, acrylic resin and vinyl chloride resin.
In addition, the said thermoplastic resin body [E] may contain 20 mass parts or less styrene resin (A1) with respect to 100 mass parts of said thermoplastic resins [C].

  When the thermoplastic resin [C] contains a styrene resin (A3), the styrene resin (A3) contains an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. It is preferable to include a rubber-reinforced styrene resin obtained by polymerizing monomers. With respect to this rubber-reinforced styrene-based resin, when the sum of the total amount of monomer units constituting the acetone-soluble component or acetonitrile-soluble component is 100% by mass, the monomer unit (a2 made of a vinyl cyanide compound) ) Is preferably 25 to 35% by mass, more preferably 26 to 33% by mass. If the total amount of the unit (a2) is in the above range, a foamed molded product having a high expansion ratio and excellent molded appearance can be easily obtained.

  The component [E] may contain an additive other than the foaming agent. For example, the fillers, heat stabilizers, antioxidants, UV inhibitors, anti-aging agents, antistatic agents, plasticizers, lubricants, flame retardants, antibacterial agents, antifouling agents, colorants, fluorescent enhancers exemplified above It may contain whitening agents, fluorescent dyes and the like.

  The shape and size of the component [E] are not particularly limited, and the shape is, for example, powdery, spherical, substantially spherical, flat (circular, square, etc.), columnar (cylinder, prism, etc.), linear, etc. It can be.

  In the thermoplastic resin composition for foam molding containing the components [D] and [E], when the sum of the styrenic resin (A1) and the thermoplastic resin (A2) is 100% by mass, Content of a styrene-type resin (A1) is 5-100 mass%, Preferably it is 10-90 mass%, More preferably, it is 15-80 mass%. If the content of the styrenic resin (A1) is in the above range, it is excellent in foamability and fine dispersibility, in particular, the formation of a foam-molded product having a high foaming ratio, uniform foamed cells and excellent molded appearance. It is suitable for.

  In the thermoplastic resin composition for foam molding of the present invention, when the component [E] contains the styrene rubber-reinforced resin, the vinyl cyanide compound constituting the styrene resin (A1) contained in the component [D] When the sum of the total amount of the monomer units (a2) and the total amount of the monomer units constituting the acetone-soluble component or acetonitrile-soluble component of the component [E] is 100% by mass, The sum of the monomer unit (a2) composed of the vinyl cyanide compound is the sum of the monomer units constituting the styrenic resin (A1) and the component constituting the component [E] [ C] is preferably 20 to 40% by mass, more preferably 25 to 35% by mass, when the sum of the total amount of monomer units constituting C] is 100% by mass. When it is within this range, it is possible to obtain a foam-molded article having excellent chemical resistance.

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 foamed molded product of the present invention has uniform foamed cells. Moreover, a density is 40-500 kg / m < ³ > normally, Preferably it is 50-400 kg / m < ³ >.

  The shape of the foamed molded product of the present invention is selected depending on the purpose, application, and the like, and can be a plate shape (sheet shape), a cylindrical shape, a semi-cylindrical shape, a linear shape, a lump shape, or the like.

  The foamed molded product of the present invention is an extrusion molding method in which the thermoplastic resin composition for foam molding of the present invention, which has been heated and melted, is extruded from a die and foamed at the same time, and the thermoplastic resin for foam molding of the present invention that has been melted by heating. The composition can be produced by injection molding into a mold and foaming at the same time, vacuum molding, pressure molding, or the like. In either case, the expansion ratio can be as high as 2 to 25 times, and the resulting foamed molded article is excellent in appearance.

In the above extrusion molding method and injection 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. It is selected according to the type of component [A].
When the said component [A] consists of styrene resin (A1) and (A3), heating temperature becomes like this. Preferably it is 130-200 degreeC.
When the said component [A] consists of a styrene resin (A1) and polycarbonate resin, heating temperature becomes like this. Preferably it is 130-240 degreeC.
When the said component [A] consists of styrene resin (A1) and (A3) and a polycarbonate resin, heating temperature becomes like this. Preferably it is 130-240 degreeC.
When the said component [A] consists of a styrene resin (A1) and acrylic resin, heating temperature becomes like this. Preferably it is 130-200 degreeC.
Moreover, when the said component [A] consists of styrene resin (A1) and a vinyl chloride resin, heating temperature becomes like this. Preferably it is 120-200 degreeC.

  The method for producing a foam molded article of the present invention is preferably a method using a thermoplastic resin composition for foam molding containing the above-mentioned foaming agent-containing masterbatch [D] and a thermoplastic resin body [E]. This thermoplastic resin composition for foam molding may be used as it is, or a mixture with a pyrolytic chemical foaming agent may be used. The pyrolytic chemical foaming agent is not particularly limited, and organic foaming agents such as ADCA foaming agents, DPT foaming agents and OBSH foaming agents, and inorganic foaming agents such as sodium hydrogen carbonate can be used. .

  In the above preferred production method, the ratio (Vd / Ve) of the melt viscosity Vd of the styrene resin (A1) constituting the foaming agent-containing masterbatch [D] and the melt viscosity Ve of the thermoplastic resin body [E]. ) Is preferably 0.40 to 0.70, more preferably 0.43 to 0.65, and still more preferably 0.47 to 0.60. If it exists in the said range, the kneadability of said foaming agent containing masterbatch [D] and a thermoplastic resin body [E] will improve, and moldability will be 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 can be obtained. In addition, the said melt viscosity is measured as a shear viscosity in the Example mentioned later.

In the above preferred production method, when the above-mentioned foaming agent-containing masterbatch [D] and the thermoplastic resin body [E] are melt-kneaded, extrusion such as a single screw extruder, a twin screw extruder, a tandem type extruder, etc. Machine is used.
When the thermoplastic resin [C] constituting the thermoplastic resin body [E] is a styrene resin (A3), the melting temperature is preferably 130 to 200 ° C.
When the thermoplastic resin [C] is a polycarbonate resin, the melting temperature is preferably 130 to 240 ° C.
When the thermoplastic resin [C] is a styrene resin (A3) and a polycarbonate resin, the melting temperature is preferably 130 to 240 ° C.
When the thermoplastic resin [C] is an acrylic resin, the melting temperature is preferably 130 to 200 ° C.
Further, when the thermoplastic resin [C] is a vinyl chloride resin, the melting temperature is preferably 120 to 200 ° C.

  After obtaining the kneaded product of the above components [D] and [E], a foamed molded product can be produced by applying the above-described extrusion molding method, injection molding method and the like. Even in the case of manufacturing by such a method, the foaming magnification can be as high as 2 to 25 times, and a foam molded product having a dense skin layer hardly ruptured on the surface is obtained, and the appearance Excellent.

  Foam molded products of the present invention include civil engineering / construction related materials such as display boards; interior and exterior materials for vehicles; daily miscellaneous goods such as containers and trays; electrical / electronic parts; sports equipment; walls, floors, frames, furniture. , Decorative sheets, partitions, lattices, fences, rain gutters, sizing boards, carports and other housing and office interior and exterior materials; toys; cushioning materials for game machines, reinforcing materials, heat insulating materials, core materials, substitute plywood, etc. Can be used as

  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 is formed by laminating a molded part (X) obtained by using the thermoplastic resin composition for foam molding of the present invention and a member (Y) made of another material. It is characterized by.
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.

In the molded part (X), the foamed cells are uniform. Moreover, a density is 40-500 kg / m < ³ > normally, Preferably it is 50-400 kg / m < ³ >.

Other materials constituting the member (Y) are not particularly limited as long as they exclude the thermoplastic resin composition for foam molding of the present invention, and those made of resin (composition), other organic materials And those made of inorganic materials.
The resin (composition) may be a thermoplastic resin (composition) or a cured resin (composition). When it is a thermoplastic resin (composition), it is a thermoplastic resin composition (hereinafter referred to as "thermoplastic resin composition (N)") different from the thermoplastic resin composition for foam molding of the present invention. . The thermoplastic resin contained in the thermoplastic resin composition (N) is selected depending on the use of the laminated product of the present invention, and the like [A component contained in the thermoplastic resin composition for foam molding of the present invention [A ] May be the same as or different from each other. Moreover, this thermoplastic resin composition (N) 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 (Y) may be one layer, two layers, three or more layers, or may be provided on both surfaces of the molded part (X) (FIG. 1). To FIG. 3).

The laminated product 1 in FIG. 1 is a cross-sectional view showing that a member (Y) 12 is laminated above a molding part (X) 11. The member (Y) 12 may be on the entire surface of the molding part (X) or may be only partly. The thicknesses of the molded part (X) 11 and the member (Y) 12 are selected according to the purpose, application, and the like. The molded part (X) 11 may be thicker than the member (Y) 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 preferable thickness of said shaping | molding part (X) 11 and member (Y) 12 is 1-50 mm and 0.1-5 mm, respectively.
As a manufacturing method of the laminated article of the said aspect, after forming the shaping | molding part (X) 11 using the thermoplastic resin composition for foam molding of the said invention, the member (Y) 12 produced separately is arrange | positioned. Method: Method of co-extrusion using the thermoplastic resin composition for foam molding of the present invention and the thermoplastic resin composition (N) that forms the member (Y) 12; Member formed in advance (Y) The method of arrange | positioning the shaping | molding part (X) 11 obtained using the thermoplastic resin composition for foam molding of the said invention on the surface of 12 is mentioned.

  The laminated product 1 ′ in FIG. 2 is a cross-sectional view showing that the molded part (X) 11 is laminated above the member (Y) 12 and the thickness of both is the same. The thicknesses of the molded part (X) 11 and the member (Y) 12 are selected according to the purpose, application, and the like. The molded part (X) 11 may be thicker than the member (Y) 12, or vice versa. Each thickness may be the same as in FIG. Moreover, the molding part (X) 11 may be on the entire surface of the member (Y) 12 or may be only partly.

When the laminate 1 ′ shown in FIG. 2 is an adhesive film (adhesive sheet) or an adhesive film (adhesive sheet), the member (Y) 12 is an adhesive layer or an adhesive layer.
When the said member (Y) 12 is an adhesion layer, the preferable thickness of the shaping | molding part (X) 11 and the member (Y) 12 (adhesion layer) is 1-50 mm and 0.02-0.1 mm, respectively. It is. Moreover, as an adhesive composition which forms the said member (Y) 12 (adhesion layer), the emulsion type composition applied by the screen method, the gravure method, the mesh method, the bar coating method, etc .; Organic solvent type composition; There are hot melt compositions formed by an extrusion laminating method, a dry laminating method, a coextrusion method, and the like, and any of them can be used. For example, a composition containing a known acrylic polymer, diene polymer, hydrogenated diene polymer, or the like can be used. In addition, in order to improve the adhesiveness between the molded part (X) 11 and the pressure-sensitive adhesive composition, before forming the member (Y) 12, the molded part (X) 11 directly or Corona treatment or the like may be performed on the surface of the molded part (X) 11 or an anchor coat layer may be formed. In the case of the anchor coat layer, polyethyleneimine, polyurethane, polyester or acrylic resin is used, and the layer has a thickness of about 0.1 to 5 μm. The anchor coat layer can be formed by applying as an aqueous solution or a solvent solution and drying. After the formation of the member (Y) 12 (adhesive layer), release paper or the like may be usually provided as a protective layer in order to protect this layer.

Further, when the member (Y) 12 is an adhesive layer, preferable thicknesses of the molded part (X) 11 and the member (Y) 12 (adhesive layer) are 1 to 50 mm and 0.02 to 0, respectively. .1 mm. Moreover, as an adhesive composition which forms the said member (Y) 12 (adhesion layer), the composition containing a well-known epoxy resin, a phenol resin, an acrylic resin, etc. can be used. In addition, after forming the said member (Y) 12 (adhesion layer), when not using the laminated product of this invention immediately, it is necessary to set it as the state which does not express adhesion | attachment.
Further, when the member (Y) 12 is an adhesive layer or an adhesive layer, usually a release paper or the like is further provided on the surface.

  In the laminate 1 ′ shown in FIG. 2, when the member (Y) 12 is a reinforcing member, the material constituting the member (Y) 12 includes a thermoplastic resin (composition) and a cured resin (composition). ), Polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyolefin resins such as polyethylene and polypropylene; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polycarbonate resins; ASA resins; A thermoplastic resin composition (N) containing at least one thermoplastic resin selected from polysulfone and the like is preferable. Various additives may be blended. In addition, the preferable thickness of the shaping | molding part (X) 11 and the member (Y) 12 in this case is 0.1-15 mm and 0.1-15 mm, respectively.

  As a manufacturing method of the laminated product 1 ′ including the reinforcing member (Y) 12 as described above, the molded part (X) 11 is formed using the thermoplastic resin composition for foam molding according to the present invention. Then, the method of disposing the member (Y) 12; the thermoplastic resin composition for foam molding of the present invention and the thermoplastic resin composition (N) that forms the member (Y) 12. And a method of co-extrusion; a method of disposing the molded part (X) 11 obtained by using the thermoplastic resin composition for foam molding of the present invention on the surface of the member (Y) 12 formed in advance, etc. Is mentioned.

Further, the laminated product of the present invention may be a laminated product having a cross-sectional structure as shown in FIG. That is, the laminated product 1 ″ of FIG. 3 includes members (Y) 12a and 12b on both surfaces of the molded part (X) 11.
When the member (Y) 12a and / or 12b is an adhesive layer or an adhesive layer, usually a release paper or the like is further provided on the surface.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the following, parts and% are Unless otherwise specified, it is based on mass.

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

1-1. Foaming agent-containing masterbatch resin A
(1) Acrylonitrile styrene resin (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. The shear viscosity according to the following method was 8,000 poise.
(2) Acrylonitrile styrene resin (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. The shear viscosity according to the following method was 7,000 poise.
(3) Acrylonitrile styrene resin (A-3)
The copolymer has a styrene unit amount of 70% and an acrylonitrile unit amount of 30%, and Mw is 200,000. The shear viscosity according to the following method was 14,500 poise.
(4) Polystyrene resin (A-4)
“HF77” (trade name) manufactured by PS Japan was used. Mw is 220,000. The shear viscosity according to the following method was 12,000 poise.

[Shear viscosity measurement method]
A twin capillary rheometer (model “RH7-2”, manufactured by Borin) was used. The resin (measurement sample) is put into a temperature-controlled cylindrical barrel to plasticize it, and the resin (measurement sample) in the barrel is pushed at a constant speed from the plunger installed at the top of the barrel. The resin (measurement sample) was discharged from a capillary having a diameter of 1 mm, a length of 16 mm, and an inlet angle of 180 degrees. The measured shear viscosity is obtained from the pressure in the barrel at a temperature of 220 ° C. and a shear rate of 100 / second. This shear viscosity is due to the flow resistance of the capillary inlet / outlet portion in addition to the viscosity resistance of the resin (measurement sample). Resistance is included. Therefore, as the shear viscosity, a capillary having a different L / D or an orifice having an L / D close to 0 was used, pressure measurement was performed at the above temperature and shear rate, and bargray correction was performed.

1-2. Foaming agent B
Butane (boiling point at atmospheric pressure—0.5 ° C.) was used.

1-3. Thermoplastic resin body E
(1) ABS resin (E-1)
A resin obtained by the following method was used.
Styrene and acrylonitrile were emulsion polymerized in a dispersion containing polybutadiene rubber particles having a volume average particle diameter of 280 nm and a toluene-insoluble content of 80% to obtain a latex containing a rubber-reinforced vinyl resin. Next, an aqueous sulfuric acid solution was added to the latex to coagulate the rubber-reinforced vinyl resin, followed by washing with water and drying to obtain a powder. The obtained rubber-reinforced vinyl resin had a graft ratio of 55%, an amount of polybutadiene of 51%, a styrene unit amount of 35%, and an acrylonitrile unit amount of 14%.
On the other hand, an acrylonitrile / styrene copolymer having a styrene unit amount of 71% and an acrylonitrile unit amount of 29% and having an Mw of 150,000 is separately prepared and kneaded with the rubber-reinforced vinyl resin at 210 ° C. An “ABS resin (E-1)” of 15% was obtained. The ABS resin (E-1) used in the following has a cylindrical shape, and the size is approximately 2 mm in outer diameter and 3 mm in length.
The obtained ABS resin (E-1) had an MFR (based on ISO 1133, temperature 220 ° C., load 98 N) of 5.1 g / 10 minutes, and a shear viscosity of 14,500 poise. The acrylonitrile unit amount in the acetone-soluble component was 29%, and the intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component was 0.71 dl / g.

(2) ABS resin (E-2)
Similarly to the ABS resin (E-1), an “ABS resin (E-2)” containing a rubber-reinforced vinyl resin having a graft ratio of 49% and a polybutadiene content of 15% was obtained. The ABS resin (E-2) used in the following has a cylindrical shape, and the size is approximately 2 mm in outer diameter and 3 mm in length.
The obtained ABS resin (E-2) had an MFR (based on ISO 1133, temperature 220 ° C., load 98 N) of 5.1 g / 10 min, and a shear viscosity of 11,000 poise. The acrylonitrile unit amount in the acetone-soluble component was 21%, and the intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component was 0.73 dl / g.

(3) ABS resin (E-3)
Similarly to the ABS resin (E-1), an “ABS resin (E-3)” containing a rubber-reinforced vinyl resin having a graft ratio of 57% and a polybutadiene content of 15% was obtained. The ABS resin (E-3) used in the following has a cylindrical shape, and the size is approximately 2 mm in outer diameter and 3 mm in length.
The obtained ABS resin (E-3) had an MFR (based on ISO 1133, temperature 220 ° C., load 98 N) of 5.5 g / 10 min, and a shear viscosity of 17,200 poise. The acrylonitrile unit amount in the acetone-soluble component was 40%, and the intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component was 0.69 dl / g.

(4) Polycarbonate resin (E-4)
Poly-4,4′-isopropylidene diphenyl carbonate “NOVAREX 7020A” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The polycarbonate resin (E-4) used in the following is in the form of powder, and the size is approximately 2.5 mm in outer diameter.

(5) Acrylic resin (E-5)
A methyl methacrylate / methyl acrylate copolymer “Acrypet VH5” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used. The acrylic resin (E-5) used in the following has a cylindrical shape, and the size is approximately 2 mm in outer diameter and 3 mm in length.

(6) Vinyl chloride resin (E-6)
“Vinica PVC SG1300” (trade name) manufactured by Vitec Co., Ltd. was used. The degree of polymerization is 1,300. The shape of the vinyl chloride resin (E-6) used in the following is particulate, and the size is approximately an outer diameter of 0.2 mm.

2. Production of foaming agent-containing masterbatch Production example 1
100 parts of acrylonitrile styrene resin (A-1) was supplied to a 120 mm single screw extruder having a cylinder temperature set to 170 to 250 ° C. to melt it. Thereafter, 4.5 parts of the foaming agent B was supplied from the injection port at the rear of the extruder and melt-kneaded.
Subsequently, it was made into a strand through a die having 50 holes (2.5 mmφ / hole) disposed at the outlet of the extruder and directly introduced into the water tank. After cooling in a water tank, it was cut into a length of 3 mm to obtain a foaming agent-containing master batch (MB-1) having an outer diameter of about 2 mm.

When the foaming agent content in the said foaming agent containing masterbatch (MB-1) was measured with the following method, the structure of a foaming agent containing masterbatch (MB-1) obtained the result as shown in Table 1 .
[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.

Moreover, the molding external appearance property of the said foaming agent containing masterbatch (MB-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.

Production Examples 2 to 4
The foaming agent-containing master batches (MB-2) to (MB-4) were carried out in the same manner as in Example 1 except that the foaming agent-containing masterbatch forming resin A and the foaming agent B were used in the proportions shown in Table 1, respectively. ) And various evaluations were made. The results are shown in Table 1.

3. Example 1 Preparation of thermoplastic resin composition for foam molding and production of foam molded article using the same
25 parts of a foaming agent-containing master batch (MB-1) and 75 parts of a thermoplastic resin body (E-1) were mixed 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 Ikegai Co., Ltd.) and melt-kneaded at 200 ° C. Next, the product was discharged from an outlet provided with a sizing die of 30 mmφ or 23 mmφ into a round die of 8 mmφ, and a foamed molded article having an expansion ratio of 3.5 by the following calculation method was obtained.
[Foaming ratio calculation method]
The mass calculated value W1 was calculated from the bulk volume and the specific gravity of the resin obtained from the outer dimensions of the foam molded product, and the ratio between this W1 and the measured mass value W2 was taken as the expansion ratio.
Foaming magnification (times) = W1 / W2
The specific gravity of the resin used for the calculation is as follows: ABS resin; 1.06 g / cm ³ , PC resin; 1.17 g / cm ³ , acrylic resin; 1.16 g / cm ³ , vinyl chloride resin; 32 g / cm ³ .

Moreover, about the obtained foaming molded article, the molding external appearance property was visually observed and it determined by the following reference | standard (refer Table 2).
A: A foam-molded product having no distortion was obtained, and its surface was smooth.
○: A foam-molded product having no distortion was obtained, but part of the surface was fluffy.
Δ: A slightly distorted foam molded product was obtained, and a part of the surface was fluffy.
X: A foamed molded product with distortion was obtained, and almost the entire surface was fuzzy.

  Table 2 shows monomer units 75 to 95% by mass composed of an aromatic vinyl compound and monomer units 5 composed of a vinyl cyanide compound based on the total amount of resin contained in the thermoplastic resin composition for foam molding. Styrenic resin [acrylonitrile styrene resin (A-) having a weight average molecular weight of 100,000 to 300,000 consisting of 0 to 20% by mass of monomer units consisting of ˜25% by mass and other vinyl compounds. 1) or (A-2)] content ratio: 75 to 95% by mass of monomer units composed of an aromatic vinyl compound, 5 to 25% by mass of monomer units composed of a vinyl cyanide compound, and other vinyl compounds A styrene-based resin [acrylonitrile / styrene resin (A-1) having a monomer unit of 0 to 20% by mass and a weight average molecular weight of 100,000 to 300,000. And / or (A-2)] content ratio of foaming agent B total amount; and the monomer unit constituting the acetone soluble component when the resin constituting the thermoplastic resin body is treated with acetone The ratio of the total amount of monomer units (a2) composed of the vinyl cyanide compound relative to the total amount is also shown.

Examples 2, 3, 8 and 9
According to Table 2, a foamed molded article was produced and evaluated in the same manner as in Example 1 except that the foaming agent-containing master batch and the thermoplastic resin body were used. The results are shown in Table 2.

Example 4
25 parts of a foaming agent-containing master batch (MB-2) and 75 parts of a thermoplastic resin body (E-4) were mixed with a Henschel mixer to obtain a thermoplastic resin composition for foam molding. Thereafter, a foamed molded product was produced and evaluated in the same manner as in Example 1 except that it was put into an extruder equipped with a screw (“FS50-22 type”, manufactured by Ikegai Co., Ltd.) and melt-kneaded at 230 ° C. The results are shown in Table 2.

Example 5
25 parts of a foaming agent-containing masterbatch (MB-2) and 75 parts of a thermoplastic resin body (E-5) were mixed with a Henschel mixer to obtain a thermoplastic resin composition for foam molding. Thereafter, a foamed molded product was produced and evaluated in the same manner as in Example 1 except that it was put into an extruder equipped with a screw (“FS50-22 type”, manufactured by Ikegai Co., Ltd.) and melt-kneaded at 200 ° C. The results are shown in Table 2.

Example 6
25 parts of a foaming agent-containing masterbatch (MB-1) and 75 parts of a thermoplastic resin body (E-6) were mixed with a Henschel mixer to obtain a thermoplastic resin composition for foam molding. Thereafter, a foamed molded product was produced and evaluated in the same manner as in Example 1 except that it was put into an extruder equipped with a screw (“FS50-22 type”, manufactured by Ikegai Co., Ltd.) and melt-kneaded at 190 ° C. The results are shown in Table 2.

Example 7
25 parts of a foaming agent-containing master batch (MB-1) and 75 parts of a thermoplastic resin body (E-1) were mixed with a Henschel mixer to obtain a thermoplastic resin composition for foam molding. Thereafter, the thermoplastic resin composition for foam molding and 2 parts of an endothermic decomposition type foaming agent (“Selfon SC-P”, manufactured by Eiwa Kasei Co., Ltd.) whose main component is sodium hydrogen carbonate, and an extruder equipped with a screw ( A foam molded article was produced and evaluated in the same manner as in Example 1 except that it was put into “FS50-22 type” (manufactured by Ikegai) and melt-kneaded at 200 ° C. The results are shown in Table 2.

Comparative Examples 1 and 2
According to Table 2, a foamed molded article was produced and evaluated in the same manner as in Example 1 except that the foaming agent-containing master batch and the thermoplastic resin body were used. The results are shown in Table 2.

Comparative Example 3
According to Table 2, a foamed molded product was produced and evaluated in the same manner as in Example 4 except that the foaming agent-containing master batch and the thermoplastic resin body were used. The results are shown in Table 2.

Comparative Example 4
An extruder equipped with a screw (100 parts of thermoplastic resin (E-1)) and 2 parts of an endothermic decomposition type foaming agent ("Selfon SC-P", manufactured by Eiwa Chemical Co., Ltd.) whose main component is sodium hydrogen carbonate. (FS50-22 type, manufactured by Ikegai Co., Ltd.) and melted at 200 ° C. Thereafter, in the same manner as in Example 1, foamed molded articles were produced and evaluated. The results are shown in Table 2.

  The thermoplastic resin composition for foam molding of the present invention includes civil engineering and construction related materials such as display boards; interior and exterior related materials for vehicles; daily miscellaneous goods such as containers and trays; electrical and electronic parts; sports equipment; Floors, frames, furniture, decorative sheets, partitions, lattices, fences, rain gutters, sizing boards, carports and other housing and office interior and exterior materials; toys; game machines and other cushioning materials, reinforcing materials, heat insulating materials, cores Suitable for forming materials, substitute plywood, etc.

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

1, 1 'and 1 "; Laminated product 11; Molded part (X)
12, 12a and 12b; member (Y)

Claims (9)

[A] When the total of all the monomer units is 100% by mass, the monomer unit composed of an aromatic vinyl compound is 75 to 95% by mass, and the monomer unit composed of a vinyl cyanide compound is 5 to 25% by mass. And a thermoplastic resin containing a styrene resin (A1) comprising 0 to 20% by mass of monomer units composed of other vinyl compounds and having a weight average molecular weight of 100,000 to 300,000, and [B And a foaming thermoplastic resin composition for foam molding,
The content of the foaming agent [B] is 2.5 to 10 parts by mass with respect to 100 parts by mass of the styrene resin (A1), and the content of the styrene resin (A1) is as described above. A thermoplastic resin composition for foam molding, which is 5 to 100% by mass relative to 100% by mass of the thermoplastic resin [A].   The thermoplastic resin [A] is at least one selected from a styrene resin (A3) excluding the styrene resin (A1), a polycarbonate resin, an acrylic resin, and a vinyl chloride resin, and the styrene resin ( The thermoplastic resin composition for foam molding according to claim 1, comprising A1). The thermoplastic resin composition for foam molding according to claim 1,
[D] When the total of all the monomer units is 100% by mass, the monomer unit composed of an aromatic vinyl compound is 75 to 95% by mass, and the monomer unit composed of a vinyl cyanide compound is 5 to 25% by mass. And a styrene resin (A1) having a monomer unit of 0 to 20% by mass and a weight average molecular weight of 100,000 to 300,000, and a foaming agent [B]. A foaming agent-containing masterbatch containing 2.5 to 10 parts by mass with respect to 100 parts by mass of the styrenic resin (A1),
[E] For foam molding, comprising a thermoplastic resin [C] (excluding the styrenic resin (A1)) and a thermoplastic resin body containing no foaming agent. Thermoplastic resin composition.   The thermoplastic resin composition for foam molding according to any one of claims 1 to 3, wherein the foaming agent [B] contains a compound having an average boiling point of -10 ° C to 55 ° C.   The thermoplastic resin for foam molding according to claim 3 or 4, wherein the thermoplastic resin [C] contains at least one selected from the group consisting of a styrene resin (A3), a polycarbonate resin, an acrylic resin, and a vinyl chloride resin. Composition.   The thermoplastic resin composition for foam molding according to claim 2 or 5, wherein the styrene resin (A3) contains a styrene rubber-reinforced resin.   The styrene rubber reinforced resin is a resin obtained by polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, and the styrene rubber reinforced resin is acetone. When the sum of the total amount of the monomer units constituting the soluble component or the acetonitrile-soluble component is 100% by mass, the ratio of the total amount of the monomer units made of the vinyl cyanide compound is 25 to 35 mass. The thermoplastic resin composition for foam molding according to claim 6, which is%.   A foam molded article obtained by using the thermoplastic resin composition for foam molding according to any one of claims 1 to 7.   A molded part (X) obtained by using the thermoplastic resin composition for foam molding according to any one of claims 1 to 7 and a member (Y) made of another material are laminated. Laminated product.

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